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Tag Archives: research
Personal learning networks and learning not to be nervous
Today is LEARNING:500, the event to celebrate the 500th post on the blog. I'm sat in my London hotel room, where i should be working on my presentation, but instead am writing this over a cuppa. I should be nervous, … Continue reading
Posted in Achievement, Blog, Collaboration, Community, Community of Practice, Conversation, Formal Spaces, Forum, Introspection, Learning, Social Learning, Social Networking, Writing
Tagged Blogging, Collaboration, Event, LEARNING:500, London, research
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Sharing in learning and the vulnerability of sharing: research into music in learning
There is a great generosity of spirit that drives people to share their time and to share the expertise and experience. I've started a piece of writing around learning from music and, as part of my research, reached out to … Continue reading
Posted in Collaboration, Creative, Dialogue, Engagement, Ideas, Introspection, Learning, Music, Narrative, Reflection, Sharing, Social Learning, Writing
Tagged Community, Musician, research, Sharing, Vulnerability
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Research Paper: Communication in online spaces – trust and disclosure.
I asked the question "Assuming you are communicating with someone you know, are you more comfortable disclosing personal information online or in person?" This is part of a wider piece of research that i'm working on looking at how relationships … Continue reading
Relationships in learning: for support, for challenge, for friendship.
Whilst driving yesterday, i was thinking about the nature of relationships. Some of the people in the car i knew well, one i had never met before. With those people who i knew, there was a dialogue based on understanding … Continue reading
The ease of engagement: how we learn to participate in social learning spaces.
If i say that riding a bike is intuitive, i mean that no conscious thought is needed to do it, that anyone can just pick it up, that no instruction is required. My statement would, of course, be wrong: it … Continue reading
Posted in Challenge, Collaboration, Community, Engagement, Environment, Informal Spaces, Learning, Social Learning, Spaces
Tagged BBC, bbc research, behaviours, Engagement, Fluidity, Learning, passive consumers, research
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First dates: exploring the nature of relationships in social learning environments.
I should start by telling you that i'm not going to answer this question today. But i'm working on it. In social learning spaces, online environments that extend and deepen the learning experience, the nature of relationships becomes of increasing … Continue reading


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The Gophers beat Florida State 77-68 in Tallahassee, Fla. Tuesday evening.
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Wednesday November 28, 2012
The Gophers finished a productive road trip by holding off Florida State in the ACC/Big...
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37 photos added for Silent Hill
Posted on Thursday, April 27th, 2006. Last Updated on Thursday, April 27th, 2006 11:27 PM by Scott Jentsch
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It made audiences scream to the tune of $20 million last weekend, and it faces competition that will surely keep it from hitting the top of the box office this weekend.
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In addition to the photos, check out the videos on the Trailers and Videos page before making the trip to the theater, just to make sure that this is the movie you're looking for.
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FollowUnveiled at the New York Auto Show
Kelley Blue Book
Palestinians are coming to the aid of Ferguson
Palestinian activists are taking to Twitter with their support and some cases, helpful tips on dealing with things like tear gas.
Warning: Don't rub your eyes | Follow micdotcom
A Palestinian man smoke water pipe in destroyed houses after returning home in the Tufah neighborhood in eastern Gaza City on August 31, 2014.
Palestinians, 1979. Thomas Billhardt,
Kelley Blue Book
GAZA CITY : Palestinian children pose for a picture on a makeshift boat
made of plastic bottles on April 18, 2015 at the port of Gaza City. AFP
August 5, 2014
Over 200 Palestinians have been abducted by occupation soldiers on the borders of Gaza during the ground invasion of Gaza, transferred to undisclosed locations, interrogated, and abused, while those same occupation forces killed over 1850 Palestinians, wounded nearly 10,000 and destroyed thousands of homes.
These civilians, who refused or who were unable to leave their homes due to massive aerial bombing and shelling, were transferred to special camps set up inside occupied Palestine '48, and interrogated for hours or days by military forces and the Shin Bet. Over 75 of them were released and left outside Beit Hanoun, and the remaining Palestinian civilians from Gaza remain unaccounted-for and under arrest, as well as wounded people, some of whom were released without treatment after two days of interrogation. Paramedics and wounded people were arrested on July 24 as they left Khuza'a.
Issa Qaraqe, a member of the Palestinian Legislative Council, cautioned on August 4 that some Palestinians who were captured by the occupation army may have been shot immediately after their arrest, as were civilians attempting to leave Khuza'a. Some of those detained were taken to occupation hospitals and another portion are still under interrogation. He warned that some of the missing may have been murdered by occupation forces or allowed to bleed to death without medical treatment, and called upon the International Committee of the Red Cross to act urgently to determine the fate of the Palestinians arrested in Gaza by the occupation forces and the circumstances of their detention.
Addameer issued the following statement on the urgent situation of Palestinians arrested from Gaza:
24 July 2014, occupied Ramallah – As the brutal assault in Gaza continues onto its seventeenth day, Addameer Prisoners Support and Human Rights Association expresses deep concern regarding the newly launched mass arrest campaign launched by the Israeli forces.
At least 150 Palestinians were arrested overnight in Gaza and forcibly transferred to an undisclosed detention center where they are now undergoing interrogation by Special Unit 504 in coordination with the intelligence services. The detainees are expected to undergo interrogation by the Shin Bet as well.
Also among those who have been arrested in recent days are 'Ammar Shami, who was injured during the shelling and is now hospitalized during his detention. Addameer's colleagues from Al-Mezan in Gaza are representing Shami as well as nine other detainees: Mahmoud Abu Saeed, Afif Al-Jarah, Imad Al-Jarah, Abd Al Rahman Balousha, Hassan Al-Astal, Mohammad Al-Agha, Ahmad Abu Lahiya, Ibrahim Abu and Mohammad Al-Qudra. The ten detainees have lawyers bans for a period of ten days, making the circumstances of their interrogation and detention unknown.
Considering the arbitrary nature of these arrests, Addameer raises concerns that the detainees will be subject to Israel's "Unlawful Combatants Law." This law allows for Palestinians from the Gaza Strip to be detained for an unlimited amount of time without being charged or brought to trial. Under this law, detainees are issued a permanent detention order and are then brought before an Israeli District Court only once every six months for judicial review of their order. In practice, the Unlawful Combatants Law contains fewer protections for detainees than even the few that are granted under administrative detention orders in the West Bank.
In addition to the egregious war crimes committed by Israel in this latest round of aggression on Gaza, in which over 703 Palestinians have been killed, the majority of them civilians, and thousands injured, Addameer is concerned about the continued violation of international humanitarian law in regards to the prisoners. The forcible transfer of prisoners by the Occupying Power is in gross violation of Article 49 of the Fourth Geneva Convention. Furthermore, although the circumstances of the detainees interrogation are currently unknown, photos of the detainees indicate that they have been stripped of their clothing, detained in crowded areas and in some cases, blindfolded. This degrading and humiliating treatment is also in violation of IHL and IHRL, as well as the dignity of the prisoners and the Palestinian people. Israel's well-known systematic and widespread use of physical and psychological torture against Palestinian prisoners also raises concerns for the treatment of the detainees as well.
