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- Press Release
Carnival Cruise Lines has named National Arbitration and Mediation, Inc. (NAM), one of the nation's leading dispute resolution providers, as its new arbitration administrator. Essentially, when passengers book a cruise, they agree to the terms of a Ticket Contract, which sets forth that that claims associated with the contract or cruise shall be resolved by arbitration.
Roy Israel, President & CEO stated, "NAM is pleased to be overseeing the administration of Carnival Cruise Line matters and we are looking forward to offering its passengers a fair, accessible and effective alternative to litigation. We expect that when disputes do occur, all parties will find this to be a fair, expedient and cost effective forum to resolve claims."
Complete details about NAM's arbitration procedures for Carnival Cruise Lines (including a downloadable copy of NAM's Comprehensive Rules and Procedures) are available on NAM's website at: www.namadr.com. Additionally, the Ticket Contract containing the applicable arbitration provision can be accessed via Carnival Cruise Lines' website here.
Headquartered in Garden City, New York, National Arbitration and Mediation, Inc. (NAM) is one of the nation's leading dispute resolution institutions, offering cost-effective alternatives to expensive and often time-consuming litigation. Founded in 1992, NAM has a nationwide panel of nearly 2,500 top-tier former judges and practicing specialists uniquely qualified to resolve legal matters in a private forum.
Read more NAM news


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Sept. 30 charity golf tourney to help battle leukemia tees
The sixth annual Tee It Up To Cure Leukemia charity golf tournament is set for Friday, Sept. 30, at Legacy Golf Course, 6808 S. 32nd St., Phoenix. Registration begins at 11:30 a.m. The tournament is special to organizer Jana Brickey, Associate/Business Development Director at Dick & Fritsche Design Group. She lost a grandfather to leukemia… Read More →
Sundt Construction completes Coyote Center in Chandler
Sundt Construction, Inc. (www.sundt.com) recently completed the $28.6 million Coyote Center at Chandler-Gilbert Community College, Pecos Campus in Chandler, Arizona. In celebration of the multi-purpose facility's grand opening, city officials came together for a ribbon-cutting ceremony on Sept. 24 to announce the achievement. Serving as a gathering place for the community and a gateway to… Read More →
Public: The Salvation Army Phoenix Kroc Center
THE SALVATION ARMY PHOENIX KROC CENTER Developer: The Salvation Army Contractor: Sigma Contracting, project manager; Haydon Building Corp., contractor Architect: Barber Rinker Seacat (Denver) in conjunction with Dick Fritsche Design Group (Phoenix) Size: 140,000 SF Location: SWC 14th St. and Broadway Rd., Phoenix The $44M community center includes a library, full-service fitness center, 350-seat chapel/performing arts center, wellness center and… Read More →


text: This is a friendly, small hotel with 18 pleasant rooms. Its walls are decked with maps of the area, it has a room for bicycles, and the staff are full of information on the town and nearby natural parks. The hotel is air-conditioned and features a lobby with 24-hour reception, a hotel safe and lift access to the rooms. For an additional fee, guests may also make use of Internet access, the car park and bicycle hire service.Rooms include en suite bathrooms with shower/bath and hairdryer, a direct dial telephone, TV, Internet access, individually regulated air conditioning and central heating. A balcony or terrace also features as standard.


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"Is It Wrong?" Vidcast
"Who The Hell Is Jesus?" Part 1
Here is the link to the Iranian women train as ninja assassins…no this is not a joke! Click here! [Read more…]
Missional X Vidcast
Pedestals & Pulpits Vidcast
Idol Change Vidcast
You can listen to the podcast featuring Steve Knight that I mention in this vidcast by clicking here. [Read more…]
The River Gathering April 23-25, 2012
April 23-25, 2012 my good friend Steve Knight and I are leading The River Gathering, a missional retreat focused on the evolution of church in our emerging context. Steve and I will explore missional church concepts and share the wisdom of our individual stories all the while immersed in the beauty of creation we find [Read More…]
OP 11 Keynote
As requested here is my keynote from the Outlaw Preachers Reunion. Hope you enjoy! [Read more…]
The 21 LGBTQ Challenge Podcast
Julie Kennedy, to friends and most of web Jules, is a recent graduate of Southeast Missouri State University with a Bachelor's in General Studies, but will soon be pursuing a Master's in Social Work. She currently works in Special Education. She is a spiritual wonderer and has been a part of the "emergent" conversation for [Read More…]
Whiskey Chat On The Creation Of The Eucatastrophe
Whiskey Chat On The Creation of The Eucastrophe from Phil Shepherd on Vimeo. [Read more…]


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Free Download MOD APK Android Axe in Face 2 | Only best games at Sbenny.com
Game Description:
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Game Requirements and Details:
Android version required: 4.1 and higher versions of Android Smartphones and Tablets
Required storage space: 40 MB or more
Internet connection NOT required to play
APK ID: com.hugogames.axeinface2.universal
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Ads? NO
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Product Catalog (pdf)
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An incredibly diverse and talented group of people has challenged themselves with designing, engineering, manufacturing, marketing and selling the very best in fluid connection solutions: They are CPC. Our employees contribute in a wide variety of engineering, marketing, manufacturing, finance, sales, customer service and administrative positions. Our corporate office in St. Paul, Minn.,supports a geographically dispersed sales force with offices in Germany, the United Kingdom, Italy, India, the Netherlands, France, Hong Kong, Japan, China, Canada and locations throughout the United States.
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indoor activities
i need new ideas....... we spend alot of time outside but, there is some days were its just to hot, but I am running out of ideas for my kids to do and it seems as if they are bored and don't want them to end up destroying the house because of boredom!
We've been coloring a lot lately. I cut out some shapes from cardboard, labeled them, and we spent time "decorating them". I also keep giving Maddie new but unexpected things--empty boxes, cardboard tubes--with the hopes that they'll keep her from getting bored by being creative.
Building a fort is a favorite here. We also stack blocks and then use nerf balls to knock them down, sorta like bowling. Blow bubbles in the kitchen. Let them take a long bubble bath with lots of bath toys.
i love the idea of using the Nerf balls to knock down the blocks.... fun...
Ours have been playing with paper dolls and listening to music in the basement where it is cooler.
i used to do bath time alot but in the place we are living in at the time doesnt have a tu..... i love the balloon ping pong and box ideas....
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a young mother of three children. My oldest son is four, my daughter is two and my youngest son is four months.
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text: GMYLE's Back Case is designed to give your Galaxy S7 Edge SM-G9350 all-round protection from bumps and scratches. It is easy to install by just snap on to your device. Back Case is the perfect combination of style. Compatible with Galaxy S7 Edge SM-G9350. Note: The device is not included in the package


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|Products » Manufacturer » Cisco
Cisco Gigabit Ethernet 1000 Base-T Mini-GBIC SFP Transceiver
1000BASE-T SFP transceiver for category 5 copper wire, support up to 100 m. Cisco MFE and MGE Small Form-Factor Pluggable (SFP) or mini Gigabit Interface Converter (mini-GBIC) transceivers (Table 1) are easy-to-install modules that provide a simple way to add fiber connectivity or to add an extra Gigabit Ethernet port to your Cisco Small Business or Cisco Small Business Pro Series switches. The transceivers are available for single-mode or multimode fiber-optic cabling and can support distances from 100 meters up to 40 kilometers. The Cisco MFE and MGE transceivers provide fast and reliable connectivity between switches that are located on different floors, in separate buildings, or on a small campus network needing connectivity between sites. These transceivers can support both Fast and Gigabit Ethernet applications.
