One week before War of the Spark is officially released, Magic: The Gathering fans can head to the Star City Game Center in Roanoke, Virginia, for a weekend of cracking packs, building decks, and trying out all the exciting new War of the Spark cards!
Join hundreds of fellow fans who love Magic: The Gathering as much as you do and make new friends as you experience War of the Spark for the first time!
Here are a few reasons why you won't want to miss the War of the Spark Prerelease Celebration at the Star City Game Center April 26-28!
To kick off War of the Spark Prerelease Celebration, we'll be hosting several exciting constructed events! Standard and Modern win-a-box eight-player pods will begin at 7pm and continue to fire throughout the evening, with first place receiving one War of the Spark booster box! Win-a-box champions will be able to collect their booster boxes first-thing Saturday morning! Additionally, we'll have FREE-Standard and Modern FNM at 7pm, with all participants receiving a Standard-legal promo card!
The Star City Game Center will host six Prerelease flights that will be firing all day—three Individual flights and three Two-Headed Giant (2HG). Events will begin at 9am and continue until 7pm that evening. As if experiencing the new set early isn't cool enough, an on-site food truck will be available, as well as prize-wheel spins for each flight you enter!
Fans who can't make the main event Saturday or have a Limited itch that hasn't quite been scratched, will be excited for the return of Sunday flights! With the Prerelease of War of the Spark, we've added two more limited events on Sunday, April 28, one Individual flight and one Two-Headed Giant! Both events will fire at 10am, so be sure to sign up early!
Featuring art by Diego Machuca, Coup D'Paw is the latest limited-edition Star City Games Prerelease Exclusive Creature Collection playmat! Fans participating in one or more of our War of the Spark Prerelease flights now have the option to upgrade any of their flight entries to include one Coup D'Paw playmat for just $5 more (or two for just $10 more in the case of 2HG)!
For each War of the Spark Prerelease flight you enter, you will receive one spin of our Prize Wheel! Prizes include playmats, sleeves, deck boxes, Standard-legal booster packs, and more—every spin's a winner!
Chef Claytor's Dream On A Plate food truck will be on-site from 11am-7pm (Saturday only!) serving up delicious food to our War of the Spark Prerelease attendees!
1st Place: 1x Booster Box of War of the Spark w/ Buy-a-Box Promo (available to be picked up Saturday or Sunday) * Events will run through the evening as pods fill!
3-0: 3 Standard-legal booster packs 2-1: 1 Standard-legal booster pack All players receive a random Standard-legal promo card!
Individual flight entry includes one Prerelease kit, from which you'll construct your sealed deck.
2HG flight entry includes two Prerelease kits, from which you and your partner will construct both of your 2HG sealed decks.
Let your friends know that you'll be attending the War of the Spark Prerelease Celebration at the Star City Game Center April 26-28 and invite them to join you!


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Third Annual Mass and Lunch (Messa e Pranzo) sponsored by the Gulf Coast Italian American Cultural Society will be January 10 after the 11:00 AM mass at Holy Family Church in Pass Christian from 11:30 AM to 2:30 PM. Menu includes homemade penne, meatballs, string beans, salad and desserts. Admission is $12 adults, $6 for children ages 4-12. RSVP to David Biagini 228-539-4571.


How would you rate the amount of crime in Urbana? Excellent. There is virtually no crime in this area. Good. There is only a little crime in this area. Poor. There is more crime than I'd like in this area. Awful. Crime is rampant in this area. View resultsWrite a review to give others more information about this area.
Do you feel safe walking alone at night in Urbana? Extremely safe. Night or day, it's a very safe place. Fairly safe. I feel safe walking in most areas. Not very safe. I avoid walking in most areas at night. Not safe at all. I never walk alone at night. View resultsWrite a review to give others more information about this area.
The Urbana crime map provides a detailed overview of all crimes in Urbana as reported by the local law enforcement agency. Based on the color coded legend above, the crime map outlines the areas with low crime compared to the areas with high crime. The Urbana crime heat map offers insight into the total crimes on a block group level.
The overall crime rate in Urbana is 41% lower than the national average.
For every 100,000 people, there are 4.42 daily crimes that occur in Urbana.
Urbana is safer than 47% of the cities in the United States.
In Urbana you have a 1 in 62 chance of becoming a victim of any crime.
The number of total year over year crimes in Urbana has increased by 1%.
Source: The Urbana, MD crime data displayed above is derived from the FBI's uniform crime reports for the year of 2017. The crime report encompasses more than 18,000 city and state law enforcement agencies reporting data on property and violent crimes. The uniform crime reports program represents approximately 309 million American residents, which results in 98% coverage of metropolitan statistical areas.


text:
<?php

namespace Graze\CsvToken\Test\Unit;

use Graze\CsvToken\Parser;
use Graze\CsvToken\Test\TestCase;
use Graze\CsvToken\ValueParser\ValueParserInterface;
use Iterator;
use Mockery as m;

class ParserTest extends TestCase
{
    public function testConstructorValueParsers()
    {
        /** @var ValueParserInterface $valueParser */
        $valueParser = m::mock(ValueParserInterface::class);

        $parser = new Parser([$valueParser]);
        static::assertTrue($parser->hasValueParser($valueParser));
    }

    public function testAddingAParser()
    {
        /** @var ValueParserInterface $valueParser */
        $valueParser = m::mock(ValueParserInterface::class);

        $parser = new Parser();
        static::assertFalse($parser->hasValueParser($valueParser));

        $parser->addValueParser($valueParser);
        static::assertTrue($parser->hasValueParser($valueParser));
    }

    public function testRemovingAParser()
    {
        /** @var ValueParserInterface $valueParser */
        $valueParser = m::mock(ValueParserInterface::class);

        $parser = new Parser([$valueParser]);

        static::assertTrue($parser->hasValueParser($valueParser));
        $parser->removeValueParser($valueParser);
        static::assertFalse($parser->hasValueParser($valueParser));
    }

    public function testParserIteratesSoNothingShouldHappenIfThereIsNoRequestForData()
    {
        $parser = new Parser();

        /** @var Iterator $tokens */
        $tokens = m::mock(Iterator::class);

        $output = $parser->parse($tokens);