Addameer calls on all international bodies to intervene immediately to implement international human rights and humanitarian law in the Gaza Strip, call for a ceasefire and hold accountable the perpetrators of the war crimes committed against the Palestinian people in the International Criminal Court.
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The brutally beaten, 15-year-old US-Palestinian cousin of murdered teen Mohammad Abu Khdeir has been placed under house arrest, despite police demands to keep him in custody. Tarek Abu Khdeir was accused of attacking police officers at a protest.
An Israeli court ruled that Tarek Abu Khdeir should be subject to house arrest in the east Jerusalem neighborhood of Beit Hanina on Sunday. Court spokeswoman Luba Samri said that police had asked the judge to extend the remand of the teenager, claiming that he attacked police officers during violent protests over the death of his cousin, 16-year-old Palestinian boy Mohammad Abu Khdeir.
Tarek's parents maintained his innocence and claim Israeli police officers committed an unprovoked attack on their son while he was handcuffed. On Saturday a video, showing how two officers violently beat Abu Khdeir while he was lying on the floor, appeared on local television, provoking outrage and condemnation on social media.
Following the uproar, the US government released a statement expressing deep concern over the incident.
"We can confirm that Tarek Khdeir, an American citizen, is being held by Israeli authorities in Jerusalem. [Tarek Abu Khdeir] was visited by an official from the US Consulate General in Jerusalem today," US State Department spokeswoman Jen Psaki said in a statement, adding that the US was profoundly troubled by the reports.
Members of the Israeli police force claim the video was "edited and tendentious" and was not an accurate reflection of events. They say Tarek was detained during the arrest of six other masked men, some of whom were armed with knives. The police are conducting an inquiry into the incident.
Tensions have been building over the past week in the area after the abduction and murder of Mohammad Abu Khdeir who was found dead in the woods on Wednesday. Israeli officials suspect Jewish nationalists may have committed the crime as a reprisal for the kidnapping and murders of three Israeli teenagers on June 12. The Israeli authorities have arrested six people in connection with Mohammad's murder, Israeli newspaper Haaretz reported Sunday.
Mohammad Abu Khdeir's death sparked fury in Palestinian neighborhoods with violent protests erupting in East Jerusalem. The Arab teen was buried on Friday after it was revealed in an autopsy that he had been burned to death by his captors.
His funeral drew thousands of mourners, but quickly descended into a full-blown rally with participants turning their anger on police, burning tires and throwing stones. Israeli police deployed stun grenades and tear gas to bring the crowds under control.
Prime Minister Benjamin Netanyahu has condemned the death of Mohammad Abu Khdeir and said he would act calmly and responsibly in the light of growing Israeli-Palestinian hostilities.
Hamas has offered Israel a 10-year truce if it accepts 10 conditions. The Jerusalem Post reported this, based on an Israeli Channel 2 newscast. According to Ma'ariv (Hebrew) these are the conditions:
Gaza teen's war tweets make her a social media sensation
As bombs explode in Gaza, Palestinian teenager Farah Baker grabs her smartphone or laptop before ducking for cover to tap out tweets that capture the drama of the tumult and fear around her.
The 16-year-old's prolific posts on Twitter have made her a social media sensation through the month-old conflict. Once a little known high school athlete, Baker's following on the Web site has jumped from a mere 800 to a whopping 166,000.
Living near Gaza City's Shifa Hospital, where her father is a surgeon, provides Baker with a live feed of blaring ambulance sirens in addition to blasts from Israeli air strikes and shelling attacks.
Travel offers to Palestine by the French and Dutch Airlines before 1948 "Declaration of Israeli state ".
6 stories of Palestinians killed in Gaza give a human face to the conflict
All of these people lived under siege in Gaza, trying to do what we all try to do: live their lives.
Please read this
so today i woke up by alarm sirens,
The beginning of summer vaction, Israel, 8:50, rockets fired at Israel from Gaza. rocket number? 226 in the past 24 hours. and it keeps going. in south Israel right now there's siren after siren, missile after missile 24/7. And i wanted to Increase the awareness, right now we suffer from a serious rockets attack and half of our country going back and forth from shelters every few minutes, and above all - living in fear. (A video from a couple of days ago - Alarm sirens in a swimming Pool) I went through the Israel tag on tumblr, Twitter, whatever, and everything there is just so wrong that i had to say something.
First, fabricated photos that being posted by Palestinians of bleeding children and women crying to make us look like monsters, truth is that those photos are from wars in iraq and syria and have nothing to do with Israel and i'm fucking tired of it, lies (here's a bbc Video research on this exact topic). we're being attacked by a ruthless terrorist organization, they have made hundreds of terror attacks through the years and lately, murderd Innocent people, and it's certainly not the first rocket attack, but nahh, Israel is a crule terror state that even dares (!!!) defend itself from over 7,000 rockets in the past ten years. are we attacking back? well, now, yes, yesterday Israel started an operation called "Operation Protective Edge" to attack back, but Unlike Hamas that fires rockets almost blindly to intentionally harm Israeli civilians, the IDF fires only where Hamas places the weapons and in the houses of the terrorists that fires them, IDF has no intention to harm innocent civilians, but sadly, Hamas hate us more then they care about their civilians, they do all this from densely populated areas and put their civilians in great danger.
I'm just asking you not to believe to every photo description you see and to know that is more complicated than you think. We have one jewish state in the whole plante, and if you try looking for it in a globe you'll see it's so small that even the name can't fit in, so that's what we have and we want to keep it safe. we have the right to defent ourselfs.
*the underlined stuff are links to news websites and proofs for what i'm saying.
*a link to the story of how it started in the last few weeks.
GAZA CITY : Flyers are dropped over Gaza City by the Israeli army urging residents to evacuate their homes on July 30, 2014. Israeli bombardments early on July 30 killed "dozens" of Palestinians in Gaza, including at least 16 at a UN school, medics said, on day 23 of the Israel-Hamas conflict. AFP PHOTO / MOHAMMED ABED
Palestinians repairing guns. Lebanon, Beirut. 1982
Palestinian women take cover as Israeli police used stun grenades to disperse a crowd trying to enter the compound known to Muslims as Noble Sanctuary and to Jews as Temple Mount in Jerusalem's Old City, November 5, 2014. Photo: Ammar Awad / Reuters
Nelson Mandela - Address by President Nelson Mandela at the International Day of Solidarity with the Palestinian People, 4 December 1997, Pretoria.
May you rest in Peace, and may Palestine find peace soon as well.
KHAN YUNIS : Palestinian youths practice their Parkour skills over the ruins of houses, which were destroyed during the 50-day Gaza war between Israel and Hamas-led militants in the Gaza Strip, on November 14, 2014, in Khan Yunis' Khuzaa neighbourhood in the southern Gaza Strip near the Israeli border. The 50-day war between Israel and Hamas militants killed at least 2,143 Palestinians, nearly 70 percent of them civilians, and 73 people on the Israeli side. AFP PHOTO / MOHAMMED ABED
As civilian casualties mounted on Monday in the Israeli ground invasion of the Gaza Strip, Israel's military reminded the world that it had warned people living in targeted areas to leave. The response from Palestinians here was unanimous: Where should we go?