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NETXUSA 231 Beverly Road Greenville, SC 29609 T 864.271.9868 F 864.233.4344 Toll Free Sales & Support 1.800.BUY.NETX (289.6389)


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Kauai Ocean Tours & Ocean Guide
- Top 10 Activities
- Fun Things to Do
- Activities for Kids
- Whale Tours
- Zipline Tours
- Adventure Tours
- Ocean Activities
- Snorkeling
- Nature Tours
- Romance
- Hawaiian Luaus
- One Day Tours
- Sightseeing Tours
- Dinner Cruises
- Helicopter Tours
- Discount Tours
- Special Discounts:
- - Military
- - Kama`aina
Kauai Ocean Tours & Ocean Guide557
Join Captain Andy's for 5½ hours of Na Pali Coast, snorkel Sail a delicious lunch. Enjoy jumping and froliking Humpback whales along Poipu and Na Pali Coast. Expect rough ocean with high surf advisory! ... More »
A private charter snorkel sail onboard Southern Star is not for everyone, so weve decided to offer this 6 hour exploration of the Na Pali. Enjoy all of the luxury and features of Southern Star as we explore one ... More »
#3 Ocean Rafting NaPali Coast
Not yet reviewed
Ocean Rafting in Hawaii along Na Pali Coast. Enjoy an adventurous, narrated, thrill-seeking ocean rafting expedition while exploring secluded beaches, mysterious sea caves and waterfalls along Kauai's majestic Na ... More »
#4 Whale Watch Tour by Kayak
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Ocean kayak tour adventure. 8-mile of kayaking along South Shore from Poipu to Port Allen. Excpect to see wild dolphins, Honu sea turtles and Humpback whales. ... More »
#5 Kayaking at Hanalei Bay Reef Lagoon
Not yet reviewed
Hanalei Kayak Snorkel provides a guided kayaking and snorkeling excursion at Hanalei Bay Reef Lagoon and Hanalei River! With this family activity you can enjoy Hawaii birds, flowers, reef fish, turtles and white-sand ... More »
#6 Ocean Kayaking NaPali
Not yet reviewed
Ocean Kayaking Na Pali Coast. Up for a righteous adventure? Try this guided 16-mile ocean kayak trip along the Na Pali Coast! Expect an adrenaline pumping test of your paddling skills in typically choppy waters ... More »
This thrilling rafting excursion along the fabulous Na Pali Coast of Kauai - a 16-mile-rugged, pristine, tropical wilderness with stops to snorkel, then enjoy a delicious picnic lunch at a remote Kauai beach. Perfect ... More »
Ocean Rafting in Hawaii along Na Pali Coast by Capt. Andy's. An incredible 5½ to 6 hour expedition with a great chance to spot a Hawaiian monk seal! A small monk seal colony has been established on Kauai's North ... More »
#9 Sailing Na Pali Coast & Luau Package
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Activities discount package for sailing Na Pali coast & Smith's luau is the easy and inexpensive way to enjoy two of Kauais premier activities as one Discount Combo - Na Pali Dolphin Sail & Snorkel aboard Holoholo ... More »
Kauai Ocean Activities, Tours & Tropical Ocean Guide. Kauai ocean activities are among the most beautiful and exciting of any water activities on the planet, because of the stark beauty of the Na Pali coast on west Kauai, romantic Hanalei Bay to the North, and the serene Southshore waters at Poipu and Port Alan. Your Hawaii vacation won't be complete without a Napali snorkel, kayak, rafting or sightseeing excursion. Hanalei Bay provides surfing lessons plus Ocean Kayaking and snorkeling tours of Hanalei Lagoon and along the Hanalei River. Kai Bear Sportfishing offers a variety of both shared and exclusive private charters, or take an 8-mile sea kayak adventure along Kauai's gorgeous south shore from Poipu to Port Allen with a relaxing lunch on the beach at Wahiawa.


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Grey's Anatomy
'It Might Have Felt Like Love'
Disclaimer: Grey's Anatomy and all characters associated with it belong to Shonda Rhimes and ABC. As much as I wish they were mine, they never will be. All other characters and places are mine. If there is a real person or place that I have named in my story, it is purely coincidental.
Summary: Callica. Set after episode 5.07 'Rise Up.' Callie and Erica didn't exactly break-up, but after their little public argument they weren't exactly still together. So, what are they? And is either willing to fight for it? FemSlash. Inspired by Sara Ramirez's amazing rendition of 'It Almost Felt Like Love' in No Ordinary Thursday – The Songs of Georgia Stitt. First chapter doesn't have the song, it's in the last part of the next chapter.
Flashback in italics
Reviews welcome, but please be nice.
Erica looked at herself in the mirror, the argument she had with Callie being on non-stop re-run across her mind.
"I went to the chief about Izzie Stevens and he completely shut me down. Well, we'll see what he says when I report this to UNOS."
"Whoa. Whoa whoa whoa, wait, why?" Callie reached out and put a hand on Erica's arm, causing the blonde to stop and turn around to face her. "I mean, what good would come from that?"
"What do you mean?"
"What possible good would it do? I mean, would it benefit your patient's outcome, or-"
"My patient wouldn't be here if it wasn't for her." Erica desperately needed someone on her side about this. The Chief had shot her down, every other doctor in this damn hospital refused to talk about it and she thought at least Callie would be on her side.
"You're going to report this to UNOS and cost this hospital its transplant certification? Cost our patient's organs? Cost people their jobs? Cost Izzie Stevens her career?"
"Wait, so you're taking Izzie Stevens side in this? Over mine?" No, this was not happening. Callie had to be on her side. Erica needed someone on her side because right now because it was her against the whole hospital and she needed Callie by her side.
"She's a doctor, one of our doctors. There's a reason we have each other's backs Erica."
"Oh please do not talk to me about a code, because this is not that."
"No, this is that. Look, I don't know what happened between Denny Duquette and Izzie Stevens that night, but unless you were in the middle of that situation I don't see how you can make a judgment."
"Easy. There's right and there's wrong, and this was wrong. And illegal." Erica silently begged Callie with everything she had to back her up in this, to be a good friend – and lover, and support her in this. 'Please Callie.' She thought. 'I really need you right now, don't shoot me down. Don't make me feel like this is a mistake, that we are a mistake.' "There is no gray area here. You can't kind of think this okay. You can't kind of side with Izzie Stevens. And you can't kind of be a lesbian." It was a low blow and she knew it, but she was beyond rational thought at this point. This wasn't even about Izzie Stevens or her patient anymore. It was a fight for their relationship and Erica needed Callie to prove she was in it as much as she was.
Callie paused for a minute, taking it all in. "Yes I can."
Erica laughed. She had just lost the one person who was supposed to be standing by her. She was totally alone. "I can't believe I didn't know this."
"Erica, the chief is right-"
"No, you." Erica interrupts. "I don't know you at all." And with that she turned and walked away, pretending that the look on Callie's face didn't stick a knife straight through her heart. Pretending that hot tears weren't burning their way down her face. Pretending she didn't need this, any of it. When the truth is, without Callie . . . what was the point?
She could not for the life of her understand why Callie was siding with Izzie Stevens. Izzie Stevens, the woman who had slept with her husband and started all sorts of nasty rumors about her. She was the reason Callie had no friends at the hospital since she started there.
"Shit." She cursed, shaking her head. It didn't matter the reason, this was not something she would let their relationship end over. Izzie Stevens did not deserve that satisfaction. She looked over to her bed where a big orange cat was lounging. "I really messed up, didn't I?"
The cat just stared back.
Twenty minutes later she was standing outside the door to the apartment Callie shared with Yang. She kept knocking, but no one answered. She raised her hand to knock for the umpteenth time when the door finally opened, revealing a very disturbed Christina Yang in a robe and slippers. "This had better be good." She said to the intruder without even looking up. "I was sle – Oh, Dr. Hahn." She changed her tone drastically at the sight of her 'mentor.' "I'm on strict instructions not to let you through this door."
"I'll let you scrub in on my next five surgeries."
Christina's eyes almost bulged out of her head. But why stop at five? Hahn obviously wanted to get into the apartment, so she figured she had a little bargaining room. "Ten."
"Five." Erica reiterated.
"Three and I'll even let you do some of the procedures." She could see the wheels turning. "By yourself."
Erica knocked lightly before quietly opening the door to Callie's room. The light from the rest of the apartment illuminated Callie's sleeping form. Her face was puffy and she had tear marks down her cheeks. Erica almost turned and walked right back out of the apartment and out of Callie's life. Callie deserved better. But she entered the room and shut the door behind her just as quietly as she had opened it. She could be better. They had something. It was real and most of the time it scared the hell out of her, but it was something and it was worth fighting for.
She slowly made her way over to Callie. The darker woman was cuddled up in her blankets, but Erica could see that she was still in the clothes she had left the hospital in.
Erica sat down next to Callie, careful not to disturb the sleeping woman. After a minute or so of trying to think of what to say, she put a hand on Callie's shoulder. "Callie?"
Callie's eyes snapped open and locked onto Erica's. "Erica?" Then she remembered she was mad at the blonde doctor and that Christina had promised not to open the door for anyone, especially Erica. "Christina!" She yelled out to her roommate as she sat up in bed, fully intent on marching into her room and giving her an earful.
"I bribed her. I'm letting her in on my next three surgeries."
Callie sat down against the headboard and brought her knees up to her chest. "Three surgeries? That's all I'm worth?"
"Three surgeries in which she'll be doing most of the procedures herself."
Callie looked at Erica. It must have taken a lot for Erica to agree to that. She took in Erica's appearance and realized she pretty much looked the same way she must at the moment. But she wasn't about to give in that easily. "So now you're here. What do you want?"
"Callie I'm . . . I'm sorry."
"Oh Erica save it." She threw the covers off herself, but Erica's hand on her arm stopped her from leaving.
"No, I . . . I have no idea what I'm doing. I . . . I don't let people in, and when I do I find the first thing I can think of to push them back out." She looked around the room, willing the tears that were so close to making themselves known to stay put. "I had, possibly the worst day of my life and I just needed you to be there for me. I keep my distance from people because when I don't, I get hurt. I let myself get too attached to this patient and it nearly broke me when he lost that heart two years ago."
Callie settled back down, unconsciously sliding a little closer to Erica.
"And now I find out that I've been working with the doctor who stole the heart from him and nothing was done about it?" She shook her head incredulously. What was she doing here? Callie would never understand any of this. Callie proved that when things got tough Erica was not the one she went to. She was sure Mark Sloan would help Callie 'figure things out' in the morning.
"I wasn't even going to go to UNOS. I just wanted someone to be on my side." That wasn't even what hurt the most. What really hurt was that Erica had lost the closest friend she's had in . . . years, and the best lover she'd ever had. Callie had made her see who she truly was and there was no going back from that. "I wanted you." And with that she got back up and walked out the front door, out of Callie's life. But how long she was gone? . . That was up to Callie.


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A young U.S. Army officer who's served in Afghanistan finds himself suffering from intermittent bouts of "hysterical" temporary blindness due to impossible and deadly orders he was forced to obey by high command in the field. When he's reunited with his fiancée in a military hospital in Germany after being separated for more than year, the couple are encouraged by doctors to travel to Venice, Italy together. There, amongst the canals and the cafes, they try to rekindle their love and fight off their personal demons while trying to comprehend the enormity of the heartbreaking role they now must play in love and war.