        static::assertInstanceOf(Iterator::class, $output);
    }
}

redpajama_set_name: RedPajamaGithub


text:
APIS PARTNERS
About Apis
Impact Investment
Realized Companies
© 2018, Apis Partners | Information Notice | Private Policy | Cookie Policy
Star Health Recognized as India's Most Valuable and Admired Health Insurance Company in 2016
Apis Growth Fund I announces its final close with commitments of US$ 287 million
Star Health Recognized as One of India's Top 25 Most Innovative Organizations
Star Health received the prestigious award of "India's Most Valuable and Admired Health Insurance Company of the Year, 2016" at The Pharma Leaders Awards, the leading award ceremony for the industry
Star Health collected the award ahead of several of its local peers after a comprehensive judging process
Star Health is a leading provider of retail health insurance in India and has received an investment by Apis Growth Fund I, a Private Equity fund managed by Apis Partners LLP
MUMBAI, India – December 8, 2016: Star Health and Allied Insurance Company Limited ("Star Health", the "Company") received "India's Most Valuable and Admired Health Insurance Company of the Year, 2016" award at the 9th Annual Pharma Leaders Awards held at Sahara Star, Mumbai. The Company was distinguished amongst its peers, including all the leading healthcare insurance providers in India, for its leadership and drive for excellence. The following companies were recognised as nominees for the award: Apollo Munich Health Insurance; Max Bupa Health Insurance Company Ltd; Cigna TTK Health Insurance Company Ltd; Religare Health Insurance Company Ltd and Reliance General Insurance Company Ltd.
The Pharma Leaders Awards are one of the most prestigious industry awards. The Awards acknowledge and honour individuals and organizations for their accomplishments in healthcare innovation which deliver the highest impact in broadening access to healthcare for the Indian population. Pharma Leaders is the largest business and technology leadership awards program in the Pharmaceutical industry and covers 30 categories spanning from biotech to Healthcare to CEO awards.
At the 9th Annual awards more than 400 leading enthusiasts from the industry, veteran healthcare leaders, politicians, policy makers, social activists and change agents gathered for the evening. Star Health was judged by an elite Grand Jury, ranging from the Hon'ble Jagat Prakash Nadda, the Union Minister of Health and Family Welfare and Member of Rajya Sabha, Ms. Kiran Mazumdar-Shaw, Chairman and Managing Director of Biocon Limited to Mr. Satya Brahma, Chairman and Editor-in-Chief, Pharma Leaders group.
On receiving the award, Mr. V. Jagannathan, Chairman and Managing Director of Star Health, thanked the Company's Directors of the Board , stakeholders and clients for the unwavering support extended to Star Health which has enabled the Company to garner such accolades and recognition at a National and International level.
About Star Health:
Founded in 2006, Chennai based Star Health (www.starhealth.in) is one of India's leading health insurance providers and is India's first and largest stand-alone business in the retail health insurance segment. Star Health provides over 3.7 million customers with health insurance, overseas medical cover and personal accident cover. The Company has a pan-India presence with more than 300 branch offices and a network of more than 7,000 hospitals. For the financial year ending March 2016, Gross Premium Income for the Company crossed INR 2,000 Cr (US$ 300 million). The Company is a pioneer of several innovations and industry firsts and has been consistently recognised as a leader in the health insurance market. The Company has a vast bouquet of products, including affordable products for the common man, contributing to all sections of society.
Apis Partners (attention Camarco); Ed Gascoigne-Pees; +44 20 3757 4984; ed.gascoigne-pees@camarco.co.uk
indiaStar HealthHealth InsuranceMost Valuable and Admired Health Insurance CompanyPharma Leaders Awards
Apis Partners invests in Hero FinCorp, a leading Indian non-bank finance company
LONDON, United Kingdom, May. 29, 2020 — Apis Growth Fund II recently completed an investment in Hero FinCorp, a leading Indian non-bank finance company (NBFC) with a diversified loan book compris
Oliver Krantz - May 29, 2020
Paytm and Star Health Insurance enter into corporate agency tie-up
Digital payments leader Paytm and Star Health and Allied Insurance Co. Ltd., (Star Health), a health insurance company in India, have announced their corporate agency partnership to provide Star He
Oliver Krantz - September 30, 2019
We back Financial Services innovators in Growth Markets who create transformative impact in their communities.
info@apis.pe
8 Lancelot Place
London SW7 1DR
Global Financial Services Investor, Apis Growth Fund II, invests US$35m in leading hyper-growth Indian digital payments company, Cashfree
DPO Group to be acquired by Network International
© 2020, Apis Partners | Information Notice | Privacy Policy | Cookie Policy
We use cookies to ensure that we give you the best experience on our website. If you continue to use this site we will assume that you agree with it.OkKnow more

redpajama_set_name: RedPajamaCommonCrawl


Iobit Driver Booster Pro Crack a most recent innovation which is utilized to recognize and examine obsolete driver naturally. It has an extensive number of database and bolster more than 150,000 drivers. With the assistance of this product you can discover most recent discharged Microsoft Windows 10 drivers including system, designs and driver processing plant brands. Online database capacity is extraordinarily intended to stay up with the latest. To make PC execution high, It clashes with mouse, scanner, printer, console, speakers, screen, and some more. Consequently examine your PC and fix missing drivers.
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A lovely bare-bones approach to managing mass transit.
Designing an efficient subway system isn't all that tough. You just have to connect all the stops and make sure people can get where they need to go relatively easily. Simple. And at first in Mini Metro, a game that challenges you to serve increasingly irate passengers, it is that simple, because you only have a few stops to connect, and plenty of trains to shuttle people around. And then things get a little more... demanding.
Building an actual subway system is a complex arrangement of timetables and geography, but Mini Metro simplifies everything into colorful lines and geometric shapes. Stops are represented by circles, squares, triangles, and suchlike, with passengers at each stop indicating where they want to go with the same shape. No budgets, no names, no information you don't need getting in the way of your planning. You're afforded a certain number of train lines, a certain number of cars, and other necessary constructions like tunnels and bridges. New stops pop up periodically as you work, forcing you to rethink or retool your current design. Setting up your lines is as easy as dragging your finger from one stop to the next, but keeping your passengers happy is a whole other thing.
Folks naturally want to get to their destination as fast as possible; fortunately, they're not overly specific. Any stop of the appropriate shape will do, but the rub is that some shapes are more plentiful than others. You might have 10 circles on your line, but only one square, which means you have to make sure you have plenty of different ways to get to it, so that square passengers aren't left tapping their feet in vain on the platform.
Mini Metro is a simple concept executed perfectly, with bright colors, pleasing shapes, and charmingly chirpy sounds handily offsetting the franticness with which you'll attempt to get people from place to place and oh my GOD what am I supposed to with that hexagon that just appeared out in the middle of nowhere? Take a cab, people!


Today I tried upgrading the odbc drivers on my server from 3.5 to 5.1. I immediately ran in to troubles and got a "Memory allocation error" when executing a non query to mySql. After reverting back to driver version 3.5 i found that the error was caused simply by a "data too long for field" error which i quickly fixed in no time at all.
I am not sure if the memory allocation error i received with the new drivers was related to this but if anyone could explain this I would love to know whats going off. If anyone gets a memory allocation error in 5.1 it might be worth checking to ensure the data your inserting fits into the row.
Categories: ASP.NET, C#, General, Nostalgia, SQL | Tags: databases, mySQL, Nostalgia, odbc | Permalink.
This is general rules adopted by most drivers and providers. However, keep in mind that these rules is not 100% accurate for every driver and every situation.
Never the less, following and knowing about these basic rules will keep some common problems out of your way. Okay? Here we go..
But!… if the PROVIDER keyword occurs multiple times in the string, the FIRST occurrence is used.
If a keyword contains an equal sign (=), it must be preceded by an additional equal sign to indicate that it is part of the keyword.
Categories: Coding, General, SQL | Tags: .net connection strings, connection strings, mySQL, SQL | Permalink.
Categories: General, SQL | Tags: database, mySQL, SQL | Permalink.
Categories: General, SQL | Tags: .net, database, mySQL, Tools | Permalink.
Can't remember that connection string?
This site shows all the most common connection string combinations for different clients and databases. Extremely useful!
Categories: General, SQL | Tags: .net, C#, connection string, database, mySQL, SQL, Tools | Permalink.


text:
Cockade House
Cockade House was originally built in the eighteenth century as a sugar plantation home set in 2.5 acres and was part of Bennetts Plantation. In 1971, it was later redesigned and transformed by the renowned English theatre designer, Oliver Messel.
With Oliver Messel's reputation and tasteful decoration Cockade House is now one of the most exclusive properties on the island. Messel reconfigured the interior of the house, raised the height of the ceilings, added the verandahs, redid the façade and incorporated a lovely swimming pool.
Today, Cockade House can be marveled as a delightful country house hidden behind a driveway of Mahogany trees with stunning views of the Caribbean Sea and Sandy Lane Golf Course. The main house offers 3 bedrooms, 3 bathrooms, study, living and dining room, a large, well-equipped kitchen with pantry, terraces and an inviting swimming pool, beauifully framed by a delightful arched folly, lily pond and garden pathway.
Additional bedrooms and bathrooms are available in the separate guest cottage and self-contained pavillion. The property therefore offers a total of 7 en-suite bedrooms. There is also a small office and staff quarters located behind the cottage.
Retaining all its characterful charm whilst conveying a timeless idiosyncrasy in design, Cockade is not only an artful masterpiece but a long standing luxury home, which so clearly tells an expressive story to its visitors without uttering a word.
Floor Area: 8,526 sq. ft.
Land Area: 24,0451 sq. ft.
Cottages on site
Ensuite bedrooms
St Thomas, Barbados
Royal Westmoreland- Sugar Cane Ridge
$1,450,000 USD - $1,550,000 USD
Sunset Crest - Villa 264


text:
class BookmarkNode;
class Profile;