United Nations shelters are already brimming, and some Palestinians fear they are not safe; one shelter was bombed by Israel in a previous conflict. Many Gaza residents have sought refuge with relatives, but with large extended families commonly consisting of dozens of relatives, many homes in the shrinking areas considered safe are already packed.
Perhaps most important, the vast majority of Gazans cannot leave Gaza. They live under restrictions that make this narrow coastal strip, which the United Nations considers occupied by Israel, unlike anywhere else.
Prime Minister David Cameron of Britain in 2010 called Gaza "an open-air prison," drawing criticism from Israel. But in reality, the vast majority of Gazans are effectively trapped, unable to seek refugee status across an international border. (Most are already refugees, those who fled from what is now Israel and their descendants.)
A 25-mile-long rectangle just a few miles wide, and one of the most densely populated places in the world, Gaza is surrounded by concrete walls and fences along its northern and eastern boundaries with Israel and its southern border with Egypt.
Even in what pass for ordinary times here, Israel permits very few Gazans to enter its territory, citing security concerns because suicide bombers and other militants from Gaza have killed Israeli civilians. The restrictions over the years have cost Palestinians jobs, scholarships and travel.
Egypt has also severely curtailed Gazans' ability to travel, opening its border crossing with the territory for only 17 days this year. During the current fighting between Israel and the Hamas militants who control Gaza, only those with Egyptian or foreign passports or special permission were allowed to exit.
Even the Mediterranean Sea to the west provides no escape. Israel restricts boats from Gaza to three nautical miles offshore. And Gaza, its airspace controlled by Israel, has no airport.
So while three million Syrians have fled their country during the war there, more and more of Gaza's 1.7 million people have been moving away from the edges of the strip and crowding into the already-packed center of Gaza City.


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23 Comments | Add Yours
by WinnieGirlie on 2/8/2013 10:47:59 AM
Hey Girlie! It's normail for young people to have feelings for both boys and girls! It's all a part of growing up!
by WinterK on 2/8/2013 10:09:14 AM
I have this feeling sometimes too! I don't wont to be gay or bi, but I just have that feeling sometimes. Everyone has a little gay in them! Lol
by YouCanCallMeCat on 2/8/2013 5:40:43 AM
QUIZ: Could you go Rogue?
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What is a notice of error under RESPA?
One of the powerful tools you have under RESPA is the "Notice of Error" which is a letter you send to your mortgage company where you tell them they made an error and you give them a chance to fix it. "What are the possibilities after I send a notice of error?" Two options: They fix it which is great. Problem solved. Or, they don't fix it. This leaves you some options: Do nothing Dispute again with a new notice… (Read more)


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No thanks to the 0rganizer.<quoted text>
It's you who are lying. We're drilling more oil wells, pumping more oil, and exporting more of it than ever before.
As usual, the truth is a stranger to you so you make shit up.
He's cut oil drilling.
There are 6 comments on the Jul 19, 2012, Reuters story titled U.S. Navy's "Great Green Fleet" debuts in Pacific. In it, Reuters reports that:
Unless Congress renews a host of expiring tax cuts the economy could fall back into a recession next year.
Join the discussion below, or Read more at Reuters.
"bar0ckalypse n0w" Since: Mar 10 19,328 |
Jul 23, 2012
No thanks to the 0rganizer. He's cut oil drilling. |
Jul 23, 2012
Are you really that stupid ??? You can't even research your own BS ???
Jul 24, 2012
No, that's pretty much just your imagination. |
"bar0ckalypse n0w" Since: Mar 10 19,328 |
Jul 24, 2012
WHITE HOUSE CRACKS DOWN ON REPORTERS' TWEETING BIDEN'S REMARKS... SOLYNDRA figures attend swank Obama fundraiser... USATODAYGALLUP POLL: Romney preferred over Obama to handle economy... Still trying to explain 'you didn't build that' comment... DICK MORRIS:'NASTY' OBAMA IN FAVORABILITY DIVE... |
Jul 24, 2012
Jul 28, 2012
LOL as the Fleet goes Green so do some landlubbers over by Californie'.
LA unveils $48 million solar power plant (KRMG-AM Tulsa) The Los Angeles Department of Water and Power has unveiled a solar plant it says can power 3,300 homes a year. Solar Power Deal Means 800 Jobs For San Antonio (Manufacturing) A solar energy deal has been announced for the San Antonio area in a project that backers say should create about 800 jobs. LOL and I havent even touched on the Parabolic solar plants out in the desert that are producing 500 MegaKWH per day. Thats per plant 3 that I know od at present. All it took the leadership of a positive orientated president like OBAMA to invest into this new techonology to get the republican's black toxic dirty hands off of our necks and holding us down Another four years of Obama's intelligent leadership and we will be once again a competing nation to be reckoned with. LOL Mitt would proably just outsource it all. Big bucks for him and a mouthfull of dust for us. |
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Ellis Minns
Sir Ellis Hovell Minns (1874 - 1953) was a British academic and archaeologist whose studies focused on Eastern Europe.
Educated at Charterhouse, he went to Pembroke College, Cambridge studying the Classical tripos including Slavonic and Russian.[1] He lived briefly in Paris before moving to St Petersburg in 1898 to work in the library of the Imperial Archaeological Commission. Returning to Cambridge in 1901 he began lecturing in Classics.
In 1927, he was appointed Disney Professor of Archaeology, a post he held until 1938. He wrote widely with books including Scythians and Greeks (1913) and The Art of the Northern Nomads (1944). He was an authority on Slavonic icons and in 1943 cleared the Russian translation engraved on the ceremonial "Sword of Stalingrad" presented by the British people in homage to the defenders of the Russian city.
- ^ "Minns, Ellis Hovell (MNS893EH)". A Cambridge Alumni Database. University of Cambridge.
External links[edit]
Wikisource has original works written by or about: Ellis Hovell Minns |
- Works by or about Ellis Minns in libraries (WorldCat catalog)
Academic offices | ||
Preceded by Sir William Ridgeway |
Disney Professor of Archaeology, Cambridge University 1926 - 1938 |
Succeeded by Dorothy Garrod |
This biographical article about a British archaeologist is a stub. You can help Wikipedia by expanding it. |


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Tech Helproom
It's free to register, to post a question or to start / join a discussion
Lost Data
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Posted May 10, 2013 at 4:42PM
Lost photos I had a problem that resulted is in all my photos being lost An attempt made by a technician I know to recover the data from my HDD on my PC. This was done and all the data was recovered to a separate HDD 1 TB. This took some time. I now have an HDD with all the recovered data on it. The trouble is I don't recognise the format and can't find the pictures. The technician said there were about a 1000. Should I be able to identify my pictures and transfer them to my PC? Or are they gone forever?. Regards
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McEvilley about Marina, Ulay, and Yves
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Addiction in America
Adolescents and Addiction
Treating addiction in adolescents can be trickier than with adults. In this episode, we will discover some of the reasons why.
Chasing Silhouettes – Emily Wierenga's Story of Recovery...
This episode will be a touching interview with this writer, revealing the inside story of her life and road out of anorexia. This interview will instill hope for those still suffering.
The Sexual Addiction Epidemic
This episode will be an eye opening interview Robert Weiss, LCSW, CSAT on the topic of compulsive and sexual addiction worldwide, how the internet exacerbates the problem, and his intervention work in the field
"Love First - Learning to Love Ourselves" - Interviews...