©2012 Vincent Zandri (P)2012 StoneHouse Audio
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text: Posted April 11, 2012 darren rovell @darrenrovell Madden 13 cover vote down to 4: Cam Newton, Patrick Willis, Aaron Rodgers & Calvin Johnson. Time to give up folks, I did a LONG time ago. Cam is going to win. Time to break the curse!!! Might as well root for him now. Share this post Link to post Share on other sites


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- 1 IPPB Assistant Manager Answer key 2017
- 2 IPPB Assistant Manager Scale-1 Answer Sheet 2017
- 3 IPPB Assistant manager Scale-I Cut off 2017
- 4 IPPB Assistant manager 7th Jan answer key download
- 5 IPPB Assistant manager Answer key 2017 Details
- 6 IPPB Assistant manager Result 2017
- 7 How to download IPPB Assistant Manager Answer key 2017
IPPB Assistant Manager Answer key 2017 for 7th January 2017 examination,IPPB Assistant manager Cut off 2017 officer Scale-1 Answer keys is made available to download at official web portal,links of which are given at our post.
IPPB Assistant Manager Answer key 2017
A recruitment notification has been pitched by Indian posts Payment Bank Ltd concerning the post of Assistant manager Scale-1,the prelims IPPB Assistant manager Answer key 2017 of which the department is to upload soon for the written preliminary examination held at 7th January/8th January onwards,the official IPPB Assistant manager Answer key 2017 will be uploaded approximately after 1 or 2 week after the commencement of the preliminary written examination,since Indian posts payment bank Ltd is a big platform for Young candidates in search of a Job,here this opportunity can prove a milestone to their career,as a lot number of candidates have participated in the recruitment plan of Assistant manager Scale-1 and thus participated in the written examination scheduled to be conducted on 7th and 8th of Jan 2017,once the examination is conducted the department will offer the answer sheets Set wise on its official website for the candidate's self assessment.
|On-line Registration Process Starts from:
|04th October 2016
|Last Date to Submit On-line Application Form:
|07th November 2016
|Online Payment of Application Fee:
|04th October to 07th November 2016
|Due Date for Printing Application Form:
|22nd November 2016
|Call Letter Download Date:
|01 (one) week before examination date
|On-line Examination Dates:
|07th & 08th January 2017
|Date for Result Declaration:
|February or March 2017
IPPB Assistant Manager Scale-1 Answer Sheet 2017
Indian Posts payment bank limited shall publish the IPPB Assistant manager Scale-1 Answer Sheet 2017,for the online preliminary examination they have conducted on 7th and 8th Jan respectively,the competitive written examination aims at selecting eligible candidates for 650 Assistant manager Scale-1 posts,candidates who have enrolled for the recruitment and thus have written the concerning prelim examination can now take access over the official IPPB Assistant manager Scale-1 Answer Sheet 2017,once the exam is commenced as the department will take a little bit of time to analyze the whole answer sheets of candidates all over the country,to get to a result,till then candidates can make use of the answer keys that are made available by the authorities to download at their web portal.
IPPB Assistant manager result 2017
IPPB Assistant manager Scale-I Cut off 2017
The Indian Posts payment bank limited will release an exact IPPB Assistant manager Scale-I cut off marks along with the announcement of IPPB Assistant manager result 2017,the cut off marks is the minimum marks that a student belonging to each category have to score in order to get shortlisted for further recruitment steps,here we are providing a expected cut off list for different category candidates,the exact IPPB Assistant manager Scale-I cut off 2017 will be published in Feb month most expected on official website i.e. www.indiapost.gov.in.
|Expected Cut off
|80-85 marks
|75-80 marks
|55-60 marks
|Physically handicapped
IPPB Assistant manager 7th Jan answer key download
IPPB will conduct several examination this year for various posts like Officer Scale 1,2 and 3,the former one is a prelims examination for Officer Scale-I post, the written exam conducted for maximum 200 marks with time duration 120 minutes. The online test has covered various topics like Reasoning, English Language, General Financial Awareness and Quantitative Aptitude. Aspirants must note that 1/4th marks will get deduct for every wrong answer marked by them on the answer paper. Participants will have to pass in each of the objective tests.
IPPB Assistant manager Answer key 2017 Details
Name of Organization: India Post Payments Bank (IPPB)
Category: Answer Key 2016-17
Name of the Post: Officer Scale 1 ( Assistant manager)
Exam Type: Online Test
Examination Date: 7th January 2017 & 8th January 2017
Exam type: Multiple choice
Total questions: 100
Time Duration: 1 hour
Exam Topics: General Awareness, General Intelligence & Reasoning, and English
IPPB Exam Answer key Release Date: January 2017
Official Website: www.indiapost.gov.in
IPPB Assistant manager Result 2017
India Post Payments Bank Officer Scale Result 2017 will decide that which applicants selected for next stage of selection process. The authority will provide further details about the main exam or GD/interview through their designated portal. We will add a minute to minute IPPB result updates on this web page.The department will take some time to announce the result,once they have done with the analysis of answer sheets,the IPPB Assistant manager Result 2017 will get published in the month of January-February 2017,stay connected to the website or just follow the links provided here under.
How to download IPPB Assistant Manager Answer key 2017
- First visit the official website of IPPB.
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- Find out the relevant (Direct) link for downloading "Answer Key of IPPB Officer Scale 1 Recruitment Examination, 2016-17" and then click on it.
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Easy Sweet and Sour Sauce for Chicken or Pork
READY IN: 10mins
Recipe by threeovens
There are 104 recipes for sweet and sour sauce on the Zaar, but none like this one. Lightly battered chicken or pork chunks, green pepper, onions, thinly sliced carrots, and pineapple chunks served with the sauce over rice make a complete meal.
Ingredients Nutrition
- 1⁄3 cup rice vinegar (do not substitute for best results)
- 4 tablespoons brown sugar
- 1 tablespoon ketchup
- 1 teaspoon soy sauce
- 2 teaspoons cornstarch
- 4 teaspoons water
Directions See How It's Made
- Mix the vinegar, brown sugar, ketchup, and soy sauce together and bring to a boil in a small pot. Mix together the cornstarch and water, add to the other ingredients and stir to thicken.
- For a thicker sauce, increase the cornstarch to 5 teaspoons.


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They couldn't be satiated by simply removing millions of jobs and shipping them overseas to exploit the poor elsewhere.
By Abby Haglage The shipping company heads to court Tuesday to face $1.6 billion in charges of conspiring to traffic illegal meds.
Samaras and I palled around a bit, especially with the son of a New York lawyer who did work for Greek shipping magnates.
The shipping out of the 20 percent-grade uranium could be a catalyst for this.
According to the brand's official site, shipping takes two to three weeks.
The movement of British shipping, on the Chilian coast had to be suspended.
Look down the river and you can see these boats cruising about among the shipping.
Her husband, who was in the shipping business, is getting old.
In 1785 the port was the second in the state in the extent of its shipping.
There was only one little difficulty in the way of my shipping these men.
c.1300, "a ship," from ship (n.). Meaning "act of sending (freight) by a ship, etc." is from late 15c. As "ships generally or collectively" from 1590s.
Old English scip "ship, boat," from Proto-Germanic *skipam (cf. Old Norse, Old Saxon, Old Frisian, Gothic skip, Danish skib, Swedish skepp, Middle Dutch scip, Dutch schip, Old High German skif, German Schiff), "Germanic noun of obscure origin" [Watkins]. Others suggest perhaps originally "tree cut out or hollowed out," and derive it from PIE root *skei- "to cut, split."
Now a vessel of considerable size, adapted to navigation; the Old English word was used for small craft as well, and definitions changed over time; in 19c., distinct from a boat in having a bowsprit and three masts, each with a lower, top, and topgallant mast. French esquif, Italian schifo are Germanic loan-words.
Phrase ships that pass in the night is from Longfellow's poem "Elizabeth" in "Tales of a Wayside Inn" (1863). Figurative use of nautical runs a tight ship (i.e., one that does not leak) is attested from 1965.
c.1300, "to send or transport (merchandise, people) by ship; to board a ship; to travel by ship, sail, set sail," also figurative, from ship (n.). Old English scipian is attested only in the senses "take ship, embark; be furnished with a ship." Transferred to other means of conveyance (railroad, etc.) from 1857, originally American English. Related: Shipped; shipping.


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Don't give up work to be a SAHM unless(937 Posts)
You have a HEFTY private income or can work from home.
I gave up work, usual reasons, wages would barely cover childcare, WE wanted kids to be at home with a parent.
Fast forward. I now have two dc, the father of my dc cheated on me, physically, emotionally and financially abused me.
One of my dc has SN and cannot attend school for the moment.
I've been out of work for 10 years now, I have no profession. In 6 years time our child support will stop as will most of our benefits. I will near fifty having not worked at all for 18 years.
My future is shit. Utterly grey and bleak. All I have to look forward to is a state pension. While my ex earns a fortune, travels the world and has new relationships.
This is reality for me. So think long and hard about giving up work to stay at home because no matter how shit your job is it's preferable to my future don't you think?
And it was all decided for me by a man who decided he hated me and didn't want to be married anymore and a child being diagnosed with significant SN.
