text:
This fall, it will be easier than ever for new students living on campus
to go green. PSU EcoReps will be there to guide them every step of the way.
As student sustainability leaders who live in residence halls, EcoReps are trained in a variety of sustainability areas, including recycling procedures, food systems, energy conservation, and social equity. They are often the go-to people for students who have questions about sustainable practices or are curious about getting involved in green organizations and activities on campus.
"We like to start a culture of sustainability at the beginning, when students are new to campus," said Danielle Grondin, a senior sociology major who started the PSU EcoRep program.
Grondin was hired by the PSU Sustainability Leadership Center to develop the program in January 2011 when she was a resident assistant living in the Broadway Housing Building. Because she was already involved with the campus housing community, she was able to quickly recruit fellow students to be EcoReps and initiate sustainability activities in their residence halls.
This year, the Sustainability Leadership Center hosted a required sustainability training for all incoming resident assistants and provided a Green Housing Guide (pdf)—which was recently created by two EcoReps—for each residence hall floor.
While schools across the nation have similar EcoRep programs, PSU's is unique in that it focuses on leadership development as a key aspect of the program.
"It's not just training in sustainability issues, but also in leadership," said Jennie Sharp, residence life sustainability liaison at Portland State. "All the EcoReps have decision-making capabilities, they're empowered to build and adapt the program."
EcoReps organize the annual Conservation Challenge, a series of activities that encourages students living in residence halls to reduce and reuse in creative ways—from having candlelight dinners to clothing swaps.
First year students living in Broadway or Ondine can apply to be one of 15 EcoReps. Because they begin developing sustainability knowledge and leadership skills early in their college career, many EcoReps move into other leadership roles across campus. The current community garden coordinator and the president of the Residence Housing Association were both EcoReps last year.
"They're role models," said Grondin. "They walk the walk instead of just talk the talk."
To learn more about the program or apply to be an EcoRep, visit ecowiki.pdx.edu/about/ecoreps.


text:
The requested news item does not exist. Please return to News
Firm bags Business Development and Project Manager of the Year awards
Singapore, 16 July 2010 – Two of Jones Lang LaSalle's professionals have won prestigious industry accolades at the 2010 RFP Outstanding Individuals Industry Asia Awards. In its third year running, the awards celebrate the contributions of the brightest professionals in the facilities and projects space in Asia Pacific.
Ong Soo Yar, Business Development Director for Integrated Facilities Management (IFM), North Asia won the Business Development award, with her implementation of an Industrial Due Diligence program that helped clients save cost, minimize risk and close service gaps. Specifically tailored for industrial facilities, the program was successfully launched with a number of industrial clients and also provided a platform for Jones Lang LaSalle to solidify its position in the emerging industrial outsourcing sector. Ms Ong drew on her international experience to identify best practice methodologies and tools which can be customized for the North Asia market. Her proactiveness and client-centric approach delivered outstanding results for our clients and contributed significantly to the growth of our IFM business in North Asia.
Ada Fung, Senior Project Manager, Project & Development Services (PDS) was named Project Manager of the year for her successful delivery of a fit-out, restacking and relocation project for a leading law firm in Hong Kong. The two-year project involved the relocation of 700 staff and the set-up of 130,000 square feet of productive space over three and a half floors with a design that enhanced the client's corporate image and promoted staff integration. This was the client's first major relocation project and under Ms Fung's leadership, it was completed satisfactorily within a very tight schedule and set budget.
John Forrest, Chief Executive Officer of Corporate Solutions, Asia Pacific at Jones Lang LaSalle highlights the significance of the awards, "Congratulations to Soo Yar and Ada on their achievements – they have done our firm proud. As a services business, our people drive our performance and to have two winners and six finalists recognised at this year's industry award illustrates the depth and quality of talent that we have in our firm. We will continue to invest in our human capital, ensuring that we have the best talent in the industry that can provide our clients with top quality advice and service, as well as drive innovation and excellence in the real estate arena."
Of Jones Lang LaSalle's participation in the Awards, Claire Saeki, co-founder and publisher, RFP Magazine, comments, "Each year, through organizing the Outstanding Individuals in Industry Awards, we come across professionals who are both prominent public figures and those who have been working hard but often out of the spotlight. It is great to see a company such as Jones Lang LaSalle who always support their teams by putting forward an excellent cross section of talent. This acknowledgement not only supports the winners of the awards but also other nominees, their teams and improves the standards of the industry as a whole."
Foo Chek Yee
+65 6494 3647

subset: commoncrawl


text:
Transform your photos into one-of-a-kind, hand painted masterpieces!
by V Boge
Image Size
The image is near the edges of the product but doesn't cover the entire product. Some of the background color may appear around the outside edges of the image.
Background Color
Our ceramic coffee mugs are available in two sizes: 11 oz. and 15 oz. Each mug is dishwasher and microwave safe.
11 oz.
Ships Within
1 - 2 business days
There are no comments for 70's Angel. Click here to post the first comment.
Average Rating (4.85 Stars):
Patricia Wilson
June 12th, 2019
David Hayhurst
June 11th, 2019
This is all pointillism on paper done in the late 70's in my pointillism phase.
I'm a youthful 78 year-old, self taught, folk artist and inventor. I enjoy making things out of natural items and I seem to always be changing and improving items, or just creating new things. Health, fitness, nature and art have always been passions of mine and while growing up in the projects during the war in Germany, these were ways that I could escape and find peace. As a teen, I was on the high school track team and was elected the best runner of my school. After school, I became a jazz dancer in Germany in the late 50's. The 50's were a glamorous time. I came to the US in my 20's with my then American husband. I had art showings in the 60's and 70's on the East Coast and raised my 3 children. After my divorce, I returned to...
Our return policy is very simple:
If you're not happy with a purchase that you made on Pixels.com, for any reason, you can return it to us within 30 days of the order date. As soon as it arrives, we'll issue a full refund for the entire purchase price. Please note - Pixels does not reimburse the outgoing or return shipping charges unless the return is due to a defect in quality.
Pixels sells thousands of pieces of artwork each month - all with a 100% money-back guarantee. We take great pride in the fact that hundreds of thousands of artists have chosen Pixels to fulfill their orders, and we look forward to helping you select your next piece!
All coffee mugs ship from our production facility within 1 - 2 business days of your order.


text:
American Physical Society Sites|APS|Journals|PhysicsCentral|Physics Magazine
- American Physical Society Sites
- Publications
- Meetings & Events
- Programs
- Membership
- Policy & Advocacy
- Careers In Physics
- Newsroom
- About APS
- Become a Member
College Park, MD – The 2013 Physics Nobel Prize has been awarded to two physicists who were instrumental in developing the theory that helps explain the origin of mass of elementary particles and predicts the existence of the Higgs Boson discovered last year. The prize, which recognizes the contributions of Francois Englert (Universite Libre de Bruxelles) and Peter Higgs (University of Edinburgh) for the theory of broken symmetry in electroweak physics, echoes the announcement of the 2010 American Physical Society's J. J. Sakurai prize, which was awarded to the two Nobel Laureates as well as four additional physicists who made comparable contributions to the symmetry breaking work.
"The discovery of the Higgs boson has captured the imagination of physicists and the public alike," said American Physical Society president Michael Turner. "It is hard to find a cab driver anywhere in the world who when he knows you are physicist doesn't ask about the Higgs boson. This is a tremendous achievement, involving more than 10,000 physicists from around the world to build, operate and analyze data from the most complex and most expensive science experiment ever built. The discovery of this new class of elementary particles not only completes one of the great intellectual achievements of the last century -- the standard model of particle physics -- but also raises new questions and has implications for other areas of physics including the birth of the Universe. Hats off to the global village of physicists who made this grand discovery possible, from Peter Higgs and Francois Englert to the thousands of scientists working at CERN --- many from the US and many not even born when Higgs wrote his paper. The particle is truly worthy of the name that Leon Lederman gave it -- the god particle."
The landmark papers the Laureates published that laid the foundation for spontaneous symmetry breaking appeared in the flagship APS journal Physical Review Letters in 1964. Both papers are available free-to-read to the general public.
Broken Symmetry and the Mass of Gauge Vector Mesons
F. Englert and R. Brout
Phys. Rev. Lett. 13, 321 (1964)
Broken Symmetries and the Masses of Gauge Bosons
Peter W. Higgs
Phys. Rev. Lett. 13, 508 (1964)
"We congratulate the Laureates and all who have contributed to this marvelous triumph for physics," said APS Editor in Chief Gene Sprouse. "APS is proud to have published the seminal papers that have led to this year's Nobel Prize."
The 2010 APS Sakurai prize cited Robert Brout (Universite Libre de Bruxelles), Gerald S. Guralnik (Brown University), Carl R. Hagen (University of Rochester), and T.W.B. Kibble (Imperial College) along with Englert and Higgs because the contributions of all six physicists were instrumental to the development of the highly successful standard theory of physics. In fact, Steven Weinberg (1979 Physics Nobel Laureate) cited them all on equal footing in his landmark paper "A Model of Leptons."
"It's unfortunate that this Nobel Prize is limited to only two recipients," said R. Sekhar Chivukula (2010 chair of the APS Sakurai Prize Selection Committee), "because failing to recognize the work of Guralnik, Hagen and Kibble is a significant oversight. I'm glad that the APS could award a prestigious prize in a way that makes clear just how important they all were in establishing the foundations of contemporary particle physics." The 2010 Sakurai Prize cites Guralnik, Hagen, Kibble, Brout, Englert, and Higgs for "elucidation of the properties of spontaneous symmetry breaking in four-dimensional relativistic gauge theory and of the mechanism for the consistent generation of vector boson masses".
APS issues press releases on research news, Society activities, and other physics tips.
General Media Inquiries
Sara Conners
Director of Communications
(301) 209-3238
Tawanda W. Johnson
Press Secretary
(202) 662-8702
Matteo Rini
Media Relations, Journals
The American Physical Society is a nonprofit membership organization working to advance and diffuse the knowledge of physics through its outstanding research journals, scientific meetings, and education, outreach, advocacy, and international activities. APS represents over 55,000 members, including physicists in academia, national laboratories, and industry in the United States and throughout the world. Society offices are located in College Park, Maryland (Headquarters), Ridge, New York, and Washington, D.C.


text:
So it's been a month since I told you all about my Fit2B Studio personal challenge! I'm going to be upfront and honest, since that's how I like to be. I made it through the first three weeks just fine, but now that the weather is nice, I find myself putting off my workouts.
I was fairly consistent with working out 3-4 days per week for the first three weeks, and it felt good. However, I definitely have noticed how very weak my core is, and that tells me I have a long road ahead of me yet. Thankfully, I will have Fit2B Studio to help me regain my strength.
Did any of you jump to the challenge? What do you like to do to keep your body healthy and your core strong?