In this episode, we will talk with Jeff Jay about relationship intervention and indicators as to when it is needed.
The Egoless Self: Interview with Dr. CC Nuckols
This episode will be a discussion of The Egoless Self: Acheiving Peace and Tranquility Beyond all Understanding, Dr. Nuckols latest book. Join us for a lively discussion of transcending character defects and working toward greater enlightenment.
Spirituality in Recovery
This episode will be a general introduction to understanding traditional 12 step concepts with excerpts and readings from the literature.
Addiction Isn't One of Life's Last Pleasures: A Look at...
n this episode, we will look at the growing problem of addiction in the aging population and interview one of the pioneers in the development of treatment in this field. We will be reviewing Dr. Colleran's book , co-written with Debra jay, entitled...
The Truth Behind the Mask
In this episode, we will interview Dr. Jon Caldwell, psychiatrist at the Meadows Treatment Center in Wickenburg, AZ. He will address how early life attachment and bonding affects Emotional Stability and addiction in later life. We will address how he...
Cutting EdgeTreatment for Eating Disorders
In this episode of Addiction in America, we will be interviewing Dr. Cathy Reto, Director of the Eating Disorders Program at Pine Grove Treatment Center. We will get a good overview of the issues and then talk about treatment methods, including...
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Dunnellon breezes past Palatka
Published: Saturday, May 2, 2009 at 6:30 a.m.
Last Modified: Saturday, May 2, 2009 at 12:33 a.m.
DUNNELLON The sting still stung, the wound never fully healed.
Heading into Fridays regional semifinal softball game against visiting Palatka, heavily favored Dunnellon just couldnt shake the memory of a jarring 6-5 season-ending loss to Green Cove Springs Clay in the exact same spot one year ago.
We were all pumped up because of what happened last year, junior ace pitcher Kasey Fagan said. We knew what was on the line.
Maybe thats why the Tiger offense was flat for three scoreless innings before erupting late for an 8-0 win and a berth in the Class 4A Elite Eight. The Tigers (29-1) will visit Osceola Harmony which knocked off Dade City Pasco 7-6 on Friday this Tuesday with a trip to the state final four on the line.
As is often the case, Kasey Fagan led the way for Dunnellon. The hard-throwing junior was perfect for 4 1/3 innings before surrendering her only hit of the game. She ended up facing just two batters over the minimum, struck out 14 and didnt walk a batter.
Kasey Fagan also broke the ice offensively in the bottom of the fourth when she ripped a single into center field to plate Tori Williams, who had led off the frame with a bunt single and stole second base.
Kasey Fagan eventually scored on a pinpoint squeeze bunt by Kristie Hanewinckel to make it 2-0. For good measure, the Tigers added two runs in the fifth and four in the sixth to pull away.
Once one person hits, we all start to hit, Kasey Fagan said. Its kind of contagious with our team.
Williams went on to single in a run in the fifth and was the catalyst for a second run that inning when her fourth stolen base of the game drew a throw, allowing Sami Fagan to score from third. Williams finished 3-for-4. while Sami Fagan was 2-for-4 and Danielle Burns was 1-for-3 with two RBIs.
Lydia Houghs single was Palatkas lone hit. Jessica Gornto took the pitching loss despite striking out the side in the first inning and holding the heavy-hitting Tigers at bay into the fourth.
Dunnellon coach Kevin Fagan attributed the slow start to anxiety.
I told them to stop pressing, they were so excited, he said. If this team has a negative, thats what it is. They can press too hard.
If Dunnellon can survive Harmony on Tuesday, it would get a full 10 days off before the state semifinals take place May 15 in Plant City.
Fagan fully expects his team to be on a bus that day.
If we play the way we should play, he said, well go through to the next round.
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Thursday, 05 Sep 2013 07:16 PM
San Antonio, Texas, approved a measure on Thursday that outlaws discrimination against gays, despite fierce opposition from conservatives and marking a victory for Mayor Julian Castro, who is considered a rising figure in the national Democratic Party.
The proposal, which added "sexual preference and gender identity" to groups protected in places such as restaurants and housing, sparked weeks of emotional debate that pitted top Republicans in the state against Castro and other supporters.
"This ordinance fundamentally is about insuring that whether you are white or black, whether you are Christian or Jew, whether you are straight or gay, this city belongs to you, too," Castro said.
By approving the measure 8-3 in the city council, San Antonio joins 180 other U.S. municipalities, including four major Texas cities, to bar such discrimination, according to Paul Guequierre, a spokesman for the Human Rights Campaign, a gay rights organization. In Texas, Austin, Brownsville, Dallas, and Fort Worth have laws on the books that are nearly identical to the one in San Antonio.
Greg Abbott, Texas state attorney general and the front-runner to be the next governor of the state, campaigned against the measure, as did Texas Sen. Ted Cruz, an outspoken conservative.
"This proposed ordinance runs contrary to the Texas constitution, which defines marriage as the union of one man and one woman," Abbott said.
Two public hearings in the nation's seventh-largest city attracted hundreds of participants who invoked everything from the famous 19th century defenders of the Alamo in San Antonio to the 1960s black civil-rights movement.
Some called homosexuality a "filthy lifestyle," and supporters said opponents were "mean spirited, and bigoted."
The Republican-led Texas Legislature has not approved similar protections statewide, and opposition to same-sex marriage or civil unions is strong among Republicans, who hold every statewide office in Texas.
"This does not attempt to legalize same-sex marriage," San Antonio City Attorney Michael Bernard said. "It does not regulate anybody's speech or action."
Gerald Flowers, a prominent San Antonio pastor, called the ordinance offensive and said it puts Christians who oppose homosexuality in the position of being permanent second-class citizens.
"This thing is so central to the heart of so many people in this city that we cannot let it rest," Flowers said. "This doesn't end today."
The Liberty Institute, a nonprofit group that advocates religious freedom, has said it may file a federal lawsuit to block the measure.
Castro, who delivered the keynote address at the 2012 Democratic National Convention, is seen by some Democrats as a potential future Texas governor or national politician representing a state with a rapidly rising Hispanic population.
© 2015 Thomson/Reuters. All rights reserved.
Tuesday, 12 Nov 2013 19:48 PM
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$70k contest for Lyttelton spruce-up
$70,000 contest to spruce up heritage site
SAM SACHDEVARelevant offers
Visual Art
Christchurch artists are being given a chance to showcase their talents and brighten up Lyttelton's future civic square.
The Christchurch City Council has opened a contestable $70,000 fund for artists to pitch temporary projects for the site at 44 London St.
In July, the council bought the site where the heritage Albion building once stood, home of the earthquake-hit Ground Culinary Centre.
The council plans to transform the site into an outdoor gathering space for Lyttelton residents.
Lyttelton artist and Harbour Arts Collective spokesman Trent Hiles, who helped the council to develop the transitional project, said residents wanted to "bring life" to the area while permanent- construction plans were being developed.
The funding could go to one large project or several smaller ones, with applicants given "a blank canvas" to work with.
Hiles said artists had been hit hard by the quakes and needed more chances to show off their talents.
"We've lost studio spaces, we've lost gallery spaces, so it's important that we provide artists with opportunities to put their work on public display within their own community."