// Small, cross platform interface that shows the correct platform specific
// bookmark editor dialog.
class BookmarkEditor {
 public:
  // Handler is notified when the BookmarkEditor creates a new bookmark.
  // Handler is owned by the BookmarkEditor and deleted when it is deleted.
  class Handler {
   public:
    virtual ~Handler() {}
    virtual void NodeCreated(const BookmarkNode* new_node) = 0;
  };

  // An enumeration of the possible configurations offered.
  enum Configuration {
    SHOW_TREE,
    NO_TREE
  };

  // Shows the platform specific BookmarkEditor subclass editing |node|. If
  // |node| is NULL a new entry is created initially parented to |parent|. If
  // |show_tree| is false the tree is not shown. BookmarkEditor takes
  // ownership of |handler| and deletes it when done. |handler| may be
  // null. See description of Handler for details.
  static void Show(gfx::NativeView parent_window,
                   Profile* profile,
                   const BookmarkNode* parent,
                   const BookmarkNode* node,
                   Configuration configuration,
                   Handler* handler);
};

#endif  // CHROME_BROWSER_BOOKMARKS_BOOKMARK_EDITOR_H_


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text:
Election /
Son of Former Dictator Leads Vice President Ahead of Election in the Philippines
Polls close at 8 P.M. on May 9
The son of the former dictator of the Philippines has emerged as a top contender for this year's presidential election.
Ferdinand Marcos was overthrown just over 30 years ago during the "People Power Revolution" in 1986. Under Marcos, the nation was subject to nine years of martial law.
Amnesty International estimates more than 70,000 people were jailed during this time and about 34,000 were tortured during Marcos's reign from 1972 to 1986.
Despite this, his family has been able to so successfully rehabilitate their reputation that Marco's son is now one of the most popular presidential candidates.
Ferdinand Marcos Jr., 64, has served as a provincial governor, congressman and senator. He was raised in the United States after his family fled the Philippines in exile following his father's removal from power. His father reportedly took billions of dollars of public funding with him when he fled the country. The family returned in 1992 after Ferdinand Marcos Sr.'s death in 1989.
His campaign has largely focused on calls for unity. Marcos Jr. has avoided addressing allegations of tax fraud.
Marcos Jr. – who is known by his childhood nickname "Bongbong" – has also refused to apologize for any of his father's actions
"One key question is how the younger demographic will vote," reports NikkeiAsia. "More than 37 million, or 56% of the voting population, are in the 18-41 age range — the country's largest-ever group of youth voters. Most were born after the Marcos dictatorship ended in 1986 and raised on social media."
Marcos Jr. has consistently increased in popularity throughout his campaign. A Socal Weather Station poll in October found that 47% of respondents supported him as the nation's future president. Pulse Asia reported his popularity peaked in February at 71% and he still lead other candidates at 57% in April.
Leni Robredo, the current Vice President of the Philippines, polled in second place in recent weeks.
The 57-year-old lawyer and economist defeated Marcos Jr.'s bid for the vice presidency in 2016. In the Philippines, the president and vice president are elected separately rather than on a joint ticket as they are in the United States.
An independent, Robredo entered politics after her husband, a politician, died in a 2012 plane crash. Her supporters dress in pink and her campaign has been noted for its effective grassroots organizations. Despite her current place in government, Robredo is considered an outsider as she does not come from one of the nation's politically dominant families, per NBC News.
The Philipines is one of a limited number of democratic nations in Southeast Asia. There are 67 million registered Filipino voters.
According to Fox News, "the election winner inherits immense problems, including an economy battered by the coronavirus pandemic, deeper poverty and unemployment, hyperinflation due to skyrocketing oil and gas prices, decades-old insurgencies and inflamed political divisions."
Other candidates include former boxers Manny Pacquiao, Manilla Mayor Isko Moreno, and former national police chief Senator Panfilo Lacson.
Voting opened on May 9. With 61% of votes counted, Bloomberg reports Marcos Jr. has more than 20 million votes — almost double those cast for Robredo.
Wordle Answer Changed From 'Fetus' by New York Times, Confusing Players


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Neither Gold Crew, ECS, nor any of their employees makes any warranty or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference to any special commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by Gold Crew or its employees. The views and opinions of the author(s) do not necessarily state or reflect those of Gold Crew or the its employees and shall not be used for advertising or product endorsement.


text:
Category: English
Elgaar Parishad case: Copying of digital data be done on day-to-day basis, say defence lawyers
Related News According to officials, each of the nine accused, currently in judicial custody, is to be given a set of 23 hard disks. (File photo) Defence lawyers in the Elgaar Parishad case on Thursday requested the court that the process of giving the copies of the seized digital data be done on a day-to-day […]
Kulbhushan Jadhav case: India to push for civilian trial
NEW DELHI: Armed with the ICJ verdict, Indian officials will push for consular access to Kulbhushan Jadhav, lodged in a Pakistani military jail for the past three years, and nudge Islamabad to shift his trial to a civilian court.If Pakistan can be persuaded to move the trial to a civilian court, India will have the […]
CPSE ETF anchor issue subscribed 8 times, opens for retail investors today
Sources said anchor investors placed bids for units worth Rs 20,000 crore against Rs 2,400 crore on offer The CPSE ETF follow-on offering (FFO) has seen encouraging demand, with the anchor investor portion witnessing 8x more demand than the units on offer. People in the know said anchor investors placed bids for units worth Rs […]
Vodafone Idea hires Bank of America, Morgan Stanley for $1.9-bn fibre sale
The bankers will initiate discussions with potential buyers for the fibre assets, which could be valued at as much as Rs 130 billion ($1.9 billion), the sources said Bloomberg Last Updated at July 19, 2019 02:26 IST Vodafone Idea has hired Bank of America and Morgan Stanley to help sell its fibre assets as India's […]
Sebi tightens disclosure framework for all listed banks: Details here
The new framework will come into effect immediately Samie Modak | Mumbai Last Updated at July 19, 2019 02:21 IST The Securities and Exchange Board of India (Sebi) on Thursday tightened the disclosure framework pertaining to 'divergence' in bad loan recognition. The capital markets regulator has said that all listed banks will have to disclose […]
K'taka: Prove majority by 1.30pm, guv tells HDK
BENGALURU: In a dramatic twist to the ongoing political crisis in Karnataka, governor Vajubhai R Vala on Thursday sent out two missives — first to speaker KR Ramesh Kumar to wrap up trust vote in the assembly by the end of the day, followed by another one to chief minister HD Kumaraswamy, setting a deadline […]
Jaishankar urges Pak to free Jadhav immediately
New Delhi: External affairs minister S. Jaishankar said in Parliament on Thursday that India wanted Pakistan to immediately "release and repatriate" imprisoned former naval officer Kulbhushan Jadhav and assured the House that the government would "vigorously continue its efforts to ensure Jadhav's safety and well-being as well as his early return to India". He added […]
Jet Airways interim RP receives claims of over Rs 24,000 crore from lenders
Only claims related to Jet are being considered and those of subsidiary JetLite will not be accepted, IRP says The interim resolution professional (IRP) handling Jet Airways insolvency has received claims of more than Rs 24,000 crore from its lenders, vendors, travel agents, and employees. The IRP has admitted 33 claims from banks worth Rs […]
Supreme Court hearings on Ayodhya begin August 2
The outcome report by the mediation panel, the court said, should reach it by August 1, 2019, a day before the next date of hearing on August 2. New Delhi: The Supreme Court will commence from August 2 hearing on the batch of cross-petitions challenging the September 30, 2010 Allahabad high court order giving two […]
Guwahati: Caught in floods, big cat curls up in bed!
Guwahati: The devastating flood is not only a tragedy for residents of Assam alone but it has brought catastrophe for wildlife of the state. On Thursday a tiger which strayed from Kaziranga National Park, which is completely under water was spotted curled up on the bed of a house near the national highway close to […]