It's that simple.
You could be right Tunip and it will be very interesting to watch how things go with these couples, especially once 2nd babies arrive.
Here's hoping though, eh, Feu?!
Although as you say, we don't know what goes on behind closed doors, I have been on holiday with a lot of other families and there definitely is more equality in couples re chores than there used to be - I know far more couples who share fairly than ones where the man sits around expecting be waited on.
Wanttowrite you make excellent points. I'm very sorry to hear about your husband. No one ever thinks they will get ill until they do- I certainly didn't, and while I'm still able to work I am in pain a great deal of the time. It can happen to anyone. I know that makes me sound like the boogieman, but it's true. It's just something that always seems to happen to other people, some distant friend or something you read about in an inspirational piece in the Guardian. Then suddenly it's your life.
Anyone who reads this: it's worth having an idea of what you would do if your OH or you became ill. A plan of some sort. You don't have to write down a thirty page research proposal on it but please, give it a little thought.
Yep Tunip, among my friends many a useless boyfriend was (eventually) dumped in our 20s for being useless wastes of space who do nothing around the house. Now pretty much all the men in the couples I know do the same work round the house (along with all the mental work of organizing life) as the woman. Except one, and they got divorced last summer, luckily before they had DCs.
I have to say though, I do think we have lower standards of housework and houseproudness than our mothers. Ahem.
That's OK though isn't it, Feu ?
Perhaps women got a bit sick of being defined and judged by how tidy their house is - there is more to life !
If stuff is shared more equally perhaps we can re-discover some house proudness ?
It is absolutely, definitely okay Juggling!
Thanks IsayHolmes - dd was only 3 when we got shock diagnosis and it really isn't that rare by the time you are 40+ I know lots of people living with illnesses of what kind or another, some more limiting than others. I never thought it would be us and think we are probably still living in a bit of denial at what future holds, however today is our wedding anniversary and all in all I'm happy.
I honestly hope MNHQ would consider moving this thread somewhere where it wouldn't disappear. So much food for thought. I have never stopped working, although I wished at the time I could stay at home and look after DD. We were not entitled to any government support at the time of DD's birth and we needed my wages as we bought a house just before I fell pregnant. At the time I was working in HR, steadily making progress and fairly happy in my job.
We left the UK to return 'home' because DH wanted to, it took him quite long to convince me. We started up a business together, which never really did well. I found another job in a totally unrelated industry. With hindsight I now know I should never have returned with him. I should not have left my career. We are pretty much financially fucked, our savings are depleted due to our failing business. Our relationship is fairly crap at the moment, if it wasn't for DD we would probably not be together anymore. And also, we need each other financially, I don't think we would be able to run two households on our current wages. DH is hoping to find work in the UK, we will be returning early next year. I'm 42 and I'm not sure what my future holds. Very scared indeed.
I've just nominated this for inclusion in 'Classics' notmydog.
I'd like to ask Emma to consider requesting its move to Relationships. That's the board where I think it will have most impact.
Agree re moving thread and how much food for thought is here. I would counter the idea that women are forced to stay at home by circumstances, societal expectation with the fact that I know several women who saw motherhood as a way to evade working in a job they didn't like.
Short sighted IMHO.
However a choice they made. I'd like to think this thread makes women make a more informed choice.
When struggling to juggle work and babies I was green with envy at their ladies who lunch lifestyle. Today I am very glad that circumstances forced me to maintain my career.
DH and I had been together for 10 years when we got engaged. He was in the oil industry and I'd always assumed that I would abandon my career and follow him around to obscure parts of the world and raise our children. Shortly before our wedding, DH was diagnosed with multiple sclerosis. All globe-trotting and SAHM plans were abandoned and we both continued our careers in London.
Twenty years later DH is wheelchair bound and medically retired, although he does still has a very enviable, part-time consultancy job. We went on to have two DDs, but because we knew the score way before they arrived, it didn't even occur to me to give up work. It's been tough at times but we are financially very stable, the DDs are fine and DH is in the position to do just enough work to keep him intellectually amused without getting over-tired.
We were sooo lucky. That early, early warning meant we could build our lives around the probability that DH wouldn't be able to continue to work. Had MS struck suddenly, when we were ten years out, with two children, in the back of beyond, with zero career prospects for me, we'd have been sunk.
Really agree Issy, we also had enough warning to make plans and savings - so glad I didn't give up working when I had my ds and dd, though I had decent maternity leave and many variations of part time working until now both in high school and I am pretty much full time working.
Cabbage - I could be accused of doing just that. Unfortunately the job i didn't like had no prospects anyway so i doubt would have made very much difference.
Also to the poster who said about women being in these dead end jobs - I totally agree. My exH and i left uni together with a similar degree and both got entry level jobs on 15k per year. However, my job in a national art gallery required nothing i had studied for and was merely an admin job which relied on excel and databases of which i have no aptitude. My husband on the other hand was developed technically and within 2 years was on 36k.
My exH, my dad and DP have all said repeatedly, 'well just earn more money'. as if it was that easy. They refuse to believe that women are funneled into these admin/caring (low paid) roles and to them they are more successful than women because they must have worked harder. frustrating is an understatement. And then you get the odd female boss which is even less understanding, because SHE did it, so other women should be able to. regardless of whatever help she had. One female boss i had hated women who had kids, feeling they had let themselves down.
sorry for your troubles op,i hope you have supportive pals
I think it's folly to be financially reliant upon other adult.folly to give up work
and whist the man career goes stellar because he can work unencumbered woman has no career no back up.and if the wallet walks..well housewife is stuffed
Spuddy I think we all make life choices which hind sight tells us might have been a mistake but at the time felt right. You can only do what you think is right, at the time.
The reason this thread is useful is it has a wealth of experiences saying think very very carefully before making yourself dependent. Some of the posters who have argued that advice is scaremongering, will be lucky. Others won't be. Most (All?) of us were also pretty confident in our marriages at one point otherwise why would you have married!
I am independent but there is nothing to insure me against my own health, job loss, breakdown. I wish there was
Have requested this be moved to Relationships .
I think that part of the problem is that, until you've lived it, being a SAHM seems like the easy option. It is anything but.
thats a truism we all assert,that no one know how hard anything is until is a lived experience
Yes, distracted by multitasking. It can make the breadwinner resentful, thinking that they are slogging away while the SAHP is doing not a lot.
It being hard work eroded my confidence.
But things can change for the better too. I was lucky enough to find a fulfilling new career and am now happier than I thought possible.
A couple of years ago, I would not have been able to imagine getting to where I am now
Emma, I really hope that your future is positive.
I was in a highly paid job with my first relationship - it was tough at times but it gave me the freedom to end that relationship. I spent years on my own and built up financial security. Then I met H and despite my own experiences I gave up my job when ds arrived (he was a very difficult baby and all the night time waking fell to me). 10 years on my H's career has flourished and I am earning less than I have ever earned. The current climate is very tough especially since we moved to be closer to H's work. I trusted H, I thought it would be OK but I was naive. No one should be financially dependant on another adult.
Turning 40 has felt a watershed (I think it's equal to a man who's 50). I feel as if I'm less employable and I think there is a prejudice towards older women.
I grew up in a single parent household. Born in the mid 1960's when this was not the done thing. My DM, who always worked, met my stepdad when I was 11yo. He was an abusive twat to both of us, sexually, physically, emotionally and financially until she saw the light and left when I was 18yo.
My DH is the most loving, kind, gentle man that you could wish to meet. He is a fantasic father to our 3 DS's, a wonderful husband, and has been for over 25 years.
But, as a result of lessons learned at a very early age, I have always worked, and had my own Bank Account. He does not know and has never asked what I earn. We share bills but I earn enough to cover all the bills. DH does not know this. I know exactly how much he earns.
It makes me feel sometimes, that I will never trust anyone else but me to provide for me and my DS's, but then I look at my DM and think that I have to protect myself and my DC's if ever the unthinkable happens.
i will never be financially dependent upon another adult.too precarious
we have separate individual accounts, and joint for mortgage,nursery etc
i couldnt bear to not have financial autonomy,id feel beholden and downtrodden
What if you are / were NOT married though?
I (stupidly, in hindsight), did not get married to the father of my 2 DC's. I thought I was too young for marriage at the time.
Before I had the DC I was on my way to having a good job with good prospects and pension etc (I was student nurse). exP was another type who is very employable (has 2 degrees, some experience) but didn't want to be "corporate" , or "sell out" and he did earn slightly more at the time than I got in bursary etc and he was adamant he would NEVER be able to do childcare and work his full time job so I gave up my course to become SAHM and we struggled along on just his wage (which was much lower than it could have been if he would accept having a boss) for years.
When we split, I was left with nothing, no money, nothing. He stayed in the house as it was soley in his name (signed over to him only by his nasty piece of work mother), me and DC had to go into a homeless unit , go on benefits and we got our own place eventually.
I do work now, but I have no qualifications past 2 A levels, I had zero job history at all because I went from school to Uni (nursing), to SAHM. I went for thousands of jobs, any jobs, and got nothing. Eventually I got part time employment through doing voluntary work (but 9 months voluntary before they offered me a job). The job I'm in just now is minimum wage and I could do it standing on my head (not boasting, just I know I could do more). However the logistics of 2 young children, housework, childcare and a nursing degree would be far too much, I know that I've done the course it took up so much time even pre-DC.