He said there was already strong interest from Lyttelton artists.
He hoped good projects could find a permanent home in the area.
"I can imagine that if there's a work created with enough significance it could well remain and be permanently installed," he said.
In the council's master plan for the township, the London St site could become the new home of the Lyttelton War Memorial Cenotaph.
Funding applications for the project will close on January 31.
- The Press
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Timothy Foley jailed for life for crowbar murder
David Havili goes from school bench-warmer to Crusaders starter
Pensioner living in his car, Mervyn Cross, overwhelmed by help
Richie McCaw focused on Crusaders win, not head or sentiment in Christchurch
Masseur jailed for indecent assault


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FANTASTIC two bedroom duplex apartment in this modern and popular development in the lovely semi rural area of Walton-Le-Dale. Finished to a high standard with dishwasher, washing machine, fridge and freezer, as well as allocated parking. Good access for motorways. More details ›Added on 14/04/2015 by Martin & Co, Preston - Lettings & Sales. Call: 01772 399112 Local call rate
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Don't get the chef's special. Stick to what you know!! by IanandSarah on 03/19/2008I recently ate dinner at the Ocean House and was lured into trying the Chef's Special (Swordfish with some kind of mango sauce) by the waitress. It sounded great, but tasted like something I could have paid $5 for at Long John Silvers. The waitress asked how my food was and I told her it wasn't very tasty. She did nothing about it at that point, which was a little unsatisfying. The scenery of the Ocean House was perfect, right on the beach. The service was also very good. We were seated rather quickly, always had fresh water, and the food was ready in no time at all. My wife had the seafood linguine and was satisfied with her dinner, but wasn't thoroughly impressed by it either. All in all I paid $100 to sit and eat dinner on the beach. I should have just bought a Subway sandwich and had dinner on the sand (same view with much more money left over for sights and attractions).
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Remember when President Obama attended the DC Correspondent's Dinner the same night the mission to kill Bin Laden was underway? Remember how awed both Republicans and Democrats were that President Obama made jokes, was cool as could be that night?
Mitt Romney, Paul Ryan and the rightwing talking heads have their panties in a bunch over President Obama allowing a pre-taped showing (taped Monday) of the View be aired on the day Foreign Leaders are in NYC at the UN.
Romney, Ryan and the rightwing talking heads are implying that President Obama must not take Foreign Policy seriously if he isn't sitting in a New York hotel holding meetings with Foreign Leaders who are attending the UN General Meeting?
So, does that mean Romney thinks President Obama should have cancelled on the DC dinner the night he ordered Bin Laden killed?
Let's see, President Obama taped the View on Monday day and ... President Obama spent Monday night at a UN Reception with Foreign Leaders of Foreign Countries. But, according to rightwinged talking heads, that fact is no excuse for Obama declining to meet with other Foreign Leaders one-on-one for you know, no apparent reason.
Eric Cantor, who on January 20, 2009 plotted to sabotage the US Economy in a 4 hour covert meeting with Paul Ryan and 10 other Republican members of Congress complained about President Obama and said:
CANTOR: "The president's unwillingness to meet with Bibi Netanyahu when he is in New York but instead willing to go on the 'The View' in New York – I mean, I think it speaks volumes to the lack of seriousness with which the president is taking the current situation,"Republicans will never be accused of letting facts get in the way of their bullsh!t. The fact is, President Obama did not turn that down a meeting with Bibi Netanyahu due to time pressure of pre-taping "The View" show. Um ... Fact is, Prime Minister Netanyahu is not in New York in the days President Obama is in New York. And President Obama is not in New York on the days when the prime minister, Netanyahu, will be in New York.House Majority Leader Eric Cantor (R) of Virginia in a Monday conference call organized by the Romney campaign.
Oh, and let's not forget, last week President Obama had an hour long telephone conversation with Bibi.
Ya know, since 2009 the rightwing have been complaining that President Obama isn't kissing Bibi Netanyahu's yahu. And the rightwing complaints have nothing to do with actual facts but everything to do with the January 20, 2009 covert meeting where 12 Republican members of Congress plotted to undermine the President of the United States as was reported in Robert Draper's book, "Do Not Ask What Good We Do: Inside the U.S. House of Representatives."
And today, right now, Romney Foreign Policy Adviser, rightwing warmonger Dan Senor, whose advice got 5000 US Troops killed searching for imaginary WMD in Iraq when he worked in Bush/Cheney Administration, is telling NBC that it's President Obama's fault that Iran is close to a nuclear weapon.
hmm ... I'm waiting for Dan Senor to tell NBC that Iran was twiddling their thumbs between 2003-2008 when Bush, Cheney, Senor and other Bush Advisers had our Troops dying and getting maimed searching for Senor's imaginary WMD.
Romney can't aim straight and talk at the same time. Consequently, the rightwing is so jealous of President Obama that they literally had to plot, in a 4 hour covert meeting, to undermine President Obama on the night he was inaugurated.
By the way, Romney keeping his Foreign Policy Plan, Economic Plan, Tax Plan, Energy Committee are "secret" from voters is not a sign of a leader -- those are signs of a sneak ... a sneak who cannot be trusted as President.


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Family: | Rosaceae (ro-ZAY-see-ee) (Info) |
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With the rapid development of internet, explosive growth of social network creates large-scale social network data. In order to discover the potential value of the social network data, many analysis methods have been developed. However, using prior knowledge about the subgraph structure of a given network, it is possible to identify a target node or infer some useful information. In this paper, we mainly consider how to prevent such subgraph attack, and propose a practical method to battle it. We use iterative hash to detect the isomorphic subgraph structures and try to greedily match the anonymous subgraphs. Empirical queries on anonymized social network shows both the security and utility advantage of our algorithm.


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US 8128959 B2 Abstract The present invention provides a polymeric agent which can incorporate a large amount of a drug, accumulate selectively in a tumor site, and has a molecular size of more than that for renal excretion. A metalloporphyrin derivative (such as zinc protoporphyrin) is associated with a styrene-maleic acid copolymer via non-covalent bond to give a SMA micelle complex, allowing provision of a polymeric pharmaceutical agent for treatment of cancer with a large amount of the drug incorporated. The SMA micelle complex can be produced by a method, wherein the metalloporphyrin derivative reacts with the styrene-maleic acid copolymer in the absence of a condensation agent under an alkaline condition, solubilized, adjusted to have a pH of 6-8, and subjected to a procedure for separating a polymer component to recover the micelle complex component for the polymeric pharmaceutical agent.
Claims(7) 1. A freeze-dried SMA-zinc protoporphyrin micelle complex comprising a zinc protoporphyrin and a styrene-maleic acid copolymer, wherein the zinc protoporphyrin and the styrene-maleic acid copolymer are non-covalently bonded.
2. A polymeric pharmaceutical agent for treatment of cancer, comprising the freeze-dried SMA-zinc protoporphyrin micelle complex according to
3. The polymeric pharmaceutical agent according to
4. A method for producing the freeze-dried SMA-zinc protoporphyrin micelle complex according to
mixing a zinc protoporphyrin with a styrene-maleic acid copolymer in the absence of a condensation agent in an alkaline solvent to dissolve the zinc protoporphyrin and styrene-maleic acid copolymer,
adding an acid to the resulting mixture to form a precipitate,
adjusting the pH to 6 to 8 to dissolve the precipitate,
subjecting to a polymeric component separation procedure to recover the SMA-zinc protoporphyrin micelle complex, and
freeze-drying the complex.