text:
Online May 19, 2016
When the tide goes out
Pearse Elliott's latest play is, as usual, being eagerly anticipated by his many fans
By Ciara Quinn
THE prolific pen of West Belfast playwright Pearse Elliott always manages to combine comedy with pathos.
His latest work As The Tide Ebbs, currently running at the Lyric Theatre, tells the story of two middle-aged men who frequent a house which doubles as a late night shebeen. It's here where stories of lost loves, lost jobs and careers pour forth – along with the beer and spirits in a style Marlon Brandon's On The Waterfront's Terry Malloy would be proud of.
"Late one night a stranger knocks on this house and is invited in," explained Pearse, "as the night passes and the drink flows the real reason for this individual's visit becomes clear.
"Of course there is a certain darkness to it. If the Holy, Holy Bus was the woman's play then this is the man's one. I'm kind've fascinated with men of a certain vintage, men whose life maybe hasn't went the way it was supposed to.
"At the beginning this is almost like a Steptoe and Son situation. These houses have been a ritual for years, they have always existed in every housing estate, the ones you go to for a late night drink. So basically this guy comes into their space and from the off seems to know an awful lot about them."
Pearse spoke of how the play addresses the issue of men suffering from post traumatic stress stemming from the Troubles.
"It is a snapshot of how the conflict has impacted on people that could've had jobs, careers but for the conflict. People dealing with post traumatic stress tend to feel most comfortable in a certain area; a certain situation with certain people and this is captured in our setting with the characters of Shasu and Fuzzy.
"I think that sometimes when people do plays they kind've caricature the conflict but this production treats it very seriously as it is a very real, very live issue," he said.
Pearse continued: "As The Tide Ebbs is the title and a line from the play. The metaphor is basically how when the tide leaves, it leaves the debris and flotsam that was originally hidden behind.
"The ceasefire is now coming up to 22-years-old. There is a generation of kids here that have no idea what living through the Troubles was like and if this play says anything it points to the damage done to people who lived and continue to live through it everyday.
"At the end of the day I'm only a dramatist, this is how I do it. The men who go to this house do so because they can't sleep, the only way they can is through drink, it's their coping mechanism."
The Rawlife Theatre production stars West Belfast acting stalwart Marty Maguire, Michael Liebmann and Billy Clarke with Martin McSharry directing.
Stepping out from the dress rehearsal on Tuesday Pearse said the set design is "brilliant" and how the audience will be "right in the action" in the intimacy of the Naughton Studio.
"Over the last ten to 15 years I've met so many people that are subconsciously traumatised by the Troubles, I mean they might not be even aware but there is no other reason why they would speak about certain things the way they do. I think the best way to get that message across is through drama."
As The Tide Ebbs runs at the Lyric Theatre until June 5. For ticket information visit www.lyrictheatre.co.uk or telephone 02890 381081.
Kids find heroin in clock
Feel Good Friday
Gerard (PG) Mulhern@puntersgThat's why Oisin Murphy jumped ship on Fitzwilly - De Sousa is just not at it at all at the minute. The head looks down.14 hours ago17 July 2019
Gerard (PG) Mulhern@puntersgRT @moneillsf: • In 2014, there were 18,067 Irish passport apps in the North. • In the first 6 months of 2019, there has been 47,645 apps.…19 hours ago17 July 2019
Gerard (PG) Mulhern@puntersg5-2 Betsey Trotter (14:30 Catterick) 2-1 Fitzwilly (15:40 Lingfield) 4-1 Victarion (15:50 Uttoxeter) #WinTrixie19 hours ago17 July 2019
Gerard (PG) Mulhern@puntersgRT @ATownNews: #WestBelfastGreatestHits We will be releasing the first 200 Tickets this Thursday for this Event. ▶ 02890 619000 ext 261 Pe…2 days ago16 July 2019


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L'église Sainte-Colette des Buttes-Chaumont est une église paroissiale de l'Église catholique située allée Darius-Milhaud dans le  de Paris en France.

Située au rez-de-chaussée d'un immeuble d'habitation près du parc des Buttes-Chaumont duquel elle tient son nom, elle a été construite en 1992 par les architectes Thaddée et Yolande Nowak.

Notes et références

Voir aussi

Articles liés
 Liste des églises de Paris
 Archidiocèse de Paris

Liens externes

Colette des Buttes Chaumont
Édifice religieux dans le 19e arrondissement de Paris
Édifice religieux du XXe siècle à Paris

redpajama_set_name: RedPajamaWikipedia


The Model CA-6 colorimetric analyzer is an on-line sequential sampling analyzer, a sequence of sampling, analysis and result processing is performed and repeated using colorimetric methods. The measurement is a colorimetric analysis using an LED light source and a heated colorimetric cell designed for measuring trace amounts of analyte in water.
The colorimetric analyzer is assembled with two separated sections with two lockable doors. The bottom section is the LIQUIDS section. It includes all of the components involved in the flow, mixing and reaction stages of the sample and reagents (sampling pump, colorimetric reaction cell, reagents micro pumps,..). Numerous analysis configurations can be programmed, depending on accessories and of the number of micro pumps mounted in the Liquid Section. The top section is the ELECTRICAL enclosure. It includes the main power supply, the controller PCB assembly and the touch screen interface.
A typical Analysis Program in the Model CA-6 Colorimetric Analyzer would have the following structure: Rinse the colorimetric reaction cell with the sample solution and take a sample, add one or more reagents, like a buffer or masking agent and then make the first measurement, the Reference measurement. The Reference measurement eliminates interfering factors such as sample color and turbidity, miscellaneous color from the reagents and refractive index variations.
After the reference reading, the color producing reagent(s) are added. The sample is mixed and allowed time to complete the color forming reactions before taking the second measurement, the Reading measurement. The reference and reading values are used to calculate the concentration using the calibration factor. The reaction cell is drained and rinsed several times before starting the next measurement.
© 2007-2019 ECD. All rights reserved.