text: Googling "goodbye in gaelic" constitutes my last act of Irish-honoring for the rest of the year, but enough about me — how was your St. Patrick's Day? Did you get super wasted and enjoy an ill-advised yet festive meal of corn beef and cabbage? Did you wear green or were you just too cool for such mindless trivialities? Speaking of green things — is it okay to dye dogs? It seems wrong somehow, but this puppy looks pretty happy.


text:
View Sub-Categories
Climbing Gear
There are no products matching the selection.
Climbing Gear & Climbing Equipment at OGEAt the Outdoor Gear Exchange we are passionate about climbing, whether it's rock or ice, and we've got all the gear you need to get out and have fun. No matter if you prefer trad or sport climbing, bouldering, mountaineering or mixed climbing, our experienced staff has used the gear we sell and can answer any questions you may have. We carry a huge selection from Black Diamond, Petzl, La Sportiva, Metolius, Mammut, DMM, Wild Country, Evolv, CAMP, and more. We also have killer deals on rock climbing harnesses, quickdraws, cams, chocks, climbing shoes, ice tools and crampons!
Can't Decide? Gift Cards Are Available


text:
23 April 2019
15:00 hrs
Aula TU Delft
Software theory seminar - Aritra Sarkar: "Implementing VHQCAs based optimization for accelerating genomics"
PhD defence - Chunhai Yin: "Conductance and gating effects at sputtered oxide interfaces"
PhD defence - Nikos Papadopoulos: "Mesoscopic transport in 2D materials and heterostructures"
Summer School Les Houches (France): Frontiers of condensed matter - register now!
QuTech Colloquium - Jens Eisert (Freie Universität Berlin): TBA
Casimir Course - Electronics for Physicists 2019 - register now (already 50% full!)!
AS researcher to lead new NWA programme
Quantum world-first: researchers can now tell how accurate two-qubit calculations in silicon really are
The most stable microscope in the world
Postdoc position: Probing the magnetic textures and spin-wave properties of 2D magnets using NV magnetometry
Delft, Toeno van der Sar lab
PhD vacancies in the Delft/Boukany group (soft living matter): "Flow and Deformation of Cancer Cells near Yielding"
Delft, Boukany group


text:
Aviva Premiership
Lewis-Roberts fails drugs test
ESPN Staff
February 15, 2013
Eifion Lewis-Roberts originally joined Sale in 2006 and then rejoined them from Toulon in 2012 © Getty Images
Sale prop Eifion Lewis-Roberts could be banned for two years after testing positive for morphine and pseudoephedrine following last season's Top 14 final.
The 32-year-old, who joined Sale Sharks last summer, failed a test after Toulon's defeat to Toulouse. Four weeks ago, seven months after his last match for Toulon, Lewis-Roberts' B sample was tested.
Sale were informed on Thursday afternoon that Lewis-Roberts had failed a drug test. A Sale spokesperson said: "The matter is in the hands of the Rugby Football Union and Premiership Rugby. Eifion has been rested for the last few weeks but he is available for selection for our match at London Welsh on Sunday."
Toulon flanker Steffon Armitage also tested positive for morphine after the French Top 14 final. He avoided a ban by successfully arguing the morphine came from two anti-inflammatory tablets he had taken before the match - a fact he had declare on his drug testing form.
The Toulon president Mourad Boudjellal said: "The player is not a drugs cheat. He took a product to relieve pain he was in and that is all there is to it."
© ESPN Sports Media Ltd.
Communication error please reload the page.


text:
Saturday, February 25, 2012
Terrible news
Yesterday in the early afternoon, our world lost one of its brightest stars.
Le Dinh Nghia (pictured in the grey jacket), an extraordinary young man from Thanh Hoa province, died in an apparent road accident. He was a few months short of his 21st birthday.
Nghia's funeral was held in his home town this morning, and at least 300 people were there. Everyone is just devastated.
I met Nghia on the streets of Ho Chi Minh City in 2006; I first wrote about him here. That photo of him shining shoes is a precious memory of my first encounter with Nghia. I knew immediately that he was somebody special. He was never a beneficiary of Blue Dragon; he was a friend and a little brother. He was a part of us.
Nghia brought sunshine and life. I have a vivid memory of hearing him one morning calling me with the words: "Mot ngay moi!" In English, he was saying: "It's a new day!" That was his bubbling, confident personality. I've never known anyone like him.
That same personality landed him in plenty of trouble over the years. He kept us busy bailing him out of a fight at school, or a run-in with the police... I had my own arguments with him from time to time. But he was so true to his name, which he once told me means: "Loyalty." No matter what conflict or argument he had with anyone, he was still their friend. Nghia would help anyone with anything - no matter the personal cost. I once asked him if he knew how to repair my CD player. He didn't, but he spent the next 3 months searching until he found someone who could. And then he refused to let me pay.
Nghia's sudden departure leaves a huge hole in many of us. So many people relied on him. After finishing some schooling, Nghia went on to study mobile phone repair, and he opened his own shop. Late last year we made this short film of Nghia for our website:
Nghia: In my own words
But there's so much he does not say in that short clip.
Like how he almost couldn't open a shop because he used all of his savings to help an older brother who was in trouble back in the countryside, so had to go into debt to start his business.
Or how he then grew the shop to employ 3 of his older brothers, and other friends who needed a job.
Or how he then started training other disadvantaged kids in mobile phone repair.
He doesn't say that he then went on to get a driver's licence and buy a taxi so he could work a second job at night; and that he paid for another brother to also get his licence so that they could work the taxi around the clock.
And he doesn't say that with all of that under his belt, he still wanted to do more, so he started studying to be a DJ.
Nghia had so many dreams, and they were never for him alone. All the money he earned was for his family; one of his brothers married just 2 weeks ago, and as far as I know Nghia paid for nearly everything.
He gave me one of my two dogs; a tiny pup I called Bear. I still have Bear, and I'm sure she senses that something is wrong.
Tonight I still find myself in disbelief that Nghia has gone. I cannot imagine a few days going by without seeing him at his shop, or sending him a text message, or having a quick drink with him at a cafe.
Nghia, you were a great person and you lived a good life. You left us far too soon, but we will do all we can to honour your beautiful memory.
10 comments:
- smash said...
I am so sorry for your loss and for everyone who was touched by Nghia. Please try to take comfort in the fact that all your lives - Nghia's, yours, his family and all those around him - were enriched in that short time he was in it.
Thank you for sharing with us what an amazing man he is - esp in view of such devastating loss. I am humbled.
- MikeInVietnam said...
Keeping you all and his family in my prayers.
- Dani said...
Words fail me.....I am so sorry......
- Regina said...
I am so sorry for your loss. Nghia sounded an amazing individual and he is an inspiration to many others. Thank for sharing such a great story, and I'll be praying for him and his family.
- Alison said...
That really is terrible news. Just heartbreaking.
Thinking of you all at Blue Dragon.
- Mosher said...
I only just posted a comment on facebook about so many young people in this country being underachievers, wanting to find the easy way to get on in life, with no ambition and happy to sit back and just have life handed to them on a plate.
Nghia is the kind of person we should all strive to be. Strong, ambitious, hard-working, kind, thoughtful, generous, brave, stubborn, unrelenting...
My best to yourself and his family and friends.
- Michael Brosowski said...
Thank you so much for your kind words. I only hope that Nghia knew how many people care for him.
Terrible to hear this news. Everyone here at UNIS Hanoi is thinking of his family at this time.
Community and Service UNIS Hanoi
The loss of a bright star in such a tragic way touches us all. Please let us know how we can help the family.
I am really sorry for Nghia loss, such a good future he had...I have no words, sorry...It is too sad...


text:
|2019 | 2018 | 2017 | 2016 | 2015
|2019 | 2018 | 2017 | 2016 | 2015
WEX virtual payment solutions can help save money, and even get cash back, when you pay suppliers. And our precise management and reporting solutions will free you to focus on your most critical mission – delivering quality educationLearn More
WEX Virtual Payment Solutions are a more secure way to pay preferred and out-of-network suppliers, which can save you money and preserve customer loyalty.Learn More
WEX Purchasing Cards, or P-Cards, help companies manage costs and reduce paperwork by providing details about employee spending. Additionally, they provide precise information, insights and control over how and where your company dollars are spent.Learn More
WEX virtual payment solutions seamlessly interface with many of the widely used media platforms, allowing for improved operational efficiencies, and real-time payment processing.Learn More
WEX offers the most popular fleet cards in the nation, accepted at over 90 percent of the nation's retail fuel locations and over 45,000 vehicle maintenance locations.Read More
Drive down costs and increase productivity across the travel spectrum. Streamline and automate even the most complex payment scenarios.Read More