5. The method for producing the freeze-dried SMA-zinc protoporphyrin micelle complex according to
6. The method for producing the freeze-dried SMA-zinc protoporphyrin micelle complex according to
7. The method for producing the freeze-dried SMA-zinc protoporphyrin micelle complex according to
Description The present invention relates to a polymeric pharmaceutical agent for treatment of cancer wherein a pharmaceutical drug for treatment of cancer is used to form a polymeric micelle complex which is selectively accumulated in lesions such as tumor regions (hereinafter designated as tumor region), is retained in the tumor regions for a longer period of time to reduce frequency of drug administration, thereby enhancing the anti-tumor effect and reducing side effects to normal organs and tissues, and also relates to an improved method for production of the same. In more detail, the present invention relates to a micelle complex wherein a metalloporphyrin (hereinafter designated as MePP) is associated with a styrene-maleic acid copolymer (hereinafter designated as SMA) to form a polymeric micelle complex having a size larger than that of a molecule that can be excreted by the kidney, a polymeric pharmaceutical agent for treatment of cancer comprising the complex as an active ingredient, and a method for producing the polymeric pharmaceutical agent for treatment of cancer wherein the aforementioned metalloporphyrin reacts directly with the SMA at a specific pH in the absence of a condensation agent to get a specific stereo-configuration. In general, a drug such as an anti-cancer drug, which is administered orally or by injection, does not have the effect specific to the target lesion, and therefore, can not sufficiently exhibit the effect even if it is a potent drug, and besides, affects the normal organs and tissues other than the lesions with severe side effects. Dosage of such a potent drug is suppressed to increase due to its possibility to cause a side effect. This is the reason why the system for a lesion-oriented drug, called a drug delivery system (DDS), is continuously and competitively researched and developed worldwide. The DDS research is important especially in the field of anti-cancer drugs which have potential to bring about many side effects. Focusing on the fact that an anti-tumor drug can be polymerized to become a lesion-oriented and sustained-release type agent, the present inventors found earlier a unique phenomenon that a polymeric agent having a molecular weight of 40 kda or more accumulates selectively in the tumor tissues and is retained there for a longer period of time, and then designated this phenomenon as an EPR (enhanced permeability and retention) effect (non-patent document 1). This phenomenon is observed in polymeric agents and lipid micro-particles and the like. Up to now, based on such observations the inventors produced many polymeric agents obtained by reacting drugs with various polymers. It was found that these polymeric agents exhibited a high rate of accumulation in tumors and inflammed lesions via the EPR effect described above, and that as the result, they became superior polymeric anti-tumor agents which were excellent in anti-tumor effect and had few side effects on normal organs as compared to low molecular weight anti-tumor drugs (Patent document 1, Patent document 2, Patent document 3 and Non-patent document 2). Among these polymeric anti-tumor agents, the polymeric anti-tumor agent described in Patent document 3, which has a polymeric micelle complex structure formed by associating a low molecular weight anti-tumor drug with a styrene-maleic acid co-polymer (SMA) via non-covalent bonding (hereinafter designated as SMA micelle complex), has been found to be a superior anti-tumor agent that has an especially superior anti-tumor effect and also had few side effects on normal organs.
Meanwhile, the present inventors proposed earlier in the aforementioned patent document 2 that a metalloporphyrin derivative such as zinc-protoporphyrin represented by Formula (1) (hereinafter designated as ZnPP) which has an inhibitory activity on heme oxygenase could be conjugated with polyethylene glycol (PEG) to provide a polymeric anti-tumor agent. The metalloporphyrin derivative is an inhibitor of heme oxygenase (HO-1) which is induced in inflammation lesions and tumor lesions. ZnPP itself is insoluble in water. In order to solubilize it in water, the present inventors have conjugated it with amphiphilic polyethylene glycol (PEG) having an average molecular weight of 100-20,000 (preferably about 5,000) (patent document 2) to create a water-soluble derivative thereof. This PEG-ZnPP conjugate has a molecular weight of about 68,000. Thus, the in vivo behavior as a polymer is important to express the EPR effect described above. The polymeric agent, which comprises only one molecule of ZnPP bound to PEG having a large molecular weight (in this case MW 11,000), must be administered by an amount as large as a few grams in order to supply a human with the active ingredient at a certain effective dosage or more. This means that an increased amount of the drug must be administered to a patient, and in reality, a few g to 250 g is needed to administer to attain the effective blood concentration, indicating that the protocol is impractical to perform. Further, in Patent document 2, polyethylene glycol (PEG) was regarded as the best amphiphilic or water soluble polymer, but had to be bound to ZnPP via a diamine structure because it was difficult to conjugate directly. In the Patent document 2, in addition to PEG, SMA also was used as the polymeric compound but there was no specific disclosure. In addition, it was described that SMA also had to be reacted by dehydration condensation with an amino group-introduced on to the porphyrin to polymerize in the similar manner as seen in PEG. Also, Patent document 3 described above, though there was no description of SMA-metal PP derivatives, disclosed a method for producing various low molecular anti-tumor drug-SMA micelle complexes, wherein a derivative of SMA such as a half-butyl ester reacts under an acidic condition in the presence of a dehydration condensation agent such as soluble carbodiimide, adjusted to have a pH of 8 or higher, then adjusted into a neutral pH zone, and subjected to separation/purification procedure for polymeric components, for example, gel chromatography such as Sephadex and an ultrafiltration membrane to recover the polymeric components. According to this method, micelle pharmaceuticals can be produced without using a generally used micelling agent or an emulsifier (such as sugar ester, phosphatidylcholine, sphingosine, and cholesterol) that is an essential component for the liposome formulation. However, this reaction requires a costly dehydration condensation agent such as water soluble carbodiimide. Further, when such a condensation agent was used, it was extremely difficult to remove the remaining condensation agent completely, and the complete removal could create problems such as a decrease of the drug activity, and it was difficult to put in practical use. The SMA-ZnPP micelle obtained by this method had a problem that the molecular weight was significantly smaller than the molecular weight limit for renal excretion. Thus, the present inventors conducted research to obtain a polymeric agent which comprises SMA added to MePP to contain a large amount of the drug, and found that reaction steps are controlled to have their respective pHs to give a micelle complex of a metalloporphyrin derivative and styrene maleic acid copolymer, allowing solubilization and incorporation of the metalloporphyrin into the micelle. This micelle complex has a polymeric micelle complex structure formed by association of a metalloporphyrin derivative and a styrene-maleic acid copolymer by non-covalent bond, and can incorporate the drug at a content as high as 10 to 60% in the micelle complex. Thus, this simple method gives a micelle a small amount of which (0.1-6 g per human) is administered to provide the efficacy. It was found that the polymeric pharmaceutical agent for cancer treatment (hereinafter designated as SMA micelle complex) thus obtained is excellent in anti-tumor effect and has few side effects on normal organs. Here, the pharmaceutical agent for cancer treatment