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Long Term Survival of Photoreceptors Transplanted into the Adult Murine Retina Requires Immune Modulation
From this month's edition of Stem Cells
By Carla Mellough
One of the limiting factors in the race to replenish ageing, damaged or dysfunctional cells by cell transplantation is the longevity of engrafted replacement cell types within host tissue. Results published in this month's edition of Stem Cells from the laboratory of Prof. Robin Ali at University College London (UCL)1, indicate a means to overcome this limitation by modulating one of the most common observations following cell transplantation – the innate host immune reaction to grafted cells. The study is focused towards the replacement of the light sensitive photoreceptors that reside within the retina of the eye, a region considered to boast relative immune privilege. The degeneration of this cell type is a feature of numerous hereditary and age-related diseases and a leading cause of untreatable blindness worldwide.
Various animal studies have demonstrated that cells grafted into the subretinal space, adjacent to host photoreceptors, can survive and integrate within the retina. Until recently2 these studies reported the failure of grafted cells to develop the mature photoreceptor morphology necessary for visual transmission, so the lack of definitive evidence for visual improvement was not surprising. A seminal study published in 20062 however, from the same group at UCL, revealed that in a mouse model of retinal degeneration the only donor cells that were capable of integrating to a degree that rendered them indistinguishable from native photoreceptors and which were able to cause an improvement in visual function, were post-mitotic cells already committed to a photoreceptor fate.
Following from their previous work, West et al.1 now examine the long term viability (up to 12 months) of these fully integrated donor cells in the wildtype retina. They show that transplanting donor cells into the eye can yield good engraftment at early stages (up to 2 months), but that over time a significant loss of grafted cells occurs. They go on to determine the immune contribution at short (1 month) and long-term (4 months) post-transplant periods and report the differential distribution of macrophages and T cells. Macrophages were found surrounding the transplanted tissue at early stages, but these persisted in the subretinal space even in the absence of the transplanted cell mass at 4 months. T cells were present in the retina, subretina and choroid near the transplant at 1 month and remained near integrated donor cells at the later stage, suggesting an adaptive immune response against donor cells. The authors demonstrate that the substantial loss of cells with time occurs not as a result of an immune response against the GFP reporter gene used to mark grafted cells, but instead due to a systemic antigen-specific immune response against donor cells. Treatment with the immune-suppressant Cyclosporine A (CsA) did not affect the survival integrated cells at the early stage (at which time acute early cell loss remained significantly negatively associated with the extent of macrophage infiltration, an acute inflammatory response unaffected by CsA treatment), but had a significant effect on the number of integrated donor cells at 4 months. At this time, immune-suppressed recipients retained approximately four-fold the number of integrated cells compared with untreated hosts, in which 90% of engrafted cells had been lost. In half of immune-suppressed graft recipients a similar number of integrated cells were found over the early and late stages, indicating that appropriately integrated, non-autologous cells can survive long-term if the T cell-mediated immune response is controlled.
This paper has particular relevance for the long term reconstitution of tissues using non-autologous cell sources, such as human embryonic stem cells, and provides some insight into the mechanisms affecting the long term survival of grafted cells. As the authors point out, a partial mismatch of H-2 haplotypes existed between grafted tissue and recipients in this study, and is likely to have contributed to the observations of this paper. Clearly, the investigation of long term graft survival in haplotype-matched tissues is of great interest as this has implications for the behaviour of MHC class matched tissue in humans, for example, the transplantation of replacement cell types derived from patient-specific induced pluripotent stem cells. Further, in this study photoreceptor precursors were transplanted into healthy eyes containing a full complement of photoreceptors. It will be interesting to compare this work with similar studies performed using models of retinal degeneration where the photoreceptor population has been depleted.
Read this article in the November edition of Stem Cells.
1. West EL, Pearson RA, Barker SE, Luhmann UF, Maclaren RE, Barber AC, Duran Y, Smith AJ, Sowden JC, Ali RR. Long Term Survival of Photoreceptors Transplanted into the Adult Murine Neural Retina Requires Immune Modulation. Stem Cells. 2010;28(11):1997-2007.
2. MacLaren RE, Pearson RA, MacNeil A, Douglas RH, Salt TE, Akimoto M, Swaroop A, Sowden JC, Ali RR. Retinal repair by transplantation of photoreceptor precursors. Nature. 2006;444(7116):203-7.


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New Release: Times Red - Not Listening
05 August Critic Jonni 0 Comments
Times Red is my new release this week, I am definitely a fan of theirs and they came to my attention when they followed me on twitter. That made me make a special on my blog, and made me realised where I had come across them before, which was on The X Factor, where they only made the Judges' Houses. They are a three piece band consisting of Scott Ritchie, Staz Nair and Luke White. They have previously released a single called "Just No Good For Me". This song is different but just as good. They call their fans TReds, I guess I'm one of them too.
The music video is something different, that's for sure. I have never come across another music video that is done the same way as this one has, with the camera, however, I wouldn't be surprised if there has been other videos using the same technique, I've just never come across them that's all, not yet anyway.
It is mainly performance based, with scenes where they're just chilling with mates, which could be a slight narrative, but not much of one.
There are many laughable bits, mainly coming from Luke White, who falls asleep on a bench and gets kissed by two old women (reminding me of Good Charlotte's "Girls & Boys"). Luke also slips near the water making me laugh, as well as pretending to be a photographer and throwing the photos behind him. And not forgetting the Usain Bolt pose.
But is that all the laughs people get? Well that definitely isn't it, people keep pausing the video at exactly 1:42... And I think we all know why.
I also find the camera monumentally great. I love how they throw it up in the air and catch it a few seconds later, it's like they are actually throwing you around. They definitely had fun that day, and I think a behind the scenes video is exactly what we would all like to see.
Overall a song that becomes more and more catchy the more we hear it, and a music video that looks like it should be bland and boring, but much like the song I keep watching it over and over again as it's so unique and fun, sometimes I feel like I'm flying through the air, which is so great. The one single problem I have is that the narrative should have been expanded more. But apart from that, an exceptionally great video!