My ex has a house bought and paid for in his name, still working no gaps, and obviously his degrees. He does see DC but pays not a penny towards their upkeep (Child Maintenance have been rubbish, no outcome for years despite me being on the case).
I don't know what the answer is, but really something needs to be done. SAHP's are vulnerable financially, WOHP's are vulnerable in the sense that access to DC could be difficult in the event of a split.
Like SGB said, the work of a stay at home parent is completely under-valued, in fact hardly even valued at all. It should have monetary value. Imagine what would happen in the country if all SAHP's suddenly decided to stop providing childcare and domestic service? . If I were ever to be a stay at home parent again I would ensure that my partner paid a set amount into my account every month, out with all the bills - just an amount for me, not for any bills, for my own savings, easily accessible and accessible only by me in the short term in the event of separation. OK, not very romantic, but I won't be in a homeless unit again with DCs.
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text: etd@IISc Collection: http://hdl.handle.net/2005/14 2017-03-23T11:15:03Z Design And Access To Disallowed And Unusual Conformers Of Peptides In Crystals And In Solution : Structural Consequences Of The Imidate And Thioimidate Isosteres For The Peptide Bond http://hdl.handle.net/2005/2511 Title: Design And Access To Disallowed And Unusual Conformers Of Peptides In Crystals And In Solution : Structural Consequences Of The Imidate And Thioimidate Isosteres For The Peptide Bond Authors: Reddy, N Damodara Abstract: This thesis entitled "Design and Access to Disallowed and Unusual Conformers of Peptides in Crystals and in Solution: Structural Consequences of the Imidate and Thioimidate Isosteres for the Peptide bond" is divided into eight chapters. Imidate Modification The range of disallowed dihedral angles for residues in peptides is governed by their local steric and electrostatic clashes. Rare tolerances of violations in these angles are attributed to distortions in both local and global bond characteristics of the peptides. Discerning the origins of such disallowed angles and the consequent distortions in body of the peptides is essential, for a complete understanding of the protein fold, to improve the crystal database for validation of rare but acceptable residue conformations and for validation and improvement of theoretical models that evaluate the interactions that define the Ramachandran space. Unlike for the ordered secondary structures such as β-sheets α-helices and β-turns currently there are no models for residues constrained in disallowed folds. We reasoned that residues may be stabilized in disallowed folds in peptides if a neighbouring group and The range of disallowed dihedral angles ( , ψ) for residues in peptides is governed by their hence its local unfavorable clashes can be selectively modified to a motif that favors such space Steric clashes of the type H•••Xi±n involving the backbone amide hydrogen (H) contribute to ~60% of disallowed ,ψspace. Conversion of an amide to an imidate (A→I) will remove the corresponding H and hence the steric clashes related to it in peptides. Importantly, this will introduce an H-bond acceptor N (of imidate) in place of an H-bond donor NH (of amide), which will allow formation of unusual H-bonding interactions between the imidate N and the neighbouring Hs and hence constrain residues in otherwise inaccessible dihedral angles. The conversion of A→I is challenging owing to difficulties in selective synthesis, stability and purification of the imidate motif. We address all these concerns by the selective conversion of a backbone amide in peptides to the relatively stable cyclic 5,6-dihydro-4H-1,3-oxazine imidate isostere, by an intra¬molecular nucleophilic cyclo-O-alkylation reaction. Chapter 1:SectionB: Autocyclo-O-Alkylation of N-(3-Bromopropyl)amides into 2-Alkyl-5,6-Dihydro-4H-1,3-Oxazinehydrobromides We are describing the reactivity of N-(3-bromopropyl)amides that are precursors for 2-peptide-5,6-dihydro-4H-1,3-oxazine. The starting materials, 3-bromopropylamides, were synthesized in good yields by coupling the corresponding carboxylic acids and anhydrides with 3-bromopropylaminehydrobromide using standard mixed anhydride peptide coupling protocol. N-(3-bromopropyl)-acylamides are unstable during the isolation. Time-dependent 1H NMR of all the acetamides revealed that they underwent clean auto-cyclization to form the corresponding 2-alkyl-5,6-dihydro-4H-1,3-oxazine hydrobromides following first order rate. The salts were easily isolated in high purity by trituration of the mixtures with ether. The t1/2 of autocycliation of decreased upon increase in electron density on the R-carbon. Notably, the tert-butyl substituent cyclized significantly faster than acetamide which have enolizable hydrogens at the R-carbon. Thus, the cyclization rate is affected predominantly by the inductive effect of the R-carbon substituents. The formamide remained stable and unchanged due to the poor electron-donating ability of hydrogen. Chapter 1: Section C: Intramolecular Hydrogen Bond Assistance Improves Autocyclization in N-(3-Bromopropyl)amides The autocyclisation do not go to 100% completion. This is because the released hydrobromic acid quenches the nucleophilicity of amide carbonyl oxygen. In order to scavenge hydro bromic acid, we used 1 equivalent of DIEA base is acting only acid scavenger which conformed by unaffecting the reaction rate upon increasing equivalents of DIEA. We found that autocyclisation of N-(3-bromopropyl)amides rates in peptides involved in intramolecular backbone H-bonding interactions improve the autocyclization rates significantly than unstructured (random coil) peptides. Even with in the ordered structures the rate depends on the proximity of H-bonding distances as well as the H-bond acceptor strength. Half-life of autocyclisation in various peptide secondary structures are determined from time variant 1H NMR studies performed at 60 mM peptide concentration in CDCl3 at 32 oC. Chapter 2: Section A: Synthesis and Isolation of 5,6 Dihydro-4H-1,3-Oxazine Containing Peptidomimetics We have introduced 5,6-Dihydro-4H-1,3-oxazine as the imidate isostere at C-terminus of a number of peptides through NaH (base) mediated intramolecular cyclo-O-alkylation of N-(3-bromopropyl)amides. The amide to imidate (A→I) modification reaction is faster (1-5.5 h), Exhibiting no electronic and structural effects under these conditions. The side product NaBr can be easily separated by filtration through celite. No side products were observed and there is no need of further purification to get pure 1,3-oxazines in quantitative yields in all the peptidomimetics. Using this synthetic protocol we have synthesised a variety of 1,3-oxazine containing peptide analogues including aliphatic, branched aliphatic, polar side chains and larger peptides. We show that the retention of configuration at Cαof peptides during the base mediated cyclo-O-alkylation reaction. that the C5i.structures are more populated at Aib due to operation of The Thorpe-Ingold effect. The strength of hydrogen bonding interaction in C5i structure is similar to those of the highly buried backbone hydrogen bonding interaction found in the middle of a model 310-helical peptide as indicated by DMSO titration experiments. Chapter 3: Section A: Consequences of "Disallowed" Conformations on Constrained β-Turn Peptides Here we are describe the consequence of disallowed conformations the on a C-terminus of a type-II β-turn. We choose stereochemically constrained Type-II β-turn Pro-Aib dipeptide analogue which is the ideal model to mirror the structural effects of introducing the A→I modification at the C-terminus. The imidate containing peptidomimetic crystallised in dichloromethane and hexane mixture. Analysis of crystal structure revealed that Aib NH is involved in 3-centered H-bonding interactions with the N of oxazine and N of proline. This constrains Aib in a conformation that is natively disallowed to it. The (, ) angles of Aib residue fall in the (180,0) region which is strictly disallowed for natural peptides due to steric clashes involving the back bone amide N-H. More importantly there are two C•••O interactions which are accomidated in the crystal structures. Both oxygen"s were place in staggered orientation of the Pro oxygen (OPro) between the two β-CH3 groups of Aib, which is again strictly disallowed in natural peptides due to strong C•••Oi-1 hard sphere clashes. However no vdW space violations are observed between these atoms. Chapter 3: Section B: Conformational Effects of "Disallowed Aib on a 310-Helical peptide In order to investigate the origins and consequences of "disallowed" conformations on a folded helical peptide body, the conformationally stable peptide sequence Boc-Leu1-Aib2-Ala3-Leu4-Aib5-Ala6-Phe7-Aib8-OMe (310-helix-OMe)was chosen which is known to adopt 310-helix in crystal structure. Analyses of the ROESY spectra, DMSO titration experiments, and CD spectra of 310-helix-OMe and its Oxa analogue reveal that their solution conformations are identical to those of the crystal structure of 310-helix-OMeSix sequential i+3→i intramolecular backbone H-bonds stabilize the 310-helical peptide fold in both peptides in solvents of varying polarity. The N-terminal and central segments of the helical molecules are quite structurally rigid and are not deformed. The presence of the disallowed Aib*8 residue in Oxa analogue has a clear conformational effect mainly on the residue Phe7. It looks like the Phe7 amide H is involved in shielding, the Aib*8 amide H through a bifurcated hydrogen bonding interactions with the nitrogen of oxazine and carbonyl oxygen of Ala6 residue. Maximum structural distortion effect on the registers closest to the putative imidate bond. Our results show that "disallowed folds need not denature order in the peptide fold". Chapter 4: Synthetic Methods for Introducing the A → I Modification anywhere along the Peptide Chain Here we describe the incorporation of imidate isostere in the middle of any peptide sequence. In Oxa selectivity is towards 5-exo-cyclo-O-alkylation in 1 : 4. In Thi it is towards 6-exo-cyclo-S-alkylation in 