text:
Rate The Last Movie(s) You Watched
I used to really like the HP series, I own all the books and I re-read them recently. And it suddenly struck me that round about the fourth book the wizarding attitude to Muggles starts to become really patronising, and later it's outright offensive. "Oh those silly Muggles, they use ridiculous things like electricity and stiches and metal wands that go bang, clearly we must wipe their memories at every available opportunity because they're just so silly and we know best." The whole thing smacks of British colonialism in the worst possible way. "oh you silly natives, you don't know how to run your country, we'll just take it off you and run it properly!"
You know what I'd like to see? I'd like to see an AU fic where the SAS storm the Death Eater hideout and shoot the bastards. Does a Shield Charm work on bullets? More importantly, can you cast one in the space of time it takes for a bullet to leave the chamber and blow your brains out, while you're choking on tear gas? MUGGLE MAGIC BITCHES.
While I like Dashing's arguments, I'd also like to toss in these rebuttals from the other side of the fourth wall.
Isn't it a bad idea to put all the sneaky, bigoted kids in Slytherin, all the brave kids in Gryffindor, etc.? The point of a school is not just to teach students about how life works, it's also to build character. If all the evil kids hang out only with other evil kids, they would always be evil! You shouldn't divide children based on their personalities, you should MIX them!
I'd like to point out that this was because the four founders of the school couldn't agree with what and who to teach and thus segregated it according to their own ideals. Yes, this is absolutely wrong and probably could've been changed by later school administration, but you don't screw with tradition apparently. Besides, three of the houses might go for integration, but the Slytherins wouldn't have it any other way.
Also, why the hell do Witches and Wizards celebrate Christmas? Isn't magic kind of AGAINST Christianity? That's like rabbits celebrating rabbit hunting season! Unless Jesus counts as a wizard or something.
And when was it ever said that magic was against Christianity? Are wizards not allowed to believe in Jesus or Kali or Allah or whoever the hell they want just like anybody else, just because of something they're able to do?
EDIT: Oh, and in The Goblet Of Fire, when Harry's name was chosen for the Triwizard Tournament, WHY DIDN'T HARRY JUST BACK DOWN?! What's the big deal? So, yeah, no one has ever backed down from the tournament, but WHAT'S THE WORST THAT COULD HAPPEN IF SOMEONE DID? Does the world end? Does every wizard explode and die? That Twilight guy would still be alive if only Harry just said "Okay, fine, I'll not go."
BINDING. MAGICAL. CONTRACT. It's spelled out in both the book and the film why Harry can't simply back down. It might even be on the same level as the Unbreakable Vow, where you drop dead if you fail to meet the requirements.
And now for something completely different.
And when was it ever said that magic was against Christianity? Are wizards not allowed to believe in Jesus or Kali or Allah or whoever the hell they want just like anybody else, just because of something they're able to do?
Exodus 22:18 wrote:Thou shalt not suffer a witch to live.Deuteronomy 18:10 wrote:There shall not be found among you any one that maketh his son or his daughter to pass through the fire, or that useth divination, or an observer of times, or an enchanter, or a witch.1 Samuel 15:23 wrote:For rebellion is as the sin of witchcraft, and stubbornness is as iniquity and idolatry. Because thou hast rejected the word of the LORD, he hath also rejected thee from being king.2 Chronicles 33:6 wrote:And he caused his children to pass through the fire in the valley of the son of Hinnom: also he observed times, and used enchantments, and used witchcraft, and dealt with a familiar spirit, and with wizards: he wrought much evil in the sight of the LORD, to provoke him to anger.Galatians 5:19-21 wrote:
19Now the works of the flesh are manifest, which are these; Adultery, fornication, uncleanness, lasciviousness,
20Idolatry, witchcraft, hatred, variance, emulations, wrath, strife, seditions, heresies,
21Envyings, murders, drunkenness, revellings, and such like: of the which I tell you before, as I have also told you in time past, that they which do such things shall not inherit the kingdom of God.
The last movie I saw was Wonder Woman I liked it a lot. One thing that pissed me off though isher invisible jet was never explained at all. There living on an amazon island cut off from everyone but they have an invisible jet with invisible missiles at there use. The guy who was stuck on the island who should be asking questions 4 the audience doesn't even question the jet at all
Rather Dashing wrote: »Another bestselling book set that trope in motion. Kind of like how vampires have had their cultural image shaped by film, the Christian stance on witches is shaped by literature.
Well, that kinda sucks for Muggle-born wizards and witches who were raised in ultra-devout Christian families, particularly with the whole unable-to-control-their-magic-at-a-young-age thing.
Well, that kinda sucks for Muggle-born wizards and witches who were raised in ultra-devout Christian families, particularly with the whole unable-to-control-their-magic-at-a-young-age thing.
Its the same for gay's in real life born to Super Christians.
I'm sure there's some Bible Belt witches and wizards that had it a great deal worse than Harry. It would probably be analogous to being a homosexual child in such families, except possibly worse.
Rather Dashing wrote: »It would probably be analogous to being a homosexual child in such families, except possibly worse.
It depends if they try to "cure" the gay child, banish them from the community or kill them.
I think witches got the test where it kills them either way.
Last movie in theatres: Skyline
absolutley terrible, filled with gaping plot holes. 1. I really didn't care if the characters died, I never got to liking them. 2.They nuked the city, but where is the damage and fallout and all that other crap? Along the same lines, why do you land troops after nuking the area?3.The ending: Oh God, what was that? I get that the guy was now an alien, but what else? Do they just die in that thing?
Last movie I saw on TV: Back to the Future. Always a classic!
It depends if they try to "cure" the gay child, banish them from the community or kill them.
I think witches got the test where it kills them either way.
And when was it ever said that magic was against Christianity? Are wizards not allowed to believe in Jesus or Kali or Allah or whoever the hell they want just like anybody else, just because of something they're able to do?
I don't remember them celebrating Christmas in a particularly Christian way. They have their own traditions for many things, why just that? Heck, I didn't know some people celebrating Christmas as the birth of Jesus before I was a teenager. (Granted, in French the common name is Noël (Yule), not Christmas, so it would be harder to pull off in English.)
The celebration itself predates Jesus, so if they want to have a winter celebration and exchange gifts, I fail to see why that would be a problem regardless of their actual beliefs.
While I like Dashing's arguments, I'd also like to toss in these rebuttals from the other side of the fourth wall.
I'd like to point out that this was because the four founders of the school couldn't agree with what and who to teach and thus segregated it according to their own ideals. Yes, this is absolutely wrong and probably could've been changed by later school administration, but you don't screw with tradition apparently. Besides, three of the houses might go for integration, but the Slytherins wouldn't have it any other way.
And when was it ever said that magic was against Christianity? Are wizards not allowed to believe in Jesus or Kali or Allah or whoever the hell they want just like anybody else, just because of something they're able to do?
BINDING. MAGICAL. CONTRACT. It's spelled out in both the book and the film why Harry can't simply back down. It might even be on the same level as the Unbreakable Vow, where you drop dead if you fail to meet the requirements.
And now for something completely different.
Ah, okay. You're the first one to point these out, thanks. Not one of my friends can ever have a nerdy discussion with me...
Back to the Future: 10/10
Professor Layton and the Eternal Diva: 9/10
and that's apparently the only movies I've seen recently... I need to watch more movies.
the new harry potter movie. Saw it on the first day it came out and I LOVED IT!!! It had a great storie, some good jokes every once and a while, and a really sad ending that made for a great cliffhanger.
Well, that kinda sucks for Muggle-born wizards and witches who were raised in ultra-devout Christian families, particularly with the whole unable-to-control-their-magic-at-a-young-age thing.
Good thing they don't exist! phew! Dodged a bullet there, huh?
Was I too hard on him?
Jen Kollic wrote: »You know what I'd like to see? I'd like to see an AU fic where the SAS storm the Death Eater hideout and shoot the bastards. Does a Shield Charm work on bullets? More importantly, can you cast one in the space of time it takes for a bullet to leave the chamber and blow your brains out, while you're choking on tear gas? MUGGLE MAGIC BITCHES.
I always thought it would have been a great idea to just send the army out against Voldemort, maybe with some sort of wizard support squad. He can't kill everyone at once and he most definitely can't block every single bullet. But of course, they had to try to fight the guy on his own terms, which just isn't really all that clever.
Ghostbusters - 11/11 - Do I really need to explain my score? I adore this film and every aspect of it.
District 9 - 11/11 - Great sci-fi film; great action; great heroes.
The Expendables - 6/11 - The action wasn't bad but I feel like this movie was better when it was Rambo. Statham and Li were the best parts; but mostly it just doesn't hold up to the type of film its trying so hard to emulate. All in all it's not a film I'll remember.
Iron Man II - 6/11 - A much less interesting rehash of the first film. Downey Jr. is still great as Stark, and Sam Rockwell is fantastic as always, but Mickey Rourke, Scarlett Johansson, and Samuel L. Jackson are criminally underused. The action is okay, but mostly not that great until the final action scenes.
Grown Ups
I only chuckled once.
(Boy this is going to be long, sorry!)
Ok, I'm going to start rating by "grades" now, because I feel the number system is too limited for my feelings and feels a little more technical than actual letter grades.
Where do I start?
Well, on a technical level it was gorgeous, as expected. I mostly enjoyed the settings and effects the best, they were wonderfully designed and interesting to look at on the big screen. And of course, there's the hair, which is not only handed fantastically in terms of animation, but hair that long, which generally any long hair at all is preferred to be avoided in animation, has to be given automatic respect to be handled that way. (especially in the case of rendering) The character animation itself, to me, felt like nothing special. There were times when it had its unique charm, but otherwise it's something that doesn't really differentiate the movie to me from other works of CGI animation. (also the physics in this movie seemed a little weird at times, even it terms of cartoony animation, but it's minor so I'll look past it I guess) That doesn't mean it isn't animated very well, I'm just saying for a movie that claims to have achieved some new "feeling" with CGI, it really doesn't seem that way to me.
It can be said of course, that the style is unique because it's transferring the old Disney style of fairy tale movies to 3D, which is true, but that's exactly why I don't find it as unique as previous animated CGI efforts. In fact, this whole "we have to prove to the audience we can make a typical Disney princess movie seem traditional through the use of CGI" is exactly the movie's main flaw, not just in terms of animation. It just seems like it's being sold on the main fact that it's a "classic Disney princess flick, but in 3D!" and that's a huge cop-out because it gives them an excuse for not trying to be different. I'm pretty sure it can easily become a welcome addition to the family of Disney fairy tale movies, because it certainly captures the spirit of them, but to say it's capable of catching the exact same feeling that traditional 2D animation captures is a huge stretch, and it baffles me that people fall for the whole "we're trying to prove we can evolve our style using CGI" because it's no evolution of 2D at all. That's like saying sculpting is an evolution of painting. If it would have been actually made in hand-drawn animation in some of the ways the art book demonstrates I'm pretty sure it would have felt totally different. As it stands, it's not as unique as it thinks it is from other movies in CGI and maybe it wouldn't have been as unique as other Disney princess movies when done in 2D, but it certainly would have been more likely to, especially in terms of standing out from other animation studios. Also, this movie has been worked on and hyped up for so long, and we have been promised all sorts of unique styles throughout (including 2D) that it just seems like so much wasted potential.
As for the story itself, again, it suffers too much from slavishly trying to be traditional, to the point of looking overdone. It wasn't as predictable as I was expecting and it's certainly a lot better and different than the "Enchanted 2" the trailers made it seem to be, but it was still pretty damn predictable. So many elements were so forced from tradition it was annoying. I mean you got your little animal sidekick that is really there for no reason, (except at the end, which actually seemed just like a last-minute convenience becauseshe was going to die anyway and could have easily tripped on the window itself) the generic horse with human-like personality, (I did laugh a little at him but he mostly just seemed waaaaay overdone, it's like "quick! This is the funny horse of the movie! Make him do something silly here! Make him have a bro relationship with his rider! QUICK, A SILLY EXPRESSION. Sleeping Beauty? El Dorado? Mulan? No, this horse is different! Really!" I mean, I thought the viking dudes were a lot funnier and unique and I felt they should have focused more on them for laughs rather than giving the horse too much personality where it's not needed.) the song numbers, (I actually really enjoyed the original score and it's one of my favorite aspects of the movie, but the lyrical songs themselves are forgettable and feel really unneeded.) the expected, forced romance, and so on. In general, the romance just seemed really sloppy. Really now? Did we need the obvious"looooook at uuuuuuuss we're falliiiiiiiiing in loooooooove on a boooaaaaat with pretty liiiiiights" song? Geez, I get some kids won't catch the obvious subtext as easily as adults but I'm sure they got the point by then.In general, I just wasn't into the romance at all! Which is terrible because to be honest, romance is one of my favorite parts of movies, especially animated ones. This one just felt, again, extremely forced. When a romance is to be expected from everyone in the first place, you have to put some effort into making it interesting, unpredictable and full of at least some sort of effective tension. Maybe it's just because Flynn and Rapunzel were generally weakly developed characters. No really! Do we ever get to find out at least a little of Flynn's background? Why he's a thief? Why we are expected to believe he has these sudden feelings? It just kind of seems like he's put in there as the love interest and then "oh by the way he's a thief, surely this would automatically make the romantic subplot/plot interesting!" Rapunzel herself was a pretty neat character, I have to admit, they made her airheadedness actually cute and endearing, (and it made sense, considering how she grew up) while still retaining personality. (Though I was sad they didn't make a character who has never had any social contact outside of Mother Gothel for all her life a little more awkward, but whatever.) In reality though, I was a bit disappointed with her overall development. I mean what was withthe sudden realization she was a princess? Was it just me or was that just plain sloppy writing?Nevertheless it was kind of annoying that she's just like"herp derp the world is a pretty ok place!" just from that realization alone, not to mention the "you're my dream now, Eugene!!!" NO, DISNEY, NO.In short, it just feels like a step down from what The Princess and the Frog tried to achieve, and generally succeeded, which was to make a traditional animated Disney princess fairy tale, but to make it unique from the rest, with twists. The "princess" being independent, with an actual dream outside of finding true love, and her dream is not replaced, but made better by the finding of love. Not to mention it actually made the generic animal sidekicks not so generic with actual purposes and small (but effective) developments.
On the plot's good points, I enjoyed the villain very, very much. She herself was a traditional villain but with unique twists. She was effectively menacing in that I felt uncomfortable when she was around. She was the classic "evil stepmom" but without being overly physically evil. She's touched up with that sort of familiarity with Rapunzel where it makes her even more unsettling than if she was downright abusive, and they give her an effective understandable, but still evil, reason for why she does what she does. Plus, her song is probably the only lyrical song I enjoyed. I didn't laugh very much overall at the movie, but my general amusement came from the viking thugs, and I wished they were made to be a bit more developed other than"let's sing about our dreams, now we're friends so we'll help you escape twice for plot convenience" so that they were more endearing and funny when shown at the end.As much as I thought the horse was too much, he's still the best animated character next to Rapunzel and when he pulls an exaggerated expression/pose it's pretty damn funny. The whole plot in general is pretty uniquely done in the whole "Rapunzel with a twist" thing, they changed story elements as expected, but it's mostly good change. Yet they also kept stuff while putting little twists on them that I enjoyed, such asthe magical tears just like in the story, except this time it also makes sense to its own individual plot.
To sum it up, as a whole, the movie isn't very revolutionary in terms of CGI animation or plot, and in fact is too traditional to the point of slavish and overdone, and pretty much a step down from what Princess and the Frog tried to do. Even so, the visuals are spectacular and it's a fun ride, even if rocky, through the plot, especially so if you love traditional Disney tales. It's worth it for the big screen on that alone, and I'm also willing to see it again in theaters if another friend wants me to come see it. Personal feelings aside, it's still easily deserved as a future Disney classic.
Iron Man 2 - 4/5
Lots of funny moments, action and great special effects.
Star Trek The Next Generation: First Contact 9.5/10 - This is still probably one of my favorite movies ever. Some of it might be nostalgia factor since I grew up with (and am still a huge fan of) Star Trek The Next Generation, but in general it's a very well constructed movie. The special effects are good, the action is tight and the character interactions are consistent and well handled. I love even the stupid crap down on Earth, like Troi getting drunk and Barclay being his usual spaz self. My one complaint would be that I felt everyone got an equally large role except for Crusher, which seems a bit unfair given she got shafted in terms of episode focus during the seven season run of the show, but even that is a fairly minor complaint.
This got me really missing Star Trek and is the reason I'm currently running TNG in the background as work on assignments. Now I feel like I should back up and run through all the Star Trek movies. Maybe I'll hate Star Trek the Motion Picture and the new movie less....And maybe I'll get the tide to turn back in and ride a unicorn to class.
VeronicanPlay wrote: »Iron Man 2 - 9/10.
Lots of funny moments, action and great special effects.
Wow, you're easy to please, must be great even watching TV with this standard.
I watched Iron Man 2 last.
I enjoyed it, and was quite entertaining as an action movie, and even though it's about a guy who wears a suit and flys around at supersonic speeds, it managed to stay somehow realistic and hardly cheesy at all!
Just finished watching The Thief and The Cobbler: Recobbled Cut, and I have to say, its a very nice film.
Admittadley I haven't been tainted with the other versions of it, so I took it as I saw it.
Despite the inconsistency, (since it was composed of different versions), the animation was absolutely fantastic, (I just love the small details here and there, like zigzags shoes, and the use of tacks to convey Tacks emotions), the mix of styles blend very well and create something unique.
I'd give it a 8.5/10, not one of the greatest films I've ever seen, but still very good and highly recommended for everyone!
Watched the new Chronicles of Narnia movie last weekend. I really liked it, pretty nice movie and adaptation. Oh, and thank ****ing god for character development, Eustace would make it unbearable to watch otherwise.
Oh, and damn, the religious elements get less subtle each time XD
DrRocketGenius wrote: »...why would you say that? I enjoyed Iron Man 2 also, and I usually hate superhero movies.
Because in my opinion relative to the first part or some of the other better superhero movies or movies generally this one had a couple of major flaws and giving it a almost perfect score therefore is overrated.
Harry Potter 7, part I....not too bad....vote 6.5!
A. Seven Samurai 8.5/10 (great film, especially for its time, nice characters but certain parts nowadays feel kind of aged).
B. House of Flying Daggers 8.5/10 (what a beautiful and partly touching movie, just wow, a couple of memorable scenes, the story and dialogues could be better).
Nice, you watched Seven Samurai.
Amazing flick.
The last seconds of that movie were so powerful, you know the hills....
I actually watched The Matrix trilogy all on Sunday as I refused to move from my warm bed all day. The original's great, most'll agree on that, but the other two are pretty unfairly slated. For all the obtuse crap there is in there, may I remind you that there's like a million Hugo Weaving's on screen at once. Please take this into account and reassess
Wow, you're easy to please, must be great even watching TV with this standard.
The whole "I don't watch TV" thing to me always smacks of elitism to be quite frank. TV caters for a wide variety of people and tastes, it's only natural that the vast majority of stuff being aired doesn't appeal to you or me or Joe Bloggs.
I don't personally watch TV a lot outside of the news, but I don't think it's necessarily a vapid wasteland by any means
Edit: All that said I wouldn't be giving Iron Man 2 a 9/10 anytime soon
Depends on your ratings scale I guess? Actually, 9/10 is a bit high, but if you're like a videogame reviewer and 7 is "it works, I guess, you know, kind of average", then an "8" would be arguably warranted.
I don't see a reason for watching TV anymore. Beside of a few football matches, a WM, cabaret and one children show it just doesn't make sense anymore as i've already seen what i wanted to, i don't need the trash and if they produce something interesting every decade, you can get it on DVD as well.
Iron Man 2, like many of the TV productions, to a large degree was a trash movie, maybe a 3/10, 4/10 if i'm really drunk and all feels magically fine. Simply one of those films you felt guilty wasting your money and time after leaving the cinema.
The Twilight Saga: New Moon - 0/5
So bad I don't even want to go into detail in fear I might throw up.
puzzlebox Telltale AlumniChico & Rita - 7.5/10
Animation for grown-ups. Follows the stormy on/off relationship between two musicans (a singer and a piano player), from Havana to New York to Paris and back, through the jazz era of the 1950s and beyond. AMAZING soundtrack, as you might imagine.
It Happened One Night - 9/10 <-- lovelovelove
1930s film about a spoiled little rich girl who runs away to New York, falling for a roguish newspaper reporter along the way. Engaging characters, beautiful story, clever script. Laughed out loud so many times. Modern romantic comedies are pale imitations of this stuff.
The Dish - 7.5/10
Australian movie about the radio receiver dish in Parkes, which was responsible for putting the 1969 moon landing footage on TV. Nerdy and fun. Subtle, gentle humour and ocker accents all over. Made me homesick.
Drunken Master - 11/11 - The story of an arrogant, disrespectful, bark-worse than-bite little git-bastard who is shown repeatedly what a worm he really is, until, humiliated, he trains in a secret art of kung fu and gains respect for himself and for others. A fantastic story of growth.
Drunken Master II - 9/11 - This sequel pales story-wise in comparison to the classic that is the first. BUT. Action-wise and acting-wise, it's just as good. Jackie Chan really impresses me sometimes with his acting in his films outside the kung fu parts, and he pulls off some strong emotions in this film, but that's nothing strange as he did the same in the first. The woman who plays his mother really is the highlight of the film. She is badass. Action wise this is one of the best kung fu films of all time, no doubt, but even though the action in this is on a bigger scale, I still prefer Drunken Master One.
Despicable Me - 10/10
I have been waiting for this to come out on Blu-ray since I first saw it. This is, hands-down, my favorite movie of the last few years. Hopefully I get a 3D TV soon so I can watch it in 3D.
DrRocketGenius wrote: »Despicable Me - 10/10
Someone gave Seven Samurai 8.5 out of 10... but generic mass market CGI comedy gets a perfect score? I think I'm done with this thread.
Comrade Pants wrote: »Someone gave Seven Samurai 8.5 out of 10... but generic mass market CGI comedy gets a perfect score? I think I'm done with this thread.
It's not my problem that I have a different opinion than you. I thought it was a fantastic movie, so I gave it a score reflecting that. If you didn't see it- or didn't like it- fine. Whatever. Not a big deal.
Sign in to comment in this discussion.