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Spectroscopic identification and stability of the intermediate in the OH + HONO2 reaction
Bridget A. O'Donnell, Eunice X. J. Li, Marsha I. Lester, and Joseph S. Francisco
†Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323; and
¶Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084
PNAS September 2, 2008 105 (35) 12678-12683; https://doi.org/10.1073/pnas.0800320105
Bridget A. O'Donnell
Eunice X. J. Li
Marsha I. Lester
Joseph S. Francisco
Edited by F. Fleming Crim, University of Wisconsin, Madison, WI, and accepted February 22, 2008 (received for review January 11, 2008)
The reaction of nitric acid with the hydroxyl radical influences the residence time of HONO2 in the lower atmosphere. Prior studies [Brown SS, Burkholder JB, Talukdar RK, Ravishankara AR (2001) J Phys Chem A 105:1605–1614] have revealed unusual kinetic behavior for this reaction, including a negative temperature dependence, a complex pressure dependence, and an overall reaction rate strongly affected by isotopic substitution. This behavior suggested that the reaction occurs through an intermediate, theoretically predicted to be a hydrogen-bonded OH–HONO2 complex in a six-membered ring-like configuration. In this study, the intermediate is generated directly by the association of photolytically generated OH radicals with HONO2 and stabilized in a pulsed supersonic expansion. Infrared action spectroscopy is used to identify the intermediate by the OH radical stretch (ν1) and OH stretch of nitric acid (ν2) in the OH–HONO2 complex. Two vibrational features are attributed to OH–HONO2: a rotationally structured ν1 band at 3516.8 cm−1 and an extensively broadened ν2 feature at 3260 cm−1, both shifted from their respective monomers. These same transitions are identified for OD–DONO2. Assignments of the features are based on their vibrational frequencies, analysis of rotational band structure, and comparison with complementary high level ab initio calculations. In addition, the OH (v = 0) product state distributions resulting from ν1 and ν2 excitation are used to determine the binding energy of OH–HONO2, D0 ≤ 5.3 kcal·mol−1, which is in good accord with ab initio predictions.
hydroxyl radical
reaction intermediate
Nitric acid is a chemically inactive and photochemically stable reservoir for reactive HOx and NOx species in the atmosphere. In the troposphere, HONO2 is usually removed by dry deposition or rainout faster than it is photochemically converted back to NOx, making it a permanent sink for NOx (1, 2). In the upper troposphere and stratosphere, where there is no rain, HONO2 can be removed by solar photolysis and reaction with OH (3, 4),
This reaction results in the conversion of HONO2 into reactive NOx species, because the unstable nitrate radical rapidly decomposes into NO or NO2.
Kinetic studies have shown that the OH + HONO2 reaction is unusual in several respects (3, 5–11), particularly under the temperature and pressure conditions found in the lower atmosphere. Under these conditions, this reaction exhibits a negative temperature dependence, a pressure dependence, and a strong kinetic isotope effect. The indirect mechanism inferred from these studies consists of initial OH radical addition forming an energized OH–HONO2* intermediate, followed by redissociation or reaction to form products. The energized intermediate can also be temporarily stabilized by collisions with bath gas M, and then redissociate to reactants or decompose to products as shown in the following scheme:
The unusual kinetic behavior arises because of enhanced formation and collisional stabilization of the reaction intermediate under lower temperature and higher pressure conditions. However, the proposed intermediate has not been identified experimentally to date.
Prior theoretical work anticipated that OH + HONO2 can form a doubly hydrogen-bonded complex with a planar six-membered ring-like structure (5, 12, 13). The stability of the OH–HONO2 complex was predicted to be De ∼ 6.9–9.8 kcal·mol−1 with an estimated binding energy of D0 ∼ 5.6–8.1 kcal·mol−1 (12, 13). The transition state to reaction has also been predicted to lie 3.5 kcal·mol−1 above the reactant asymptote as shown in Fig. 1 (13), with reaction presumably occurring by tunneling through the barrier as evidenced by the large kinetic isotope effect (3).
Reaction coordinate for the OH + HONO2 → H2O + NO3 reaction, illustrating the presence of a hydrogen-bonded OH–HONO2 intermediate. The stability of the OH–HONO2 intermediate is derived from the present experiments and the transition state (TS) separating the intermediate from products is adopted from theory (13). The OH–HONO2 intermediate is characterized by infrared action spectroscopy of the OH radical stretch (ν1) and the OH stretch in nitric acid (ν2), which involves detection of OH products by UV laser-induced fluorescence.
This paper reports the experimental identification of the OH–HONO2 intermediate associated with this significant atmospheric reaction. The structure and stability of the reaction intermediate are obtained from direct spectroscopic characterization of the OH–HONO2 complex and its unimolecular dissociation dynamics by using an IR pump–UV probe technique (14), in which the UV laser probes the OH products after vibrational predissociation of OH–HONO2 as illustrated in Fig. 1. Two transitions are identified in the fundamental OH stretch region: the OH radical stretch (ν1) and OH stretch of nitric acid (ν2) of the OH–HONO2 complex. In addition, these same vibrational transitions are identified for the fully deuterated OD–DONO2 complex. Complementary high-level ab initio calculations are also presented in support of the experimental findings.
Infrared Action Spectra.
The OH–HONO2 intermediate has been stabilized in a pulsed supersonic jet by combining photolytically generated OH with residual nitric acid precursor as described in detail in Materials and Methods. A spectroscopic search in the fundamental OH stretching region has revealed two features that we attribute to the OH–HONO2 intermediate based on a combination of experimental and theoretical results. Both spectral features were detected with the probe laser fixed on the OH A–X (1, 0) R1(3) transition. One feature is a rotationally structured band at 3516.8 cm−1 (origin) and the second, much broader, feature is centered at ∼3260 cm−1, as shown in Fig. 2. The significant shift, −290 cm−1 from the OH stretch of the HONO2 monomer, and broadening associated with the second feature are characteristic of strong hydrogen bonding, whereas the modest shift of the structured band, −52 cm−1 from free OH, suggests a weaker interaction (15). The vibrational frequencies of these features and their shifts relative to the monomers strongly suggest their assignment as the OH radical stretch (ν1) and the OH acid stretch (ν2) modes of OH–HONO2, particularly when compared with theoretical predictions of the spectral shifts (see below and Table 1).
Infrared action spectra of features assigned to the fundamental OH radical stretch (ν1, blue) and the OH stretch of nitric acid (ν2, red) of the OH–HONO2 complex. These spectral features are observed with the UV probe laser fixed on the OH A-X (1, 0) R1(3) line. The fundamental vibrational frequencies of the OH radical and the OH stretch of the nitric acid monomers are indicated with blue and red dashed lines, respectively. The integrated intensity of the OH acid stretch relative to the OH radical stretch feature in the infrared action spectrum is 5.5(4):1. The OH acid stretch can be modeled as two broad components (black) at 3248.1(6) and 3270.8(5) cm−1 with Lorentzian linewidths of 22 cm−1.
Vibrational frequencies, spectral shifts relative to the monomer vibrations, and binding energies of the OH–HONO2 complex predicted by various theoretical methods and observed experimentally
The assignment of the 3516.8 cm−1 feature as the OH radical stretch (ν1) of the OH–HONO2 complex is further supported by analysis of the rotational structure of the band. Preliminary simulations with rotational constants derived from ab initio theory [see supporting information (SI) Tables S1 and S2] for the optimized geometry, assumed unchanged upon vibrational excitation, and the transition dipole along the OH radical axis capture much of the rotational structure. The observed band structure shown in Fig. 3 was more faithfully reproduced, however, by including a spin-rotation interaction to account for the effects of electronic state mixing in the open-shell species; this effect has been demonstrated previously in high-resolution studies of the OH–water complex (16–18). The resultant rotational band simulation shown in Fig. 3 extends over ∼12 cm−1 at 10 K. The rotational band also exhibits some line broadening (homogeneous linewidth of 0.25 cm−1 compared with the laser bandwidth of 0.02 cm−1) that likely arises from intramolecular vibrational redistribution (IVR), dissociation, and/or reaction after vibrational excitation.
High-resolution infrared action spectrum of the OH radical stretch of OH–HONO2 (black) at 3516.8 cm−1 (origin). A simulation of the rotational band structure (blue) is generated using rotational constants predicted for the OH–HONO2 complex (Table S2) and assumed spin-rotation parameters, εaa = −0.25 cm−1, εbb = −0.55 cm−1, to account for the open-shell character. A simulation of the intensity profile by using the b-component of the transition dipole moment, rotational temperature of 10 K, and a homogeneous linewidth of 0.25 cm−1 provides a good representation of the observed band structure. Atmospheric water absorption lines are indicated with asterisks.
By contrast, a much broader feature centered at 3260 cm−1 and ∼80 cm−1 in breadth was assigned as the OH acid stretch (ν2). The resultant spectrum appears to be composed of two broad components, although some rotational substructure is still observable. As shown in Fig. 2, the two broad components can be modeled as bands at 3248.1(6) and 3270.8(5) cm−1 with a corresponding intensity ratio of 1:1.4(1) and Lorentzian linewidths of 22 cm−1. The fact that the 3260 cm−1 feature (as well as its two subcomponents) is much broader than the OH radical stretch feature is consistent with strong anharmonic coupling between two (or possibly more) vibrational states. We carried out a vibrational deperturbation analysis (19) in an effort to characterize the energies and couplings of zero-order states that might give rise to the two components of the 3260 cm−1 feature. A two-state deperturbation analysis indicates that the experimentally observed mixed states would arise from coupling between zero-order states at 3257.6(7) and 3261.2(7) cm−1. The analysis also indicates a very strong coupling of 11.2(2) cm−1 between the zero-order states. One of the zero-order states is the optically bright OH acid stretch (ν2) of OH–HONO2; the identity of the second zero-order state is as yet unknown.
The OH stretch in nitric acid is predicted to have a transition intensity ∼10 times stronger than that of the OH radical stretch (12). Our experimental measurements yield an integrated intensity ratio of 5.5(4):1 for the acid stretch to the radical stretch in infrared action spectra. The fractional population in the OH product channel being detected is essentially the same (20%) after ν1 and ν2 excitation; however, the branching between dissociation and reaction after ν1 and ν2 excitation is not known.
In addition, these same vibrational transitions have been identified for the fully deuterated OD–DONO2 complex by infrared action spectroscopy. The spectra were recorded with the probe laser fixed on the P1(3) line of the OD A–X (1, 0) transition (20). The OD radical stretch (ν1) of OD–DONO2 is observed at 2594 cm−1, shifted 38 cm−1 to lower frequency than that in free OD (21). The OD stretch of DONO2 (ν2) is observed at 2425 cm−1, corresponding to a −197 cm−1 shift compared with the OD stretch of the monomer (21). The OD radical stretch band spans ∼15 cm−1, whereas the OD acid stretch feature is spread over ∼40 cm−1. The integrated intensity of the OD acid stretch is approximately 5 times greater than the OD radical stretch. These spectral properties are consistent with a strong hydrogen bond for the acid and a weaker interaction for the radical.
OH Product State Distribution.
The IR excitation provides sufficient energy to induce dissociation and/or reaction between the components of the OH–HONO2 intermediate. In this work, we examine the nascent OH X 2Π (v = 0) product state distribution to provide a direct experimental determination of the stability of the intermediate. For both ν1 and ν2 excitation, the product state distributions peak at the lowest rotational level that can be observed, N = 2, F1,‖ and fall off with increasing rotational energy, as shown in Fig. 4. There are no noticeable fine structure (Λ-doublet or spin-orbit) preferences. After ν1 excitation of OH–HONO2 at 3516.8 cm−1, the highest energetically observed OH level is N = 9, F1, Π(A″) with an internal energy of 1654.6 cm−1; the same OH product state appears to be closed after ν2 excitation at 3268.4 or 3250.7 cm−1. In the latter case, the highest energetically observed OH channel is N = 8, F1, Π(A″) with an internal energy of 1324.3 cm−1. For ν1 excitation, the infrared photon, hνIR, combined with the energy of the highest open OH product channel, EOH, indicate that 1862.2 cm−1 (5.3 kcal·mol−1) is available for dissociation of OH–HONO2, D0, internal excitation of the HONO2 cofragment, EHONO2, and translational energy of the recoiling fragments, Et, according to the following energy balance equation:
The internal energy of OH–HONO2 is negligible at ∼10 K; EHONO2 and Et are unknown. As a result, our experiment provides a rigorous upper limit for the OH–HONO2 binding energy of D0 ≤ 5.3 kcal·mol−1. The same calculation for ν2 excitation yields D0 ≤ 1935.7 cm−1 (5.5 kcal·mol−1); the large spacing (∼330 cm−1) to the next higher OH rotational level, N = 9, which appears to be closed, precludes further refinement of this limit.