3 : 1 ratio. This is because of better nucleophile of sulphur (S). We saw that Thi is stable to peptide coupling, N-and C-terminus protection, deprotection conditions and can be easily incorporated in middle of peptide. Chapter 5: Section A: Cis-trans Isomerism in the X-Pro Peptide Bond In tertiary amides like X-Pro peptides having high propensity to access cis conformations due to similar environment in both cis and trans around the Cof X. X-Pro peptide bonds, constrained in s-cis conformations are prevalently found in the turn regions of peptides with the residue "X" in the i+1position and Pro at the i+2position of the β¬turn. These types of turns are termed as the type VI β-turns. For better understanding of the molecular recognition at specific cis X-Pro peptide bonds in biological events, the structure and dynamics of various constrained cis X-Pro peptide bond analogues with varying steric and electronic perturbations have been studied. Many models have been developed for stabilizing cis conformer by perturbation of molecular recognition surface of proline by employing steric and electronic interaction. In biological functions proline molecular recognition surface and cis X-Pro peptide bond more important. There is need of novel method for stabilizing X-Pro peptide bond in cis conformer without modifying the pyrolidine ring in proline. Chapter 5: Section B: Biasing the cis/trans Equilibrium in X Pro Peptides using Reverse ni → ni-1 * Interactions Here we present our findings that peptidomimetics containing the 5,6-dihydro-4H-1,3¬oxazine (Oxa) and 5,6-dihydro-4H-1,3-thiazine (Thi) functional groups at the C-terminus of Pro selectively and remotely stabilize the s-cis rotamers of the preceding pyrrolyl (Xaa-Pro) 3° amide bonds, while conserving these recognition elements. The cis/trans equilibrium of Xaa-Pro peptide bonds is shifted significantly in favor of the satirically disfavored cis isomers in these peptidomimetics (upto ~90%). We also provide evidence for the influence of an unusual n→ πi-1 * interaction in the cis, and the n)(n repulsion in the trans, conformers of these molecules to beat the origin of such the origin of such cis stabilization. Chapter 6: Steric Interactions in the cis Piv-Pro Peptide Bond The inaccessibility of cis Piv-Pro rotamer in any peptide is believed to be because the steric clashes between substituents on CX and CPro are unavoidable in this conformer. Here we access the cisPiv-Pro conformer in crystal structure of Piv-Pro-Aib-OMe and that it is sufficiently flexible to undergo bond distortions and avoid all steric clashes between substituents on CPiv and CPro . It is however the unavoidable distortions in the dihedral angle of the Prothe cisPiv-Proconformer. The cisPiv -Pro conformer is indeed accessible, if such distortions are accommodated in the peptide. Chapter 7: Steric and Electronic Interactions in the cis Isomer of Piv-Pro Peptide Bond in Solution We have studied the electronic and steric interactions and the conformational equilibrium in two sets of homologous peptides, X-Pro-Aib-OMe (which contain Aib) and X-Pro-NH-Me, where X is acetyl, propionyl, isobutyryl and pivaloyl, in solvents of varying polarities consisting of carbontetrachloride, chloroform or dimethylsulfoxide, by means of their 1H and 13C-NMR, and FT-IR spectra. Formation of n * interactions between the carbonyls that flank the Aib residue, influences the alleviation of steric interactions that are believed to preclude access to the cis conformer of the Piv-Pro peptide bond. The cis Piv-Pro conformer is observable in the Aib containing peptides, at ambient conditions by FT-IR and at temperatures as low as 273 K by NMR. We estimate that the steric interactions contribute < 0.5 kcal/mol to the conformational free energy of X-Pro peptide bond isomerism, irrespective of the steric bulk on the acyl (X) group. The relative strengths of intramolecular hydrogen bonding interactions involving the X-Pro peptide motif in different conformers of these peptides influence their relative conformational stabilities. Chapter 8: Remote Effect of Oxa and Thi Functional Groups on cis-trans Isomerism at X-Pro Peptide Bonds The C5a interaction at Pro residue occurs in the transition states for the intramolecular acid catalysis of cis → trans isomerization in peptidyl prolyl isomerases (PPIs) and enables the decrease in transition energy barrier for the isomerization process. We show that the NPro….HAib interactions in C5a structures can be remotely effected in order to control in equilibrium constant values of the cis/trans isomerism (Kc/t) in X-Pro¬Aib-Oxa and Thi containing peptides. By this method we observed improvement in Kc/t values from 0.18 in esters to 0.56 in Thi and 0.66 in Oxa containing peptides. Analyses of the ROESY spectra, DMSO titration experiments, variable temperature experiments and FT-IR spectra of R-CO-Pro-Aib-Oxa (R = Me, Et, iPr) and its Thi analogues reveals that both interactions (C5a and C5i) are persistent in cis and trans conformers of this peptidomimetics. (for structural formula pl. see the abstract.) 2016-03-03T18:30:00Z Design And Development Of Synthetic Methods Using Metal-Mediated And Metal Free Redox Reactions : Novel C-H Activations, Reductions And Oxidative Transformations http://hdl.handle.net/2005/2501 Title: Design And Development Of Synthetic Methods Using Metal-Mediated And Metal Free Redox Reactions : Novel C-H Activations, Reductions And Oxidative Transformations Authors: Lamani, Manjunath Abstract: The thesis entitled "Design and Development of Synthetic Methods using Metal-mediated and Metal-free Redox Reactions: Novel C-H Activations, Reductions and Oxidative Transformations" is presented in 4 chapters Chapter 1; Iodine catalyzed amination of benzoxazoles: efficient metal free route to 2-aminobenzoxazoles under mild conditions. The Chapter 1 of this thesis describes iodine catalyzed C-H activation of benzoxazole with primary and secondary amines to form oxidative aminated products. Selective C-H oxidation is a frontline area of modern chemical research as it offers the opportunities to new avenues and more direct synthetic strategies for the synthesis of complex organic molecules.1 In this context, transition metals such as palladium copper, nickel etc, are used extensively for the functional group directed C-H activation, and thus provides new, rapid, low-cost, and environmentally benign protocols for the construction of new chemical bonds.2 During the past two decades iodine and hypervalent iodine have been focus of great attention as they provide mild, chemoselective and environmentally benign strategies in contrast to toxic metal oxidants.3 In this chapter, a facile metal-free route of oxidative amination of benzoxazole with secondary or primary amines in the presence of catalytic amount of iodine (5 mol%) in aq tert-butyl hydroperoxide (1equiv) and AcOH (1.1 equiv) at ambient temperature, under the solvent-free reaction condition is presented. This user-friendly method to form C-N bonds produces tert-butanol and water as the by-products, which are environmentally benign. A wide range of benzoxazole derivatives containing electron-donating and electron-withdrawing groups were coupled with both primary and secondary amines (Scheme 1). Application of this methodology is demonstrated by synthesizing therapeutically active benzoxazoles by reacting 5-chloro-7-methylbenzoxazole with N-methylpiperazine and N-ethylhomopiperazine to obtain corresponding N-aminatedbenzaxozoles, which exhibit antidiarrhetic activity (Scheme 2).4 Scheme 2 Chapter 2: NIS catalyzed reactions. amidation of acetophenones and oxidative amination of propiophenones Chapter 2 is divided in to 2 parts. Part 1 describes the synthesis of α-ketoamides by using acetophenone and secondary amine in the presence of N-iodosuccinamide and TBHP in acetonitrile at room temperature, whereas Part 2 reveals the synthesis of 2-aminoketones by reacting aryl alkyl ketones and suitable secondary amine in the presence of NIS and TBHP. Part 1: Oxidative amidation, synthesis of α-ketoamide: Alpha α-ketoamides are important intermediates in organic synthesis that are present in a variety of natural products, and pharmaceutically active compounds. Herein, a mild and efficient conversion of acetophenones to α-ketoamide is documented by using aq.TBHP and N-iodosuccinamide (NIS) as a catalyst, at ambient temperature. This amidation reaction was found to be versatile as several aetophenone derivitives containing electron-withdrawing and electron-donating substituents underwent a facile amidation. It was also found that acetyl derivatives of heterocylic compounds could be easily converted to their corresponding ketoamides (few examples are shown in Scheme 3).5 Scheme3 Part 2 of Chapter 2 narrates a novel amination of propiophenone and its derivatives catalysed by NIS in the presence of TBHP to furnish their corresponding 2-aminoketone derivatives (Scheme 4). These derivatives are ubiquitous scaffolds that are present in a wide variety of therapeutic agents. Some of these compounds are used in the treatment of depression, smoking cessation, as monoamine uptake inhibitors, rugs for cancer. They are photoinitiators, precursors to β-aminoalcohols, such as pseudoephedrine analogues. 