includes not only anti-tumor drugs that kill tumors directly but also drugs used for cancer treatment such as photosensitizers that are given before performing radiation and laser therapy, or inhibiting drugs of intracellular signal transduction. Further, the pharmaceutical agent for cancer treatment includes agents not only for solid cancers but also for all various cancers such as lymphoma and leukemia (including adult T-cell leukemia, AIDS related T cell leukemia). Furthermore, the inventors studied a simpler and less costly method for producing such an anti-tumor agent, and as the result found that SMA can directly react with a drug at a specifically adjusted pH in the absence of a condensation agent to produce a high purity of the agent efficiently. In addition, this method does not need a reaction procedure for adding diaminoethane to protoporphyrin to introduce an amino group as disclosed in Patent document 2. That is, the present invention is an SMA micelle complex, wherein a metalloporphyrin derivative is associated with a styrene-maleic acid copolymer via non-covalent bond, and also a polymeric pharmaceutical agent for cancer treatment comprising the same as an active ingredient. Also, the present invention is a method for producing the aforementioned SMA micelle complex, wherein a metalloporphyrin derivative reacts with a styrene-maleic acid copolymer in the absence of a condensation agent under an alkaline condition to get a dissolved product, which is then adjusted to have a pH of 6 to 8 and subjected to a polymeric component separation procedure (for removing a low molecular weight fraction) to recover a polymeric micelle complex component. The SMA micelle complex of the present invention is a micelle complex wherein a metalloporphyrin derivative is associated with an SMA via non-covalent bonding as is quite different from what is described in Patent document 2 mentioned above, and has a greatly increased molecular weight of around 130,000, or 160,000 or above, and hence is more selectively accumulated in a tumor region and retained there for longer period of time. Thus this is more useful as an anti-cancer agent in respect to a superior anti-tumor effect and few side effects on normal organs. Furthermore, according to the method for production of the SMA micelle complex of the present invention, the product can be synthesized by a simple procedure from a metalloporphyrin derivative and an SMA without using a condensation agent, and the highly purified product can be obtained by a simple purification process. The metalloporphyrin derivative is a complex compound in which a metal coordinates with a compound having a porphyrin ring. The compound having a porphyrin ring includes protoporphyrin which is available and preferably used. The metal to coordinate is not particularly limited so long as it is not toxic like mercury or difficult to coordinate like a univalent metal, but may be different depending on usage. When used as an anti-tumor drug, iron that does not possess a heme oxidase inhibitory activity is unsuitable, but zinc, tin, cobalt, nickel, copper and the like can be used and especially zinc is preferable. Zn-protoporphyrin (ZnPP) in which protoporphyrin coordinates with zinc are shown in following Formula (1)
Further, a heme in which iron is coordinated, although it is unsuitable for an anti-tumor drug, can be used as a radiation sensitizer in radiation therapy. The SMA micelle comprising the heme can be administered to accumulate in a tumor site, allowing site-selective radiation therapy. Alternatively it can be used to provide a catalytic function required for generating radical molecules (R., ROO., R.). The heme that can be used includes a heme that is an iron complex of porphyrin and a hemin (hemin chloride) that is trivalent iron porphyrin coordinated with a chloride ion. Various metal PPs used as anti-tumor drugs described above such as ZnPP can also be used as radiation sensitizers. SMA used as a polymerization agent in the present invention is obtained by co-polymerization of styrene and maleic anhydride, and is a co-polymer having the repeated units shown by following formula (2) or (3) and contains styrene and maleic anhydride as essential components. In the present invention, the SMA may be used intact as the anhydride copolymer or may be a styrene-maleic acid (or a half alkyl ester) with the completely opened ring as disclosed in Patent document 3. The anhydride copolymer is preferably used because it can be simply and easily produced without additional operations such as hydrolysis, while the styrene-maleic acid with the completely opened ring also can be preferably used because it advantageously does not need an extremely high pH (12 or above) to form the micelle in a short period of time, allowing prevention of a drug from degradation caused by strong alkalinity. SMAs have various molecular weights depending on polymerization degree. SMA to use in the present invention as a polymerization agent has preferably a size of a trimer (about 660 Da) to about 40 kDa. More strictly, the molecular weight from 800 to 2500 is preferable because the SMA is not accumulated in the body and excreted easily out of the body. For producing the polymeric micelle complex by the reaction of MePP and SMA, in the case of using Znpp, SMA (anhydride or hydrolysate) is mixed with ZnPP, and the mixture is supplied with an alkaline solution such as sodium carbonate to alkalize and heated under stirring. Sodium carbonate is appropriately added to maintain the alkaline condition. After all the components are solubilized, the mixture is neutralized with an acid to precipitate the micelle product. The drug is efficiently incorporated into the micelle. The mixture is further is adjusted to have a pH of neutral region to dissolve, and subjected to a separation/purification procedure of polymeric component such as ultrafiltration and column chromatography to recover the polymeric component. The procedure described above changes the stereostructure of the SMA to facilitate incorporation of the low molecular weight drug into the SMA micelle by inter-molecular interaction, and thus the micelle structure of interest is formed. The reaction between MePP and SMA may be performed by dissolving MePP and/or SMA anhydride in an organic solvent. Compounds insoluble in water can be dissolved in the organic solvent such as tetrahydroxyfuran and dimethylsulfoxide. The solvent to use for SMA include, acetone, teterahydrofuran, dimethylformamide, dimethylsulfoxide, methyl cellosolve, acetonitrile, ethyl alcohol, and glycerin, and especially acetone and acetonitrile are preferable. The concentration in the organic solvent solution is preferably 1-30%. Here, pyridine, diaminoethane and the like may be added as a catalyst. The reaction between MePP and SMA may be sonicated with ultrasonic waves. They can be sonicated with ultrasonic waves to form the micelle in a shorter period of time more efficiently. The condition of ultrasonication is, for example, 1 minute on and 1 minute off for 5 to 60 minutes, and it is continued at least for 5 to 10 minutes. An ultrafiltration membrane having a cutoff molecular weight of 3,000-50,000 is preferably used to separate polymeric components. More preferably the cutoff molecular weight is 30,000-50,000. SMA-ZnPP produced by the present method has a molecular weight of 40,000 or higher. More preferably the apparent median molecular weight is 130,000-180,000. As described above, only the materials, MePP and SMA, can be used to produce the polymeric pharmaceutical agent for treating cancer of the present invention without a subsidiary component such as a surface active agent and a dehydration condensation agent(s) needed to use. The stable micelle complex structure consisting only of SMA and MePP can be prepared by a simple procedure. Further, as necessary, these micelles can be prepared in the presence of a stabilizer such as lactose, mannitol, amino acid, glycerin, and lecithin in an amount 1 to 100 times as much as the drug. The polymeric micelle complex pharmaceutical agent for treating cancer of the present invention has a polymeric micelle complex structure formed by the interaction between MePP and SMA, wherein MePP is incorporated in the micelle, and the bond formed between MePP and SMA is a hydrogen, hydrophobic or ionic