text:
TheWildGeese.com is a leading destination for those passionate about the history and heritage of the Irish. The webzine has drawn millions of readers to its more than 600 online features during its 14+ years online. Planning its first major redesign, TheWildGeese.com 2.0 will have Irish Family History as a major focus, with a standalone channel and blog serving as the channel's herald. To learn more, contact Alannah Ryane, our Genealogy Channel Producer, at firstname.lastname@example.com. TheWildGeese.com: The History of the Irish . . . Worldwide.
About The Founders:
Gerry Regan, (email@example.com) the co-founder and executive producer of TheWildGeese.com, has an extensive background in journalism and New Media, along with intense interest in American and Irish history. He has studied modern British and Irish history in Trinity College, Dublin, and as a journalist and devotee of history, has had articles published in the Irish Echo, The Civil War News, The Washington Times, Medical Tribune, Newsday, and various other publications. Gerry served as a staff writer and copy editor for Gannett Westchester Newspapers and USA Today, and worked at Prodigy Services Inc. as a news editor, at newsday.com as a producer, and at office.com as a copy editor. He is a magna-cum-laude graduate of Duke University, majoring in mathematics, and has a masters degree in journalism from New York University.
Joseph E Gannon (email@example.com), Research Director. Based in Connecticut, Joe is a talented writer, editor and researcher and devotee of both the online world and military history. Joe attended the University of Connecticut, and is a US Army veteran who served in the Military Police in Vietnam in 1971-72. He has an extensive background researching both Irish and Civil War history, and is a contributor to the newsletter of the 27th Connecticut Volunteer Infantry, which is one of the largest such organizations in the USA. He is a research librarian at a corporate library.