2-Aminoacetophenone analogues are also important intermediates for the formation of several heterocyclic compounds and are active moieties in several important drugs such as ifenprodil, Scheme 4. Chapter 3: Efficient oxidation of primary azides to nitriles This Chapter is divided in to 2 parts, which presents the oxidation of primary azides to their corresponding nitriles. Part 1: An Efficient oxidation of primary azides catalyzed by copper iodide: a convenient method for the synthesis of nitriles In Part 1, an efficient oxidation of primary azides catalyzed by copper iodide to their corresponding nitriles is reported. Herein, the oxidation of primary azide to nitrile is performed using catalytic amount of copper iodide, and aq TBHP in water at 100 ° C. This methodology is compatible with a wide range of primary benzylic azides that contain electron-donating and electron-withdrawing functional groups. The oxidation was found to be selective and a number of oxidizable functional groups were well-tolerated during the reaction conditions (few examples are shown in Scheme 5).6 Scheme 6 Furthermore, oxidation of secondary azides furnished the corresponding ketones in excellent yields (Scheme 6).6 In the Part 2 of Chapter 3, a non-metal catalysed oxidation of primary azides to nitriles at ambient temperature is reported. This part reveals the oxidation of primary azides to nitriles by employing catalytic amounts of KI (25 mol%), DABCO (25 mol%) and aq. TBHP (3 equiv., 70% solution in water). This reaction provides a good selectivity, as double and triple bonds were not oxidized under the reaction conditions. Additionally, chemoselective oxidation of benzylicazides against aliphatic azides increases the potential application of the present method (Scheme 7).7 Chapter 4: Chemoeselective reduction of olefins Part 1: Iron chloride catalysed aerobic reduction of olefins using aqueous hydrazine at ambient temperature Chapter 4 describes the reduction olefins and acetylenes, which is presented in two Parts. Part 1 documents utility of hydrazine (1.5 equiv) for the chemoselective reduction of nonpolarised carbon-carbon bond using iron catalysts. In this part, a chemoselective reduction of alkenes and alkynes in the presence of a variety of reducible functional groups is demonstrated (Scheme 8). The highlight of the present method is that the reduction proceeds well at room temperature and requires only 1.5 equiv of hydrazine hydrate. The olefin reduction by hydrazine depends upon the controlled release of diimide during the reduction. Generally, metal catalyzed reduction of olefins employ a large excess of hydrazine (10-20 equiv), which might be attributed to uncontrolled release of diimide during the reduction.8 Scheme 8 Part 2: Guanidine catalyzed aerobic reduction: a selective aerobic hydrogenation of olefins using aqueous hydrazine In Chapter 4, part 2, organocatalytic generation of diimide and its utility to reduce the double bonds is presented. Generation of diimide in situ by using organo catalysts and its use for the reduction of carbon-carbon double bond is one of the interesting topics in organic chemistry. It has been shown in this part of the thesis that the reduction of olefin at room temperature can be efficiently performed by using 10 mol% of guanidine nitrate, 2 equiv of aqueous hydrazine in oxygen atmosphere. This method tolerates a variety of reducible functional groups such as nitro, azido, and bromo and protective groups such as methyl ethers, benzyl ethers, and Cbz groups. It is also shown that terminal olefin can be selectively reduced in the presence of internal olefin (Scheme 9). Unlike other methods that employ diimide strategy, the present method is shown to be efficient in reducing substrates those contain internal double bonds such as cinnamyl alcohol and its derivatives 2016-02-15T18:30:00Z Bile Acid Based Supramolecular Gels, Semiconductor Nanocrystals And Soft Hybrid Materials http://hdl.handle.net/2005/2513 Title: Bile Acid Based Supramolecular Gels, Semiconductor Nanocrystals And Soft Hybrid Materials Authors: Chakrabarty, Arkajyoti Abstract: Chapter 1. General Introduction This chapter gives an introduction to supramolecular organo/hydrogels and the related bile acid chemistry touching upon the gelation properties of the bile acid derivatives. Diverse applications of the supramolecular gels are illustrated with several examples. In the concluding section of this chapter, a brief introduction on the semiconductor nanocrystals is provided. Finally, the content of the thesis is outlined. Chapter 2. Bile Acid Derived Novel Organo/hydrogelators Part 1. Bile Acid Derived Organo/hydrogelators With a Basic Side Chain Cationic analogues of bile acids which showed remarkable gelation properties in water were reported from our laboratory. This led us to investigate the aggregation behaviour of some of the lithocholic and deoxycholic acid derivatives having a basic side-chain. Figure 1. Bile acid based organo/hydrogelators containing a basic side-chain. In this part, an organogelator 1 and a hydrogelator 2 derived from parent bile acids have been described with respect to their gelation properties, morphology, thermal and mechanical stability of the gels. The organo/hydrogels were shown to be responsive to acid-base stimuli as the organogel formed only in the protonated state and the hydrogel formed in the neutral form of the tertiary amines. The xerogel fibres obtained from the organogel were found to be solid-like and stable up to 200 oC as confirmed by variable temperature polarizing optical microscopy. The non-fluorescent organogel was doped with a fluorescent dye (coumarin 153) to design a novel dye-organogel composite material which was investigated with laser scanning confocal fluorescence microscopy showing the dye molecules were uniformly deposited on the organogel fibres. Part 2. Serendipitous Organogelation by Dimeric Bile Acid Esters This section highlights our work on the organogelators based on a number of dimeric esters consisting of different bile acid units. Figure 2. The three different dimeric bile acid esters as organogelators. In this part, three bile acid derived dimeric esters (1, 2 and 3) were shown to possess organogelation properties in aromatic and halogenated aromatic solvents. We studied the morphological features and rheological properties of these organogels. Next, the organogel matrix was exploited to generate and stabilize gold nanoparticles and prepare AuNP/gel hybrid material. Chapter 3. Cholate Hydrogels and Soft Gel-nanoparticle Hybrid Materials Sodium cholate does not form gel in water under any condition as compared to other sodium salts of other bile acids such as sodium deoxycholate and lithocholate which show pH-dependent gelation behaviour. Figure 3. Metal cholate hydrogels derived from sodium cholate and a variety of metal ions. In this chapter, super hydrogelation of sodium cholate induced by a variety of metal ions (Ca2+, Cu2+, Co2+, Zn2+, Cd2+, Hg2+ and Ag+) is highlighted with respect to their morphology and mechanical strength/stability. The calcium cholate supramolecular system showed the presence of helically twisted nanofibres which were utilised in the synthesis of soft hybrid materials containing metal (Au and Ag) and metal sulphide (CdS, ZnS, HgS, etc.) nanoparticles. Chapter 4. Cadmium Deoxycholate and Highly Luminescent CdSe Nanocrystals Bile acid derivatives have very high chemical and thermal stability owing to the presence of a rigid steroidal nucleus. We explored the possibility of utilizing the bile salt derived from Cd as a metal complexes as precursor to high quality nanocrystals (NCs) which can only be accessed at high temperatures (>200 oC). Figure 4. Synthesis of high quality CdSe NCs from cadmium deoxycholate. In this chapter, the synthesis of high quality CdSe nanocrystals is discussed using a novel bile acid based precursor: cadmium salt of 7-deoxycholic acid, which has high thermal stability and can be conveniently used at very high temperatures (>300 oC) required for the synthesis of high quality nanocrystals. Syntheses were done both by 'injection' and 'non-injection' modes. The as-prepared nanocrystals have high photoluminescence quantum yield, multiple excitons, narrow size-distributions and zinc blende/wurtzite crystalline cores. Appendix. Steroidal Thiols in Design of Novel Quantum dot (QD)/Gel Hybrid Materials Bile acid derived steroidal thiols were reported to be efficient capping agents for silver and gold nanoparticles from our laboratory. So, we wanted to check whether they could stabilize the semiconductor nanocrystals as well. Figure 5. Steroidal thiols as stabilizers of semiconductor quantum dots. In this short report, we describe the efficient capping by bile acid derived thiols of group II-VI semiconductor nanocrystals/quantum dots (QDs) (CdS, CdSe). After synthesizing the thiol capped QDs, we tried to disperse the capped nanoparticles into the gel fibres. The hybrid gels showed the presence of nanoparticles inside the fibres as observed by transmission electron microscopy, although the photoluminescence of the QDs was very low in the gel matrix, which might be due to the inefficient surface passivation of the nanoparticles in the gel. 2016-04-11T18:30:00Z Studies On 2,3-Unsaturated Sugars : Reactivity Switching, Rearrangements And Conjugate Additions http://hdl.handle.net/2005/2500 Title: Studies On 2,3-Unsaturated Sugars : Reactivity Switching, Rearrangements And Conjugate Additions Authors: Mukherjee, Arunima Abstract: Unsaturated sugars constitute as an important category of carbohydrate precursors in synthesis. Specifically, 1,2- and 2,3-unsaturated glycosides are excellent intermediates to derivatize monosaccharides and as building blocks in organic synthesis. For example, a major utility of 1,2-unsaturated sugars, namely glycals, is the addition reactions to afford 2-deoxy glycosides under acidic conditions and rearrangement reactions to produce 2,3-unsaturated glycosides. Lewis acids favour the formation of 2,3-unsaturated glycosides, whereas, Brønsted acids lead to normal addition products. A mixture of both the product is obtained often, depending on the nucleophiles and the stereochemistry of glycal. Chapter 1 of the thesis describes (i) reactivities of glycals under acidic condition and (ii) a general survey of reactions involving on C2-C3 carbons of monosaccharides. Glycals are useful precursors to derive a number of functionalized monosaccharide derivatives. A well-known acid catalyzed reaction of glycals is their conversion to 2,3¬unsaturated glycosides, known as the Ferrier products. In a research programme, reactivity switching and selective activation of C-1 or C-3 of 2,3-unsaturated thioglycosides under acid catalyzed condition was undertaken. Thioglycosides are excellent glycosyl donors and can be activated easily. In identifying the reactivities of 2,3-unsaturated thioglycosides, obtained through Ce(IV)-mediated reaction of a glycal, it was intended to study the glycosylation reaction and also the reactivity control of C1-C3 carbons during a glycosylation reaction. Experiments showed that a reactivity switching was possible through activation of either C-1 or C-3. Thus, C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid alone led to a transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. Oxocarbenium