bond, and is not a covalent bond such as an amide or ester bond. This will be demonstrated by an infrared absorption spectrum of Needless to say, the micelle type SMA-MePP complex produced in this way, as seen in conventional polymeric agents, is provided with unique pharmacological characteristics compared to the original low molecular weight drugs, and also has the following superior characteristics as an agent compared to the product produced by the method of Patent document 3. While the SMA-drug micelle complex according to the conventional method had a molecular size of 40,000 or less, the SMA micelle complex obtained by the present invention is highly polymeric to have a molecular size of as much as 100,000 or more, about 130,000-180,000, which exceeds the molecular weight of 40,000 for the renal excretion limit. This results in a big improvement in blood concentration and retention to exhibit the EPR effect. The SMA micelle complex obtained by the present invention contributes greatly to improving various anti-cancer drugs to convert to tumor-selective agents. In addition, the micelle has a greatly increased drug content (w/w 40-60%) compared to normal liposomes (w/w 10-20%). A dehydration condensation agent such as carbodiimide, which is generally used to form a micelle, is very difficult to remove from the formed micelle, and is recognized to remain as a residual nitrogen even after 5 times purification. However, since the present invention does not use a condensation agent and a catalyst, the formed micelle is not contaminated with them, and thus is expected to be free from side effects caused by them. Furthermore, since this product is intravenously administered to accumulate in tumor tissues via EPR effect, only the tumor tissues incorporating ZnPP can be irradiated with a same dosage of electromagnetic wave (gamma ray, x ray, ultraviolet ray, and alpha ray) to damage more by the radiation sensitizing effect of ZnPP (or other metal PP), allowing cancer therapy with a higher anti-tumor effect. That is, the polymeric pharmaceutical agent for treating cancer can be used not only as an anti-tumor agent but also as a photosensitizer. 200 mL of 0.1 M NaOH is added to 1.5 g of styrene/maleic anhydride copolymer having an average molecular weight of about 1,500 to bring to pH 13, and the mixture is stirred by a magnetic stirrer. While stirring, 1.5 g of finely powdered zinc (Zn)-protoporphyrin is added and continuously stirred. In the course of time, the turbid suspension becomes a dark wine-red clear solution. Insoluble ZnPP and other residues are removed by centrifugation (3,000 rpm) and the pH is lowered to around 7, and this solution is mixed with about 3 volumes of 10 mM Na2CO3/NaHCO3 solution and stirred continuously. After 2 hours, the mixture is supplied with an appropriate amount of 0.1M HCl to adjust the pH to about 7, and stirred continuously for another 2 hours. Next, the solution was concentrated to 50 mL under pressure using an ultrafiltration membrane with a molecular cutoff size of 3,000 (Amicon Inc.). By this procedure free ZnPP, or non-micelled SMA or derivatives and degradation products thereof are removed. Still further, this concentrated SMA-ZnPP micelle-containing fraction is diluted with about 20 volumes of pure water, and then concentrated/washed using an ultrafiltration membrane (cutoff molecular weight 5,000) under pressure as described above. The SMA micelle of ZnPP does not leak out of this membrane and only each free low molecule component is leaked out. By this operation the micelles can be washed. The last 3 or more operations are performed using distilled water and similar operations are repeated a total of 3-5 times and then the micelles are freeze-dried to obtain powder for an injection material. It is seen that SMA-ZnPP micelles of the present invention do not have covalent bonds between SMA and ZnPP and are associates via non-covalent bonds. To demonstrate this point, the infrared absorption spectra are shown in comparison with that of PEG-ZnPP. The purified product does not pass through an ultrafiltration membrane with a cutoff molecular weight of 100,000, and the size distribution is relatively homogeneous. The UV/visible absorption spectrum is shown in (Treatment Efficacy) Table 1 demonstrates the efficacy of the treatment on rabbit VX-2 tumor using the SMA-ZnPP micelle complex obtained in Example 1.
As shown above, the SMA-ZnPP micelle complex demonstrates a strong anti-tumor effect, and the potency is superior to PEG-MePP. (Photo Sensitization Effect by Laser Flash Photolysis) The photosensitizing effect of SMA-ZnPP was evaluated by comparing with that of PEG-ZnPP by the flash photolysis method on Jurkat cells under normal cell culture conditions. The results of (Cytotoxicity of SMA-Znpp and Peg-AnPP Under Light Irradiation) Jurkat cells that are lymphocytes were cultured in Dulbecco's MEM medium under a 5% CO2 air atmosphere at 37° C., and the survival rate of Jurkat cells was spectrophotometrically determined by MTT method 24 hours after the light irradiation. The results are shown in
50 ml of deionized water is added to 300 mg of completely alkali-hydrolyzed SMA placed in a 200 ml beaker, and the mixture is dissolved under stirring by a magnetic stirrer, and then 0.1 M NaOH is added dropwise to adjust the pH to 10. 100 mg of Hemin (Sigma Inc.) is dissolved in 4 ml of DMSO (dimethylsulfoxide) in a 20 ml glass vial, and this solution is added dropwise in the aforementioned beaker under stirring to mix. Then, 1 M NaOH is added dropwise to lift the pH up to 12, and the mixture is stirred for 15 minutes and then supplied dropwise with 1 M HCl to bring the pH down to 2. The mixture turns to a dark brown suspension, and is stirred continuously for 30-60 minutes to dissolve. Next, the precipitates and supernatant are separated by centrifugation (3000-6000 rpm), and further 30 ml of 0.02 M acetic acid solution is added, and after stirring again (30 minutes), 0.1 M NaOH is added dropwise to this aqueous suspension of SMA-micelles to lift the pH up to 10. After stirring for 30 minutes, the pH is brought down to 7.4 again with 0.1 M HCl to obtain a dark brown, perfectly clear solution. The above operations are performed at room temperature. This solution is repeatedly concentrated and washed in the similar manner as in Example described above using an Amicon molecular sieve membrane with a cutoff molecular weight of 10 kDa, and then freeze-dried to make powder. A part of the micelles thus obtained (0.5 mg/ml) is dissolved in water, and this aqueous solution was used to obtain a light scattering profile shown in Many low molecular weight pharmaceutical agents for treating cancer are not selectively accumulated in tumor regions, and for that reason cause severe side effects on normal organs and tissues, even if they have a strong anti-tumor effect. Thus their dosages are limited. The micelle complex is formed between such a drug and SMA and the polymeric pharmaceutical agents for treating cancer having a molecular weight of 50,000 or more is produced to exert the EPR effect, thereby to improve the anti-tumor effect and to reduce markedly the side effects on normal organs and tissues. The present invention makes it possible that an anti-tumor drug, ZnPP, or a radiation sensitizer, MePP such as heme protoporphyrin is associated with SMA by non-covalent bonds to form the micelle complex, allowing incorporation of a large amount of the drug into the micelle. Further, the complex, which has a molecular weight of the renal excretion limit of 40,000 or more, is greatly improved in blood concentration and blood retention, and is incorporated into cells efficiently with the EPR effect exerted, thereby to show a greater biological activity and to provide a superior efficacy as a pharmaceutical agent for treatment of cancer. Furthermore, the present invention makes it possible that such a drug reacts with SMA to form the micelle complex at a specific pH, thereby to need neither a dehydration condensation agent nor other emulsifier that is generally difficult to remove from the complex. Thus, the method can omit the purification step to simplify the process, and can avoid the use of a dehydration condensation agent to provide a high purity product. Patent Citations
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