text:
Organosulfur compound
Organosulfur compound, also spelled organosulphur compound, also called organic sulfur compound, a subclass of organic substances that contain sulfur and that are known for their varied occurrence and unusual properties. They are found in diverse locations, including in interstellar space, inside hot acidic volcanoes, and deep within the oceans. Organosulfur compounds occur in the bodies of all living creatures in the form of certain essential amino acids (such as cysteine, cystine, and methionine, which are components of proteins), of the tripeptide glutathione, and of enzymes, coenzymes, vitamins, and hormones.
Typical organisms contain 2 percent sulfur dry weight. Coenzyme A (CoA), biotin, thiamin chloride (vitamin B1), α-lipoic acid, insulin, oxytocin, sulfated polysaccharides, and the nitrogen-fixing nitrogenase enzymes are but a few examples of important natural sulfur-containing compounds. Certain simple organosulfur compounds, such as thiols, are repugnant to humans and most higher animals even at extraordinarily low concentrations; they are used as defensive secretions by a variety of animal species and figure in unpleasant odours associated with polluted air and water, particularly that resulting from the use of sulfur-rich fossil fuels. However, related types of organosulfur compounds found in such foods as garlic, onion, chive, leek, broccoli, cabbage, radish, asparagus, mushroom, mustard, truffle, coffee, and pineapple are sources of olfactory and gustatory delight.
Mustard gas, or bis(β-chloroethyl) sulfide, (ClCH2CH2)2S, is a potent chemical warfare agent, whereas other sulfur compounds such as sulfanilamide (a sulfa drug), penicillin, and cephalosporin are valued antibiotics. Synthetic organosulfur compounds include polysulfones, inert polymers used in astronauts' transparent face shields; polythiophenes, materials possessing the metal-like ability to conduct electricity; agricultural chemicals, insecticides, and organic solvents, such as dimethyl sulfoxide, CH3S(=O)CH3, and carbon disulfide, CS2; dyes; lubricating oil constituents; food additives; and substances used to make rayon. In chemical research, organosulfur compounds are valued reagents widely used for synthesizing new compounds. A global sulfur cycle exists that interconverts natural organosulfur compounds with either inorganic sulfide or sulfate ions. Sulfide or sulfate ions can also be formed in nature from elemental sulfur.
The sulfur atom
Differences between the chemistry of sulfur compounds and that of other common heteroatomic organic compounds (i.e., organic compounds containing elements other than carbon [C] and hydrogen [H], such as those of oxygen [O] and nitrogen [N]), are primarily due to the fact that sulfur is a member of the third period of elements, employing 3s, 3p, and sometimes 3d orbitals, which are significantly larger than the more compact 2s and 2p orbitals of second-period elements such as oxygen and nitrogen. The larger orbital size means that the outer valence electrons are more loosely held, being further removed from the influence of the positive nuclear charge. Such loosely held electrons are said to be more polarizable, allowing them to engage in bonding interactions with electrophilic partners more easily and earlier during the course of a reaction than in the case of lighter elements, where bonding interactions require close approach of partner atoms. In addition, in protic hydrogen-bonding solvents such as water and alcohols, sulfur is more weakly solvated than lighter heteroatoms. In these solvents, heavier heteroatoms such as sulfur show enhanced nucleophilicity compared with lighter heteroatoms because of their higher polarizability combined with decreased solvation (the solvation shell must be disrupted in reaching the transition state), despite the fact that stronger bonds are formed by the lighter heteroatoms. Thus, divalent sulfur compounds, such as thiols (containing an ―SH group) and sulfides (containing an ―S― group), readily bind to heavy metal ions such as silver (Ag), mercury (Hg), lead (Pb), and cadmium (Cd). Indeed, another name for thiol is mercaptan (from Latin mercurium captans, meaning "seizing mercury"), reflecting the use of thiols in treating mercury poisoning. Interactions between divalent sulfur and the metal ions iron (Fe), molybdenum (Mo), zinc (Zn), and copper (Cu) are crucial in metalloenzymes—for example, cytochrome C, in which the sulfur of methionine is coordinated to the iron in heme; the iron-sulfur proteins, in which cysteine sulfur is bound to iron; and molybdenum-containing enzymes, some of which involve dithiolate (two-sulfur) cofactors.
It is useful to compare features of the compounds of sulfur (electron distribution 1s22s22p63s23p4) with those of oxygen, which lies directly above sulfur in the periodic table (electron distribution 1s22s22p4), and with those of the heavier member of the chalcogen family, selenium (electron distribution 1s22s22p63s23p64s23d104p4), which lies directly below sulfur. There are structural similarities, for example, between alcohols (R―OH), thiols (R―SH), and selenols (R―SeH), between hydroperoxides (R―OOH), sulfenic acids (R―SOH), and selenenic acids (R―SeOH), between ethers (R―O―R), sulfides (R―S―R), and selenides (R―Se―R), between ketones (R―C(=O)―R), thioketones (R―C(=S)―R), and selenoketones (R―C(=Se)―R), between peroxides (R―OO―R), disulfides (R―SS―R), and diselenides (R―SeSe―R), and between oxonium (R3O+), sulfonium (R3S+), and selenonium salts (R3Se+), where R represents a general carbon group—e.g., the methyl group, CH3, or the ethyl group, C2H5.
There are significant differences in the properties of these groups of related compounds. For example, thiols are somewhat stronger acids than the corresponding alcohols because the S―H bond is weaker than the O―H bond and because the larger sulfur atom better disperses the resulting negative charge as compared with oxygen. For the same reasons, selenols are even stronger acids than thiols. At the same time, SH hydrogen bonding is much weaker than OH hydrogen bonding, with the consequence that thiols are more volatile and have lower boiling points than the corresponding alcohols—for example, 6 °C (43 °F) for methanethiol compared with 66 °C (151 °F) for methanol. Compared with alcohols and ethers, low-molecular-weight thiols and selenols as well as sulfides and selenides have highly unpleasant and obnoxious odours, although the perception of the odour as unpleasant or pleasant can sometimes vary with the concentration of the particular compound. Disulfides and diselenides are far more stable than peroxides, and sulfonium and selenonium salts are much less reactive than oxonium salts; at the same time, simple thiocarbonyl (C=S) and selenocarbonyl (C=Se) compounds are much more reactive than simple carbonyl (C=O) compounds. In the case of the homologues of carbonyl compounds, the difference in reactivity is attributed to the poorer match in the size of the orbitals of the carbon and sulfur double bond (carbon 2p and sulfur 3p) or the carbon and selenium double bond (carbon 2p and selenium 4p) compared with the similar 2p orbitals used for the double bond between carbon and oxygen.
Both sulfur and selenium also have the ability to form compounds in which atoms of these elements have higher valences; these compounds have no counterpart in oxygen chemistry. In the case of sulfur, some examples are sulfoxides (R2S=O, typically written R2SO), sulfones (R2S(=O)2, typically written R2SO2), sulfonic acids (RSO3H), and oxosulfonium salts (R3S+=O). Analogs of the above sulfur compounds also exist for selenium. These higher-valence compounds of sulfur (or selenium) are stabilized through bonding involving 3d (or 4d) orbitals, not available to oxygen, as well as other factors associated with the larger size of sulfur and selenium as compared with oxygen. The longer, weaker bonds and higher degree of polarizability of selenium compared with sulfur lead to differences in properties and reactions of compounds of these two elements.
Analysis of organosulfur compounds
In addition to routine methods of analysis that can be used with all classes of organic compounds (see analysis), certain procedures reflect specific characteristics of sulfur. In a mass spectrometer, organosulfur compounds frequently produce strong molecular ions in which the charge is located predominantly on sulfur. The presence of sulfur is indicated by the occurrence of sulfur-34 (34S) isotope peaks, 4.4 percent of the abundance of 32S. Organically bound sulfur in the form of the natural isotope 33S can be directly examined by nuclear magnetic resonance (NMR) spectroscopy, although the low natural abundance (0.76 percent) and small magnetic and nuclear quadrupole moments make analysis more difficult than for protons (1H) or carbon-13 (13C). Levels of organosulfur compounds in crude petroleum as low as 10 parts per billion or less may have a detrimental effect on metallic catalysis or may cause unpleasant odours. These very low sulfur levels are detected using gas chromatographs with sulfur chemiluminescence or atomic-emission detectors with high sensitivity to detect sulfur compounds in the presence of other compounds.
Organic compounds of bivalent sulfur
Thiols, or sulfur analogs of alcohols, are sometimes referred to as mercaptans. In naming these compounds, the suffix -thiol is appended to the name of the appropriate hydrocarbon; e.g., CH3CH2CH2CH2SH is named butanethiol. The prefix mercapto- is placed before the name of a compound if the ―SH group is to be named as a substituent, as in mercaptoacetic acid, HSCH2COOH. A third naming system uses the prefix thio- in front of the name of the corresponding oxygen compound, as, for example, thiophenol (C6H5SH), also called benzenethiol. A number of thiols are found in nature, such as cysteine and glutathione. In addition, 2-butenethiol is found in the defensive spray of the skunk, 2-propanethiol (allyl mercaptan) is found in the breath of people who have eaten garlic, and furfurylthiol contributes to the aroma of fresh coffee. Lower-molecular-weight thiols have strong, generally repugnant, skunky or rotten-egg-like odours, which can be detected by humans in air at very low concentrations—for example, 0.5 part per billion (0.5 × 10−9) in the case of ethanethiol or benzenethiol. For some thiols such as 4-mercapto-4-methylpentan-2-one (C6H12OS), which occurs in Sauvignon Blanc wines, the odour varies from pleasant at trace levels to unpleasant at higher levels. Because of their strong odours, thiols, such as 2-methyl-2-propanethiol, are used as odourants and warning agents for natural gas leaks. 2-Mercaptobenzothiazole is a thiol that finds use as an accelerator in the vulcanization of rubber (see below Disulfides and polysulfides and their oxidized products) and as a corrosion inhibitor, whereas 6-mercaptopurine has been employed in cancer therapy.
When long-chain alkanethiols are exposed to metallic gold, they bind to the gold surfaces, functioning as a type of "molecular alligator clip" and forming self-assembled monolayers (SAMs), of interest in the field of nanotechnology. SAMs can be formed on planar (two-dimensional) as well as particle (three-dimensional) surfaces. The ordering of long-chain alkanethiols is driven by the substantial gold-sulfur binding energy of approximately 160 kilojoules per mole (kJ/mol), as well as by the lateral van der Waals forces between the tethered alkyl chains (10–20 kJ/mol). Dipole interactions between polar end groups on alkyl chains can become important for functionalized thiols. Nanoparticles consisting of alkanethiolate monolayer-protected clusters (MPCs) in the form of ultrafine suspensions (colloids) of gold particles are 3-D analogs of the 2-D SAMs. The 2-D and 3-D SAMs can be prepared from ultraclean gold surfaces upon interaction with thiols (unprotected or S-acetyl or S-(N-ethyl)carbamoyl-protected) and disulfides, which are adsorbed about 40 percent more slowly than thiols. These sulfur compounds may have a wide range of alkane chain lengths (C3–C24) and diverse end-of-chain substituents, such as water-soluble groups (e.g., amino acids and polyethylene glycol), aromatic groups, silicon functionalities, fullerenes, porphyrins, ferrocene, crown ethers, and tetrathiofulvalenes, among others. There are many potential applications of SAMs and MPCs in fields ranging from materials science (e.g., nanoscale electronics, thin films, and electro-optics) to chemistry (e.g., catalysis, nanoreactors, and chemical sensors) to biology (e.g., membrane mimicry, biosensors, and drug delivery).
The interconversion of natural thiol pairs and disulfide groups constitutes a key oxidation-reduction reaction (or redox reaction) used in biochemistry; the redox potential, or tendency to attract electrons and thus become reduced, of the thiol-disulfide system is such that most disulfides are reducible by the biological reducing agent nicotinamide adenine dinucleotide (NADH), which has an optimum redox potential for this system. (See chemical reaction: Oxidation-reduction reactions for a discussion of redox reactions.) Proteins containing the mercapto (thiol) group from the component amino acid cysteine play key roles in many enzymatic processes. The cytoplasmic component glutathione (GSH), which also contains the mercapto group, is important in cellular oxidation and reduction, in nitric oxide (NO) transfer processes, and in protecting cells against damage from radicals. GSH reacts with NO to form the S-nitrosoglutathione (GSNO), which displays powerful antiplatelet aggregation properties and is therefore useful in coronary angioplasty operations. S-Nitrosothiols such as GSNO are found in vivo and play an important role as NO donors and in the transport and storage of NO, a small molecule that controls a remarkable range of physiological functions. In vivo release of NO from nitrosothiols may be catalyzed by copper ions. The selenium-containing enzyme glutathione peroxidase, which plays a crucial role in prevention of damage due to radicals derived from lipid hydroperoxides, is believed to function via formation of an intermediate with a sulfur-selenium bond that is significantly more reactive toward a thiol nucleophile than a sulfur-sulfur (disulfide) bond. Thus, the enzyme, which contains a selenocysteine (or selenol; RSeH) at its active site, is oxidized to a selenenic acid (RSeOH) in the course of reducing the hydroperoxide R′OOH. The selenenic acid is then converted by GSH to a selenyl sulfide (ESeSG), which reacts further with GSH to regenerate the enzyme RSeH. This reaction also gives glutathione disulfide (GSSG), which is reduced back to GSH, thereby continuing the cycle.
The sulfur in cysteine—and sulfur in other divalent sulfur compounds found in plants and animals—is ultimately derived from sulfate (―SO42−) in the soil, which is reduced in the cell. In plants and bacteria that utilize sulfate as a source of sulfur, the first step in the reduction process is the formation of adenosine phosphosulfate (APS), since direct reduction of sulfate itself is extremely difficult. The ―OSO2O1− group of APS is reduced to a sulfite ion (SO32−) or a protein-bound sulfite, which is then further reduced to hydrogen sulfide (H2S), a direct precursor of cysteine and other natural organosulfur compounds.
In animals, sulfur-containing amino acids and other compounds are excreted as inorganic sulfate.
Thiols and thiol-derived compounds have several important roles in biology. As thiolate, RS−, they can function as bases, as ligands (e.g., in the binding of metals, as in hemoglobin), and as agents for the transfer of acetyl groups (e.g., in acetyl CoA) in lipid biosynthesis. In acetyl CoA, sulfur exists in the form of a derivative of a thiol, a thioester, CH3C(O)―SCoA; the (O) represents a (=O). The C(O)―S bond in this coenzyme is weaker than the corresponding C(O)―O bond in an ester. Furthermore, the thiolate anion (in this case, −SCoA) is a better leaving group than the analogous alkoxide anion (−OR) because in the larger sulfur atom the negative charge is spread over a larger volume of space. In general, the superior attacking-group (nucleophile) as well as leaving-group qualities of thiolate make it an excellent biocatalyst.
Low-molecular-weight thiols such as methanethiol (CH3SH) are found in crude petroleum. As such, they pose serious problems, associated not only with objectionable odours but also with their corrosive effect on equipment and their ability to poison (render nonfunctional) catalysts for air-pollution control or for other chemical processes. If they can be efficiently recovered from crude petroleum, these low-molecular-weight thiols can be used in the manufacture of agricultural chemicals and other chemical commodities.
Thiols were first prepared in the laboratory in 1834. They can be synthesized by several procedures, including reaction of an alkyl halide (RX, where X is a halogen) with the sulfur reagent thiourea, (NH2)2C=S, or with thiocyanate salts; reaction of organomagnesium (RMgX) or organolithium (RLiX) compounds with elemental sulfur; or addition of hydrogen sulfide or thioacetic acid (CH3C(O)SH) to alkenes (olefins). 1,2-Dithiols can be prepared by addition of thiocyanogen, (SCN)2, to olefins, followed by reduction. Aromatic thiols are frequently made from the reduction of arenesulfonyl chlorides (see below Other sulfinyl and sulfonyl compounds).
Similar to alcohols, thiols react with alkalies and other bases to form salts. In the presence of heavy metal salts (such as those of mercury, lead, silver, or copper), thiols form mercaptides (metal thiolates), which are insoluble in water but are frequently soluble in organic solvents. The formation of a black precipitate of lead mercaptide (or lead sulfide, PbS) upon the addition of lead salts to liquid petroleum products is the basis for the so-called doctor test for the detection of thiols.