Nascent quantum state distribution of the OH (v = 0, N) products observed after excitation of the radical stretch (ν1) at 3516.8 cm−1 (Upper, blue) and the nitric acid stretch (ν2) at 3268.4 cm−1 (Lower, red) of the OH–HONO2 intermediate. Ticks identify OH rotational levels in the F1 spin-orbit manifold, whereas the Π(A′) and Π(A″) Λ-doublet components are distinguished by triangles and circles, respectively. The OH product state distributions peak at low rotational states and fall off with increasing rotational excitation. For ν1 excitation, the highest observed product state is N = 9, F1, Π(A″) with 1654.6 cm−1 of internal energy, whereas for ν2 excitation the highest state is N = 8, F1, Π(A″) with 1324.3 cm−1 of internal energy. The smooth curves through the data are prior statistical distributions with Eavail derived from the IR excitation frequency and the upper limit for the binding energy, D0 ≤ 5.3 kcal·mol−1.
The experimental OH X 2Π (v = 0) product rotational distributions were also modeled by a statistical prior distribution (22). The prior distribution assumes that the product states associated with the translational, rotational, and vibrational motions of the OH and HONO2 fragments are populated with equal probability subject only to a constraint on the energy available to products, Eavail = hνIR − D0 (23). In this experiment, we examine the probability of the OH products being released in a given quantum state and, therefore, we sum the usual formulation (22) over the unobserved HONO2 rotational and vibrational states. The density of HONO2 vibrational states is obtained from a direct count, assuming harmonic vibrations. The density of HONO2 rotational states is treated classically. The prior distributions computed for ν1 and ν2 excitation of OH–HONO2 with D0 = 5.3 kcal·mol−1 are illustrated as smooth curves through the experimental data in Fig. 4, demonstrating that the distribution is statistical and further validating the binding energy derived from the highest open OH product channel. The statistical distribution clearly indicates some degree of IVR before dissociation and/or reaction.
Insights From Theory.
The optimized geometry of the OH–HONO2 complex is detailed in Table S1 for the QCISD and CCSD(T) methods with various basis sets and is illustrated in Fig. 5a. The hydrogen bond between the acidic proton of nitric acid and the oxygen of OH (O7–H5) is predicted to be near linear (172.5°) with a bond length of 1.83 Å at the highest level of theory. A secondary interaction between the hydrogen of the OH radical and a nitric acid oxygen atom (O3–H6) is nonlinear (121.2°) with a bond length of 2.28 Å. Natural bond orbital (NBO) analysis, shown in Fig. 5 b–e, has been used to investigate the nature of hydrogen bonding in the complex (24). A characteristic feature of the radical–molecule complex is the cyclic double hydrogen bonding. The strongest interaction is between the σ antibonding orbital of the acid, σ*(O2–H5), and the lone pair of the OH radical, O7. There is also a second interaction involving the lone pair of O3 of HONO2 and the σ antibonding orbital of the OH radical, σ*(O6–H7). The unpaired electron of the OH radical does not directly participate in the hydrogen bonding of the OH–HONO2 complex. The unpaired electron is in a pπ-type orbital that lies perpendicular to the plane of interaction.
Natural bond orbital analysis. (a) Optimized geometry and labeling scheme for the OH–HONO2 complex. (b and c) Natural bond orbital analysis reveals the primary interaction of the σ antibonding orbital σ*(O2–H5) of nitric acid with the lone pair O7 of the OH radical (b) and the secondary interaction of the lone pair of O3 of HONO2 with the σ antibonding orbital σ*(O6–H7) of the OH radical (c). (d and e) The half-filled pπ orbital of the OH radical in the OH–HONO2 complex lies perpendicular to the plane of interaction as shown from the top view (d) and the side view (e).
The spectral shifts for the radical stretch (ν1) and acid stretch (ν2) of HONO2 predicted from previous B3LYP (12, 13) and the present QCISD/aug-cc-pVDZ calculations, listed in Table 1, are in good accord with observed shifts, −52 and −290 cm−1, respectively. The computed shifts are derived from harmonic frequency calculations for the complex and monomers. A small spectral shift is predicted for the weakly coupled OH radical stretch (ν1), whereas a much larger shift is predicted for the strongly coupled OH acid stretch (ν2). The integrated intensities of the features are also consistent with the intensity ratio predicted theoretically (12). Both the spectral shifts and intensities indicate that the rotationally structured feature at 3516.8 cm−1 and the broad feature at 3260 cm−1 correspond to the ν1 and ν2 fundamentals of the OH–HONO2 intermediate, respectively. For the fully deuterated complex, the calculated shifts (13) are again in good agreement with the observed spectral shifts.
The binding energy of the OH–HONO2 complex has been computed by the CCSD(T) method with various basis sets permitting extrapolation to the complete basis set limit (CBS-∞). The resultant zero-point corrected binding energy of D0 = 5.9 kcal·mol−1 is in good agreement with the limiting experimental value of D0 ≤ 5.3 kcal·mol−1.
The properties of the OH–HONO2 complex are expected to be similar to those of the nitric acid–water complex, which has been investigated by ab initio theory (25–28) and observed experimentally by microwave spectroscopy in the gas phase (29) and infrared spectroscopy in argon matrices (28, 30). The nitric acid–water complex forms a six-membered ring with the free hydrogen of the water molecule lying out of plane. The microwave study demonstrated that the hydrogen bond between the acidic proton of nitric acid and the oxygen of water is near linear (174.5°) with a bond length of 1.779 Å. The second, weaker, interaction between the hydrogen of the OH radical and a nitric acid oxygen atom is nonlinear (119.3°) with a bond length of 2.30 Å (29). The doubly hydrogen-bonded nitric acid–water complex is computed to have a greater stability than OH–HONO2 with D0 ∼ 7.5–8.1 kcal·mol−1 (25, 26, 28). From the argon matrix measurement (30), the frequency shift of the OH acid stretch of the nitric acid–water complex from the monomer is −496 cm−1, which is a significantly greater shift than that observed for OH–HONO2 (see Table 1); however, one must be cautious in comparing argon matrix data to gas-phase data, particularly in hydrogen-bonded systems (28). Ab initio calculations also predict a greater spectral shift for the OH acid stretch in the nitric acid–water complex than in the OH–HONO2 complex (25, 28, 31), implying both a stronger and shorter hydrogen bond in the nitric acid–water complex.
We can estimate the lifetime of an energized OH–HONO2* intermediate based on rate constants deduced from kinetic modeling of the bimolecular OH + HONO2 reaction (3). Using the rate constants for redissociation of the energized OH–HONO2* adduct back to reactants (k−a ∼ 2.5 × 1010 s−1) and unimolecular reaction of OH–HONO2* to form products (kb ∼ 5.0 × 108 s−1), we estimate a lifetime (τ−1 = k−a + kb) of ∼40 ps for an energized OH–HONO2* intermediate. This compares favorably with the lifetime of 21 ps derived from the homogeneous line-broadening in the experimental spectrum for the OH radical stretch (ν1) of OH–HONO2.
Fundamental OH radical stretch excitation takes the OH–HONO2 complex in close proximity to the transition state for reaction as shown in Fig. 1. Because the initial OH stretch excitation is rapidly randomized in the intermediate, the branching ratio for inelastic to reactive decay may be analogous to a collision experiment. Kinetic modeling of such experiments (3) suggests that most of the energized OH–HONO2* adducts will redissociate back to reactants rather than forming products (k−a/kb ∼ 50), favoring production of OH fragments. This situation is quite favorable for obtaining infrared action spectra of OH–HONO2, as illustrated in the present work. The branching ratio may change for the OH stretch of HONO2, which may enhance reactive decay. Such a change would clearly have an impact on the relative intensities of vibrational bands in infrared action spectra. Because deuteration will slow tunneling to reaction products, dissociation to reactants should be more strongly favored for OD–DONO2.
The OH radical stretch of OH–HONO2 is expected to be weakly coupled to the reaction coordinate, whereas elongation of the OH bond in HONO2 should drive the transformation from the intermediate to the transition state for reaction. As a result, excitation of the OH acid stretch of HONO2 in OH–HONO2 is particularly fascinating because it both induces the necessary geometrical changes to move along the reaction coordinate and provides sufficient energy to reach the barrier to reaction (13). Future studies should explore the possibility that this excitation enhances production of the NO3 reaction product.
We have successfully stabilized the OH–HONO2 hydrogen-bonded intermediate in the OH + HONO2 → H2O + NO3 reaction in a pulsed supersonic expansion. Vibrational features at 3516.8 and 3260 cm−1 observed by infrared action spectroscopy have been attributed to the OH radical stretch and the OH nitric acid stretch of the OH–HONO2 complex. These findings have been confirmed by high-level ab initio theory and experimental studies of the fully deuterated complex. The identification of this intermediate is important experimental validation of key steps in the mechanism of the OH + HONO2 reaction, which is an important atmospheric reaction that influences the residence time of nitric acid in the atmosphere.
The OH–HONO2 intermediate is produced by combining photolytically generated OH radicals with residual nitric acid precursor (99.8% fuming) entrained in pure He or a 20% N2/He gas mixture (200–250 psi), or alternatively Ar carrier gas (60 psi). The production of OH–HONO2 is optimized when HONO2 is photolyzed (ArF excimer laser, ∼5 mJ·cm−2) within a quartz capillary tube (0.5 mm inside diameter, 10 mm length) attached to the pulsed valve assembly, indicating that the high pressure conditions in the capillary tube facilitate collisional stabilization of OH–HONO2. The OH–HONO2 intermediate and residual OH radicals are then cooled in the ensuing supersonic expansion to their lowest quantum states.
Infrared excitation in the OH fundamental stretch region (2.8–3.1 μm) is achieved with a single-mode optical parametric oscillator (OPO, 0.02 cm−1 linewidth, ∼10 mJ·cm−2) pumped by an injection-seeded Nd:YAG laser. The OH X 2Π (v = 0) fragments resulting from infrared excitation are detected by laser-induced fluorescence (LIF) on the A 2Σ+–X 2Π (1, 0) transition at 282 nm by using a frequency-doubled Nd:YAG pumped dye laser. The IR and UV lasers are calibrated by using a wavelength meter and/or the well known positions of OH lines (20, 32). The focused IR and collimated UV laser beams are counterpropagated into the vacuum apparatus, where the two beams are spatially overlapped ∼10 nozzle diameters downstream of the exit of the capillary tube. The IR pump laser (10 Hz) is present for every other UV probe laser pulse (20 Hz), which permits data acquisition with active background subtraction of UV only signal arising from residual OH. The time delay between the IR and UV lasers is 50 ns. Similar methods were used for OD–DONO2.
For a given OH X 2Π (v = 0) product rotational level, N, there are four fine-structure substates that correspond to Π(A′) or Π(A″) Λ-doublet level levels (in the high-J limit) within both the F1 and F2 spin-orbit manifolds. Fine-structure resolved detection is relatively straightforward, because P- and R-type main branch transitions originate from Π(A′) levels whereas Q-type main branch transitions originate from Π(A″) levels. Typically, four transitions probing different rotational/fine-structure states were recorded at least three times for the determination of the statistical uncertainty in the signal intensities. The intensities were determined from the amplitudes of the spectral lines. Conversion of line intensities to ground state populations includes a degeneracy correction factor.
All calculations were performed using the GAUSSIAN 03 software (33). The geometries were optimized by using the QCISD method with aug-cc-pVDZ basis set as well as the CCSD(T) method with aug-cc-pVDZ and aug-cc-pVTZ basis sets (see Table S1). Frequency calculations were performed by using the QCISD method with the aug-cc-pVDZ basis set (see Table S3). The corresponding rotational constants at the equilibrium position are given in Table S2. We carried out a detailed study of the hydrogen-bonded orbitals by using a natural bond orbital (NBO) analysis at the MP2/aug-cc-pVDZ level of theory (34). The three-dimensional figures of the orbitals derived from this work (Fig. 5) were plotted using NBOVIEW 1.0 (35). The binding energies, both at the equilibrium position De and zero point corrected D0, were extrapolated to the complete basis set limit (CBS aug-cc-pV∞Z) by using the CCSD(T) method as shown in Table S4.
We thank M. D. Marshall (Amherst College, Amherst, MA) and A. R. Ravishankara (National Oceanic and Atmospheric Administration, Boulder, CO) for helpful discussions. We are grateful to E. L. Derro and T. D. Sechler for their help in obtaining the spectra of the deuterated species. We also thank Bryan Putnam of Information Technology at Purdue for help with computer resources to complete this project. This work was supported by the Chemistry Division of the National Science Foundation.
§To whom correspondence should be addressed. E-mail: milester{at}sas.upenn.edu
Author contributions: M.I.L. designed research; B.A.O., E.X.J.L., and J.S.F. performed research; B.A.O. and E.X.J.L. analyzed data; and M.I.L. wrote the paper.
↵‡Present address: ITT Advanced Engineering and Sciences, 2560 Huntington Avenue, Alexandria, VA 22303.
This article contains supporting information online at www.pnas.org/cgi/content/full/0800320105/DCSupplemental.
↵‖ The population in the lowest rovibrational state, OH X 2Π (v = 0, N = 1), could not be probed because of the large jet-cooled background.
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(2005) Effects of partially quenched orbital angular momentum on the microwave spectrum and magnetic hyperfine splitting in the OH-water complex. Chem Phys Lett 401:420–425.
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You are going to email the following Spectroscopic identification and stability of the intermediate in the OH + HONO2 reaction
Bridget A. O'Donnell, Eunice X. J. Li, Marsha I. Lester, Joseph S. Francisco
Proceedings of the National Academy of Sciences Sep 2008, 105 (35) 12678-12683; DOI: 10.1073/pnas.0800320105
Article Classifications