ion is the reactive intermediate during activation of a glycosyl donor, and in the case of a 2,3-unsaturated thioglycosides, the oxocarbenium ion may stabilize further by the presence of a C2-C3 unsaturation. Reaction of a nucleophile with allylic oxocarbenium ion may lead to two regio-isomers. Initially, NIS/TfOH was attempted on 2,3–unsaturated sugar with various alcohols and it was found that C-1 was the preferred reactive centre (Scheme 1) Scheme 1 In order to optimize the reaction for selective nucleophilic attack at C-3, further study was continued by using stoichiometric TfOH, in presence of acceptors alcohols with the intension to activate the double bond. The reaction led to the formation of 2-deoxy O-glycosides with the concomitant transposition of C-1 ethylthio-moiety to C-3 (Scheme 2). Scheme 2 An important observation was that the transposition of thioethyl group from C-1 to C-3 was highly regioselective. For example, with thiocresol as the nucleophile, there was an addition across the C-2-C-3 double bond to afford C-1, C-3-dithio derivative (Scheme 2). Thus, hard-soft nature of the nucleophiles, as well as, carbon centres helped to rationalize the reactivites. It was also observed that the intramolecular transposition of thioethyl group is highly stereo-controlled by equatorial C-4 acetoxy group. Thus, thioethyl nucleophile approached selectively at C-3 and afforded trans-diequatorial products. This rationalization was further confirmed through (i) reaction of benzyl protected 2,3-unsaturated thioglycoside, wherein a C-3 epimeric mixture was observed in 1:1 ratio; (ii) galactosyl derivative under similar reaction condition afforded anomeric mixture of 3-(4-methylphenylthio)-O-glycosides, with trans-diaxial orientation of substituent at C-3 (Scheme 3). Scheme 3 These reactions confirmed the role of C-4 substituent on the carbocation at C-3, through the presence or absence of a neighbouring group participation. In summary, in Chapter 2 the selective activation of either anomeric carbon or C-3 with proper choice of activation and reactivity control at each carbon will be described. Thioglycosides are excellent glyosyl donor and their glycosylation reactions were well explored. Upon indentifying the intramolecular transposition of thioalkyl/aryl functionality from C-1 to C-3, further investigations was undertaken to utilize the newly formed carbon sulfur bonds at C-3. Realizing a potential for such 3-alkyl/aryl thio 2-deoxy sugar, the Pummerer rearrangement was investigated. For this purpose, the thioalkyl/aryl moiety at C-3 was oxidized first to a sulfoxide. The resulting sulfoxide was allowed to undergo Pummerer rearrangement to afford vinyl sulfide (Scheme 4), resulting from the elimination of HOAc in the thioacetal formed in situ. Having implemented Pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl sulfide was undertaken. An effort to implement conjugate addition reaction was undertaken, which required the conversion of vinyl sulfide to vinyl sulfoxide in the first step. The conjugate addition reactions were first conducted with alkoxide nucleophiles. The reaction showed that addition of nucleophiles occurred from axial face to furnish manno-configured derivatives as a single diastereomer at sulfinyl sulfur in a moderate yield along with O-deacetylated product. It was also found that O-benzyl protected sugar vinyl sulfoxide was totally resistant to the conjugate addition reaction (Scheme 4). Scheme 4 In order to find the influence of the substituents in sulfoxide moiety in the addition of nucleophiles, additional study was conducted in which a less hindered thioethyl moiety was installed in place of p-tolylthio moiety. To install ethylthio moiety, a similar sequence of reaction was undertaken as described previously in Scheme 4. Conjugate addition reaction with alkoxide nucleophiles was conducted and analysis of the reaction showed that the addition of alkoxides remained similar, leading to the formation of manno-configuration of substituents (Scheme 5). Scheme 5 The configuration of the Michael adducts were ascertained from 1H NMR, as well as 2D NMR spectroscopies. H-1 of all adducts appeared as an apparent singlet, consistent with very small J1,2 values. Aryl vinyl sulfoxide afforded conjugate addition product at much higher ratio than corresponding alkyl vinyl sulfoxide. Thus, among aryl and alkyl vinyl sulfoxides, conjugate addition occurred better with the aryl vinyl sulfoxide, indicating a strong electronic effect of aryl group in stabilizing the conjugate anion which would form in situ during nucleophilic addition with vinyl sulfoxide. Therefore, p-tolylthio substituted vinyl sulfoxide served as a more efficient Michael acceptor when compared to the thioethyl substituted vinyl sulfoxide. Asymmetric environment of vinyl sulfoxides play a vital role during the reaction. Vinyl sulfoxides can exist in two stereochemically distinct conformation which makes the vinyl group electronically dissimilar. In one of the conformer S-O and C-C bonds are coplanar, whereas in the other conformation, these two bonds are opposite to each other. It is agreed generally that vinyl sulfoxides generally try to adopt the most reactive conformer during the reaction in which the C-C and S-O bonds are syn to each other. Thus, the preference for an axial attack would originate from a face anti to the lone pair of electrons on the sulfur of sulfoxide functionality, leading to the formation of the product with manno-configuration. As O-deacetylated vinyl sulfoxide was obtained along with the Michael adducts, it was assumed that one of the epimers of vinyl sulfoxide appeared to be more reactive when compared to the other. Chapter 3 describes implementation of a Pummerer rearrangement in order to synthesize a sugar vinyl sulfoxide and its conjugate addition reactions with alkoxide nucleophiles. The nucleophilic addition reactions of vinyl sulfoxide with other nucleophiles were studied further. The effect of the substituents of chiral sulfoxides in conjugate addition reactions was also incorporated in the course of reactions. Reactions of amines, carbon and sulfur nucleophiles were undertaken with p-tolylthio-substituted vinyl sulfoxides. The reactions showed formation of the addition-elimination products (Scheme 6). All primary amines, carbon and sulfur nucleophiles afforded C-2 axial epimer, namely, threo-epimer exclusively, wherein secondary amines furnished the equatorial vs axial epimer in 3:1 ratio. Scheme 6 In order to assess the course of the reaction, vinyl sulfoxide presenting a p-cumenethio¬moiety was installed in place of p-tolylthio moiety. Conjugate addition reactions were performed with both primary as well as secondary amines that showed formation of the C-2 epimeric mixtures. With both the primary and secondary amines C-2 equatorial epimer was found to be as the major product (Scheme 7). Scheme 7 In conjugate addition of vinyl sulfoxides, nucleophiles approach the olefinic face preferentially, which is anti to the electron rich sulfur lone pair of electrons and syn to the bulky aryl group. Therefore, C-2 axial epimer was observed as most favourable product. However, secondary amines remarkably influenced the pattern as well as selectivity of the reaction. Steric considerations were likely to dictate the overall reactivity with secondary amines which was even more pronounced when using p-cumenethio-substituted vinyl sulfoxide. Chapter 4 describes the conjugate additions as well as remote effect of aryl substituent on the selectivity of addition of amines on sugar sulfoxide In summary, the Thesis establishes: A new reactivity of switching and a selective activation of 2,3-unsaturated thioglycoside; A Pummerer rearrangement route in order to synthesize sugar vinyl sulfide for the first time, which on selective oxidation furnish a sugar vinyl sulfoxide, a useful precursor for conjugate addition reactions; An assessment of the stereoelectronic, as well as, steric effect of the chiral vinyl sulfoxide with various nucleophiles in conjugate addition reactions; Influence of the protecting groups were also studied in conjugate addition reactions. Overall the study presented in the Thesis provides a new insight to unsaturated sugars. The salient features of the present findings also showed that the intermediates such as C-3 substituted thioalkyl/aryl glycosides, vinyl sulfides, a variety of new C-2 substituted vinyl sulfoxides are also the potential sites for many types of modifications in monosaccharides. (For structural formula pl see the pdf file) 2015-12-20T18:30:00Z


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Dynasty 8
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Only at that age she has demonstrated plenty of possibility and she takes a bright future ahead of her. She was born in a location called Lismore, which lies in Australia.
Lots of info about her and her fascinating biography could be extracted from wiki websites like Wikipedia and IMDb. She's a star in social media sites like Twitter and Facebook. She's 607 thousand followers in Twitter, which shows her stardom in the website. She's huge in Instagram too as she's 804 thousand followers in Instagram. She uploads her most recent and best pictures in Instagram to share them together with her lovers and nearest and dearest. She's popular and happening and carried a great character. She flaunts her hot legs in a bikini , which may flatter any guys. Her hot legs and sexy feet can capture any guys and can get them fall for her. She's hot body as well as the key behind it's her perfect body measurements of 33-26-34. She's not so tall as her height is just 5 feet 6 inches.
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|Mr. Fish's Chips
|Employee of the Month
|List of objects
Mr. Fish's Chips is a type of food sold in Bikini Bottom.
It appears to be Mr. Fish on the cover along with a blue background and also on the inside is supposedly chips.
- Mr. Fish's Chips were only seen in the game, Employee of the Month.
- SpongeBob's chips went stale.
- The name of these chips is based off of "Fish and Chips."
- The name is quite ironic; it's usually "Fish and Chips," but since Bikini Bottomites are fish, its Mr. Fish's Chips.
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