Thiols form sulfides and thioesters in reactions analogous to those of alcohols. They react readily with aldehydes and ketones to form thioacetals and thioketals, respectively. Thioacetals and thioketals are more stable than the corresponding oxygen compounds and so are especially useful as protecting groups (temporarily suppressing the reactivity of the carbonyl group) as well as reagents in organic synthesis. Thiols are efficient radical scavengers (a radical X∙ abstracts a thiol hydrogen atom, giving a thiyl radical RS∙ and XH). The ability of thiols to serve as hydrogen atom donors makes them useful as radioprotective agents, especially since radiation can produce radicals; they are also useful as hydrogen atom donors in various other processes and synthetic reactions. Thiols add across to the multiple bond of unsaturated compounds, either under catalysis by light or acid or, in the case of unsaturated compounds activated by adjacent carbonyl groups, under catalysis by base. In all cases the products are sulfides.
Oxidation of thiols initially affords disulfides, which can also be formed by the combination of thiyl radicals. Sulfenic acids, R―SO―H, can be isolated as the first-formed oxidation product from sterically hindered thiols; these react further with thiols to form disulfides. There are a number of practical applications associated with the oxidation of thiols. Spills of obnoxious-smelling low-molecular-weight thiols are neutralized by oxidizing the thiols with sodium or calcium hypochlorite (bleach) solutions. Milder oxidants (e.g., 3 percent hydrogen peroxide, made alkaline with sodium bicarbonate, or 2 percent aqueous potassium iodate) have been used to deodorize pets that have encountered skunks. In petroleum refining, the process of "sweetening" involves oxidation of evil-smelling thiols in crude oil to more innocuous disulfides. Reaction of thiols (or disulfides) with chlorine yields sulfenyl chlorides (RSCl), which are useful reagents in synthesis reactions.
Sulfides, in which two organic groups are bonded to a sulfur atom (as in RSR′) are the sulfur analogs of ethers (ROR′). The organic groups, R and R′, may be both alkyl, both aryl, or one of each. If sulfur is simultaneously connected to different positions of the same carbon chain, a cyclic sulfide (a heterocycle) results. If no other functional group is present in the molecule, sulfides are named as such; e.g., ethyl methyl sulfide is CH3SC2H5. In molecules with other functional groups of higher priority, the sulfide group is designated by thio- (as in thiodiacetic acid, HO2CCH2SCH2CO2H) or by methylthio- (as in methylthioacetic acid, CH3SCH2CO2H). In saturated cyclic sulfides, the prefix thi- precedes the root associated with ring size; for example, thiirane, thietane, thiolane, and thiane for three-, four-, five-, and six-membered rings, respectively. Unsaturated cyclic sulfides, such as thiophene, which is very stable, are well known. Sulfides have low water solubility and are soluble in organic solvents. Similar to the thiols, lower-molecular-weight sulfides have strong, generally unpleasant odours. For example, allyl methyl sulfide is a major contributor to human "garlic breath."
A variety of biologically important sulfides occur in nature. Acyclic examples include the essential amino acid methionine, which is involved in biological methyl transfer, and 2-phenylethyl methyl sulfide, C6H5CH2CH2SCH3, 5-methylthio-2,3-pentanedione, CH3C(O)C(O)CH2CH2SCH3, and di(3-methylbutyl)sulfide, ((CH3)2CHCH2CH2)2S, which are trail-marking secretions from the red fox, the striped hyena, and the polecat, respectively. Heterocyclic structures include, among others, the four-membered ring 2,2-dimethylthietane, from the mink; the five-membered rings from penicillin, biotin (involved in the biosynthesis of fatty acids and in carbon dioxide fixation), and thiamin (a coenzyme, as is biotin) and the terthienyl pesticide from marigold; and the six-membered ring 5-thio-d-mannose, a novel sugar having a sulfur atom in the ring instead of oxygen, isolated from an orange marine sponge, Clathria pyramida. In nature, sulfides can serve as ligands, as in cytochrome C, in which the sulfur of methionine is coordinated to the heme iron.
Most crude oils contain organosulfur compounds such as thiols, sulfides, and polysulfides, presumably formed from the reaction of hydrocarbons with elemental sulfur, in turn generated from microbial action on sulfate in rocks. As the oil ages, the thiols and sulfides are slowly converted into more stable compounds such as benzothiophene. Molybdenum-containing hydrodesulfurization catalysts are used in the removal of the undesirable sulfur compounds from petroleum, giving hydrocarbons and hydrogen sulfide as the final products. There is considerable interest in the use of monomeric and polymeric compounds made from heterocyclic sulfur compounds—such as thiophene, tetrathiafulvalene (TTF), and the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) cation—as organic metals and superconductors (e.g., for use as switching elements and light-emitting diodes). Indeed, the 2000 Nobel Prize for Chemistry, awarded to American chemists Alan J. Heeger and Alan G. MacDiarmid and Japanese chemist Shirakawa Hideki, recognized the discovery of plastics that conduct electricity. Poly(phenylene sulfide) (PPS), a polymeric material derived from diphenyl sulfide, which has been known for more than 100 years, is used in electrical, electronic, and mechanical applications. Polythiophene conductors are of great interest for use in molecular electronic devices. Research has led to the preparation of macrocyclic α-conjugated oligothiophenes; for example, α-cyclo[12]thiophene, which has a perfect hexagonal "honeycomb" solid state structure.
Many fungicides and herbicides incorporate organically bound sulfide sulfur.
A number of examples of syntheses of sulfides were described above as reactions of thiols. A unique synthesis of sulfides is illustrated by the reaction of ethylene with sulfur dichloride to form bis(β-chloroethyl) sulfide, known as sulfur mustard, or mustard gas, a blister-forming (vesicant) chemical warfare agent. This reaction has been applied to the synthesis of cyclic and bicyclic dichlorosulfides as well.
Like thiols, sulfides can form metal complexes, particularly in the case of cyclic polysulfides with crown etherlike structures, such as the hexathia-18-crown-6. Oxidation of sulfides yields sulfoxides or, under more vigorous conditions, sulfones; reaction with alkyl halides gives sulfonium salts; and reaction with halogen compounds produces halosulfonium salts. Halosulfonium ions and related species formed from sulfoxides are key intermediates in the synthesis of polysaccharides from 1-phenylthioglycosides, facilitating replacement of the phenylthio, PhS (or phenylsulfinyl, PhS(O)), group by a nucleophile from a second saccharide molecule, joining the saccharides in a process termed glycosylation. One-electron oxidation of sulfides gives radical cations, of importance in conducting materials; these radical cations can dimerize to give dithia dications, R2S+―S+R2, which can also be formed in reactions involving bis-sulfides, molecules with two spatially separated sulfide groups. With fluorinated reagents, diphenyl sulfide, (C6H5)2S, can be converted into the hexavalent sulfur compound tetrafluorodiphenylsulfur, (C6H5)2SF4. If one of the carbon groups, R, in a sulfide RSR′ is olefinic, aromatic, or acetylenic and the other group, R′, is a saturated carbon (e.g., methyl or ethyl), the bond to the saturated carbon can be cleaved with sodium or lithium metal in liquid ammonia—for example, RSR′ + Na/NΗ3→ RSNa + R′―H. Using Raney nickel (Ra-Ni; a type of active nickel), carbon-sulfur bonds in sulfides can be replaced by hydrogen—for example, RSR′ + Ra-Ni → R―H + R′―H. These reduction reactions are useful in synthesis or in determining the structure of an unknown organosulfur compound. Raney nickel desulfurization was a key step in first establishing the structure of penicillin. The high polarizability of sulfur stabilizes a negative charge on the carbon adjacent to divalent sulfur, as in RSCH2−(usually as α-lithium sulfides, RSCH2Li), which proves useful in organic synthesis through nucleophilic reaction with alkylating agents and carbonyl compounds.
Of particular value in this type of reaction is the 2-lithio derivative of the cyclic bis-sulfide 1,3-dithiane, widely used in the synthesis of ketones and aldehydes (the Corey-Seebach reaction, shown below). 1,3-Dithiane and other thioacetals can also be converted to olefins by the Takeda olefination reaction.
The cyclic sulfide thiophene undergoes reactions similar to those of benzene, although somewhat more easily.
Disulfides and polysulfides and their oxidized products
A unique property of sulfur is the ability to form chains of sulfur atoms with organic groups at either end—e.g., RSnR′, where n can range from 2 to 20 or more. They are named by designating, in alphabetical order, the groups attached to sulfur, followed by the word sulfide, which is preceded by the prefix appropriate to the number of sulfur atoms, as in disulfide, trisulfide, tetrasulfide, and so forth or by use of dithio-, as in dithiodiacetic acid. Polysulfides are also named polysulfanes, with individual compounds being named trisulfane, tetrasulfane, and so on. A variety of disulfides occur in nature. The amino acid cystine, a disulfide, is an important component of many proteins; the sulfur-sulfur bond plays a key role in maintaining the molecules in shapes (so-called tertiary structures) essential for their biological activity. Interconversion of cysteine sulfhydryl (―SH) and cystine disulfide groups plays an important role in transport across cell membranes, in the immune process, and in blood clotting. The process of hair waving involves cleavage of the cystine disulfide link of keratine into the cysteine moiety, providing flexibility for the hair to assume the new wave or curl desired, followed by oxidative treatment to fix the hair in its new shape.
The coenzyme lipoic acid, a cyclic disulfide, is a growth factor—ubiquitously distributed in plants, animals, and microorganisms—and is used in photosynthesis and lipid and carbohydrate metabolism in plants and animals. It is involved in biological oxidations, where it oscillates between the oxidized cyclic form and the reduced acyclic dithiol form. Lipoic acid suffers from ring strain caused by repulsion of lone-pair electrons on adjacent sulfurs in the near planar ring, making it a better oxidizing agent than a six-membered cyclic disulfide, such as 1,2-dithiane, would be. At the same time, in the reduced dithiol form, the thiol groups are in sufficient proximity to facilitate reoxidation. Asparagusic acid (4-carboxy-1,2-dithiolane), found in asparagus roots, is considered to be a major factor in the natural resistance (i.e., survival in the soil) of this plant; 4-methylthio-1,2-dithiolane is a photosynthesis inhibitor from the stonewort. The characteristic flavour of the shiitake mushroom is due to the presence of the acyclic disulfide-sulfone CH3SO2CH2SCH2SCH2SSCH3 together with several cyclic polysulfides, including lenthionine; thiarubrine is a novel biologically active acetylenic cyclic disulfide found in plants related to marigolds. Dimethyl trisulfide (CH3SSSCH3), detectable at levels as low as 0.1 part per billion, is a key contributor to the flavour of beer, wine, whiskey, and various food products. It is also one of a number of organosulfur compounds present in coal.
When garlic cloves are distilled with water, garlic oil is isolated and is found to contain a mixture of compounds including diallyl disulfide, trisulfide, and polysulfides—e.g., (CH2=CHCH2)2Sn, where n = 2–8. None of these compounds occur naturally in garlic; rather, they are formed from the action of water and heat on allicin, a biologically active thiosulfinate, or disulfide S-oxide, CH2=CHCH2S(=O)SCH2CH=CH2, in turn formed enzymatically from sulfoxide precursors in the intact garlic bulb (see below Sulfoxides and sulfones: Reactions). Sulfurized olefins are used in extreme pressure lubrication, while a highly resistant sulfur cement and concrete can be prepared from cyclopentadiene Diels-Alder oligomers linked by polysulfide chains. Polysulfides with four or more sulfur atoms have a variety of useful properties and have been employed as industrial lubricants, sealants in the glass-insulation industry, and binders in solid propellants for rockets (e.g., Thiokol A, (CH2CH2S4)n). In the vulcanization of rubber, polyolefins are converted to an elastomeric substance with desirable mechanical properties by cross-linking the chains with two or more sulfur atoms.
Disulfides are generally prepared by oxidation of thiols, whereas polysulfides can be made by reaction of an excess of thiols with sulfur chlorides, SnCl2. Some cyclic disulfides and polysulfides can be prepared by reaction of elemental sulfur with unsaturated compounds; for example, the reaction of acetylene with sulfur yields a 1,2-dithiete, a four-membered ring compound with two sulfur atoms that exhibits aromatic stability similar to thiophenes. 1,2-Dithiins, six-membered ring disulfides found in thiarubrines, can be prepared by reaction of titanacyclopentadienes (formed in one step from acetylenes) with sulfur monochloride (S2Cl2) or thiocyanogen (SCN)2 and samarium iodide (SmI2).
Disulfides can be reduced to thiols both in the laboratory as well as in vivo (biologically). Biological reduction of thiols and the reverse process, oxidation of thiols to disulfides, are essential biochemical processes. Disulfides can be further oxidized to the S-oxides (thiosulfinates, RS(O)SR), the S,S-dioxides (thiosulfonates, RSO2SR), S,S′-disulfoxides (or α-disulfoxides, RS(O)S(O)R), and, ultimately, with cleavage of the sulfur-sulfur bond, to sulfonic acids, RSO3H. Polysulfides also undergo certain reactions of this kind. A number of the disulfide S-oxides are flavourants, formed on cutting plants of the Allium genus (onion and garlic) as well as cabbage, cauliflower, brussels sprouts, and so forth. With chlorine, disulfides give chlorinated cleavage products such as sulfenyl chlorides, RSCl, or, in the presence of water, RSO2Cl. The S―S bond can also be cleaved with alkyllithiums and other organometallic compounds to form sulfides.
Calichimicin (esperamicin) is a highly potent antitumour agent produced by bacteria of the Actinomycetales order and containing a pendant methyl trisulfide component (CH3SSS―). Acting much like a molecular "mouse trap," cleavage of the sulfur-sulfur bond is thought to trigger a chain of events culminating in formation of a phenylene diradical, which removes hydrogen atoms from deoxyribonucleic acid (DNA). The initial sulfur-sulfur bond cleavage is favoured because this bond is significantly weaker in trisulfides than it is in disulfides.
Thiocarbonyl compounds
The thiocarbonyl functional group (―C(=S)―), analogous to the carbonyl group, is found in thioaldehydes and thioketones, as well as in a variety of compounds with nitrogen or oxygen (or both) attached to the thiocarbonyl carbon (e.g., ―XC(=S)Y―, where X and Y = N or O). These compounds are named by analogy with the corresponding oxygen compounds—e.g., thioacetone, CH3C(=S)CH3, or 2-propanethione. Many thiocarbonyl compounds tend to be deeply coloured and highly reactive, owing to the fact that the double bond (π bond) between carbon and sulfur uses orbitals of quite different sizes (2p on carbon and 3p on sulfur), which do not overlap well. The parent thiocarbonyl compound, thioformaldehyde (CH2=S), is extremely reactive and cannot be isolated. However, it is very stable in the gas phase in low concentrations and is formed when various small organosulfur compounds are heated to extremely high temperatures. Thioformaldehyde has been detected in interstellar space by radio astronomers. Carbon disulfide, S=C=S, is a common and important organic solvent and raw material containing a thiocarbonyl group; it is used in the manufacture of rayon. Isothiocyanates, R―N=C=S, have cumulated bonding similar to that in carbon disulfide. Allyl isothiocyanate, CH2=CHCH2N=C=S, gives horseradish its distinctive flavour; related compounds are found in mustard and radish. The dithiocarbamate thiuram, R2NC(S)SSC(S)NR2 (R = CH3), is used as an antioxidant and accelerator in rubber vulcanization and is also employed as an insect repellent and fungicide. The related compound disulfiram (Antabuse; R = CH2CH3) is used in treating alcoholism. A thioamide, ethionamide, is an important drug used in the treatment of tuberculosis, and other thioamides are used as peptide analogs and in peptide synthesis.
Thioketones are usually prepared through reaction of ketones with phosphorus sulfur reagents, such as Lawesson reagent, Ar2P2S4. Xanthates (from the Greek xanthos, meaning "yellow," named for the colour of their copper salts), thiocarbonyl derivatives of carbonates, ROC(=S)OR, are prepared from alcohols and carbon disulfide. This reaction is used to produce a soluble form of cellulose that can be extruded into an acidic solution, which disrupts the xanthate group, regenerating the cellulose in the form of fibres (rayon) or films (cellophane). Thiourea, the diamide of thiocarbonic acid, is manufactured by heating ammonium thiocyanate, NH4SCN + heat → H2NC(=S)NH2. Thiourea can be used in syntheses of thiols that avoid formation of sulfide by-products. Divalent sulfur-containing derivatives of phosphoric acid, H3PO4, with P=S bonds have been used in pesticides (e.g., malathion and parathion), lubricant additives, and ore-flotation agents. They are generally synthesized from tetraphosphorus decasulfide (P4S10) or thiophosphoryl chloride (PSCl3).
Thioketones can be oxidized to give the corresponding thioketone S-oxides, also known as sulfines, such as thioacetone S-oxide, CH3C(=S=O)CH3. Thioformaldehyde readily trimerizes to 1,3,5-trithiane or polymerizes to poly(thioformaldehyde). The presence of a π bond in thioketones makes these compounds reactive in Diels-Alder reactions and related cycloaddition reactions. Similar to carbonyl compounds, thioketones can also undergo enolization (thioenolization), giving isomeric enethiols, which in some cases can be isolated. Thioenolization of thioacetone would give 2-propenethiol, CH3C(SH)=CH2. Thioketones reversibly add hydrogen sulfide to yield gem-dithiols (i.e., having both ―SH groups on the same carbon)—for example, propane-2,2-dithiol, CH3C(SH)2CH3, in the case of thioacetone. It is probably the gem-dithiols rather than the thioketones themselves that are responsible for the extremely offensive smell associated with low-molecular-weight thioketones. Thionocarbonates of type ROC(S)OR′, derived from an alcohol ROH, are widely used in organic synthesis in a procedure that ultimately affords the deoxygenated product R―H (Barton-McCombie deoxygenation).


text:
Transform your photos into one-of-a-kind, hand painted masterpieces!
by Jouko Lehto
Image Size
The image is near the edges of the product but doesn't cover the entire product. Some of the background color may appear around the outside edges of the image.
Background Color
Our luxuriously soft beach towels are made from brushed microfiber with a 100% cotton back for extra absorption. The top of the towel has the image printed on it, and the back is white cotton. Our beach towels are available in two different sizes: beach towel (32" x 64") and beach sheet (37" x 74").
Don't let the fancy name confuse you... a beach sheet is just a large beach towel.
Care Instructions
Machine wash cold and tumble dry with low heat.
Ships Within
1 - 2 business days
There are no comments for Moonshine 02. Click here to post the first comment.
Average Rating (4.68 Stars):
Mandy Roberts
June 6th, 2019
Kuutamolla - Moonshine 02
I am a photographer and teacher, and live in Nokia, a town just outside Tampere, Finland. I have been a more or less professional photographer about all my adult age - I got my first slr-camera at age 15, got a job at photoshop as assistant and photographer at age 18... have done journalistic jobs, weddings, funerals and portraits since then. Born in 1961, there has been a lot of time to do different things... For myself, nature is the main source of inspiration. Traditional nature photography was for a long time my main hobby, but now I am leaning towards less natural and more abstract and sometimes surrealistic expression. On this site you'll find more of these works, among others. From this site you can buy prints of my...
Our return policy is very simple:
If you're not happy with a purchase that you made on Pixels.com, for any reason, you can return it to us within 30 days of the order date. As soon as it arrives, we'll issue a full refund for the entire purchase price. Please note - Pixels does not reimburse the outgoing or return shipping charges unless the return is due to a defect in quality.
Pixels sells thousands of pieces of artwork each month - all with a 100% money-back guarantee. We take great pride in the fact that hundreds of thousands of artists have chosen Pixels to fulfill their orders, and we look forward to helping you select your next piece!
All beach towels ship from our production facility within 1 - 2 business days of your order.


text:
It was recently suggested to me to seek comparable, alternative, journals to the above two (I am not interested in discussing why one would want to do so here). I am wondering if anyone has suggestions of comparable journals to these two, which I rate as middle-of-the-road specialized journals in algebra.
Optimal answers will be names of journals whose likelihood of accepting any given paper, and esteem amongst people in the field, correlates highly with these two; so, they will consequently be specialized in algebra, and of approximately equal caliber. Also, it would be good if the rigor of the referee process is comparable.


text:
By John McMullen
NFL commissioner Roger Goodell has already decided what he would like his legacy to be.
While Pete Rozelle and Paul Tagliabue will be forever revered as economic
geniuses, there was a dark side to their respective watches -- the NFL turned
into a clearinghouse for felons and miscreants.
Goodell wanted to clean that up and has been far more aggressive in terms of
disciplining players, something which has made him fairly unpopular with some
because of it.
The "gotcha" type of nature of the NFL's public relations-fueled performance-
enhancing drugs policy and who it really serves can always be dissected, but
sidelining players for crimes or drug offenses should never be questioned,
even by the NFLPA.
That said, most fans don't really care if their favorite stars are failures as
human beings as long as they can deliver the Vince Lombardi Trophy to the
hometown team. That doesn't mean the leader of the NFL can't or shouldn't grab
for the moral high ground whenever possible, though.
My problem is a selective enforcement of morality and why Goodell doesn't take
a look at some of the decision-makers in his league who embarrass the NFL far
more than an abuser of Adderall ever could.
Maybe Goodell's next ethical outage should be aimed at people like Miami
Dolphins general manager Jeff Ireland, who once asked Cowboys star Dez Bryant
if his mother was a prostitute.
Or maybe Goodell should try to find out who wanted to know if Colorado tight
end Nick Kasa "liked girls" at the scouting combine earlier this week.
After all, U.S. Equal Employment Opportunity Commission has decreed "sex-
stereotyping" as a form of discrimination illegal under Title VII of the
Civil Rights Act of 1964
Notre Dame star Manti Te'o was the lead story during much of the combine and
the microscope he was placed under was largely a self-inflicted nuisance.
Te'o, of course, claims he was led to believe a "girlfriend" he had met
online, Lennay Kekua, was a real person who died from leukemia. In reality, a
man named Ronaiah Tuiasosopo created Kekua out of thin air.
Tuiasosopo later claimed he concocted the whole "catfishing" scam because he
was in love with Te'o. Subsequent Te'o lies to his own father, his teammates
and coaches, coupled with a failure to come clean immediately are troubling
but tame in comparison to what other NFL prospects have done in the past.
Yet when Te'o ran a predictably slow time of 4.82 seconds in the 40-yard dash
at the combine, you might have thought the sky was falling on the runner-up for
the Heisman Trophy.
In reality, Te'o was supposed to run in the 4.75 range, so chalking up a pair
of runs just over 4.8 were hardly a surprise to anyone, perhaps a slight
disappointment but nothing which couldn't have been cured at Notre Dame's
upcoming pro day.
Speed is certainly an important part of success in the NFL, but it's hardly
some kind of definitive stamp on future success.
Perhaps the best pure football player since Jim Brown, Hall of Fame wide
receiver Jerry Rice, ran a 4.72 at the NFL Combine. Cris Carter was probably a
tick slower than that and he'll be joining Rice in Canton this summer.
A natural instinct in this game turns a 4.72 to a 4.4 rather quickly, just as
a false step renders a 4.4 virtually meaningless.
Te'o's performance, however, was a chance for his detractors to pile on.
Katie Couric of all people exposed what many in the NFL are actually thinking
about Te'o during a high-profile interview with him on her syndicated talk
show last month, and it has nothing to do with speed or lack thereof.
Couric, the former host of "Today" and current ABC News contributor, asked the
6-foot-1, 241-pound Te'o if he was gay.
In a pie-in-the-sky world, that kind of thing shouldn't matter. In the
testosterone-fueled world of the NFL, however, sexuality might be the
final frontier.
After ex-San Francisco 49ers tackle Kwame Harris was arrested for a domestic
incident in late January -- one that revealed he was gay -- comedian Artie
Lange asked current 49ers cornerback Chris Culliver what he would think about
having a gay teammate.
"I don't do the gay guys man," Culliver said. "I don't do that. No, we don't
got no gay people on the team, they gotta get up out of here if they do. Can't
be with that sweet stuff. Nah -- can't be -- in the locker room, man."
Culliver then went on to suggest homosexual athletes should keep their
sexuality private until 10 years after they retire.
Harsh but indicative of the intolerance pervading the NFL culture.
Culliver was vilified, of course, and spent the rest of his Super Bowl week
backpedaling, something that satiated the politically correct crowd but
added little to the discourse and the fact that so many share his views.
No active NFL player has ever come out of the closet yet various studies on
sexuality have pegged up to 10 percent of the population as gay. That number
seems high to many, so let's say it's 5 percent. That would mean 85 current
NFL players are homosexuals.
Statistics aside -- understand there are gay men playing in the NFL right now
and the actual number is -- or at least should be -- inconsequential. The fact
that people go to ridiculous lengths in an effort to conceal who they really
are, is.
The real question surrounding Manti Te'o is a simple one -- can he play?
In fact, that should be the only question.
Unfortunately to some of the more shallow and superficial power-brokers in the
NFL, it's a query which will remain awash in a sea of stereotypes, never to be


text:
Kosher Corporate Holiday Gifts
Kosher Corporate Gifts for Jewish Colleagues
It's tricky enough to find the ideal corporate gift. When it's a company holiday gift for a Jewish colleague, it can be even more complicated! Not all Jews keep kosher, but when you're sending a holiday gift you want to be extra careful to make the best impression. Sending kosher corporate holiday gifts from the Challah Connection will give you total peace of mind, and we'll make the selection process super easy. We even help you with the most appropriate gift card language!
Our kosher certified company gifts will make you look like a gifting superstar! Whether your colleagues keep kosher or not, they'll appreciate that our corporate holiday gifts are very high quality and kosher certified. Here are some kosher corporate gifts to consider sending your Jewish colleagues.
This Corporate Holiday Gift is a Best Seller
This is a kosher holiday gift that's been one of our top sellers for close to 8 years. Fresh and delicious baked goods that are great for Hanukkah and Christmas – a fresh challah (think:french toast), our signature babka and favorite rugelach, and gourmet dried fruits. These baked goodies are always shipped in peak freshness, so they can't be in transit more than 3 days. Send it soon! BUY! $94.99
When you need a corporate holiday gift that makes a whole office happy, this is the one to choose! It's for up to 12 people, and includes a mix of delectable sweets and special savories. Granny Smith Apple Coffee Cake, rugelach, and California dried fruits are complemented by savory treats including gourmet Brazilian cashews, Meditalia Basil Tapenade and Smoked Salmon Pate. And they'll love the non-denominational white tin and wicker basket adorned with snowflakes. BUY! $199.99