text:
An "Ice" Time at the Brrrgh
Posted by Professor Flake on December 2, 2014 at 2:00 PM
G-G-Greetings!
Professor Flake, here once again for the first time in a while.
In case you were wondering, we (Don't be mistaken -- it's still just me) finally got a building set up for the Precipitation Foundation right on Polar Place, and I've been studying the weather there ever since. Eh, I've studied the occasional Lawbot too, but they're boring.
Things have been getting chilly here in the Brrrgh. It's f-f-freezing, and more than usual. You see, ever since Doctor Surlee's Super-Duper Air Conditioner went crazy, it has been snowing every d-d-day for years. It'd be great to turn it off every now and then, but no one can find the blasted thing under all of this snow!
My colleague at Loony Labs responsible for the forever-winter wonderland around us, Doctor Surlee, told me today that it has been helping with the silly levels that the S.I.L.L.I. Team (Scientists Interested in Laugh Levels Increasing) have been tracking. Whether or not they're helping with the silliness, however, I want to get to the bottom of this pile of snow so we can keep this machine from freezing my research!
Mark my words, one of these days we're going to regret letting that thing create an eternal blizzard. Who knows what catastrophe it could cause over this upcoming Winter season.
As always, I'll be up to my research. Feel free to stop by Toon HQ for an opening -- my Junior Research Scientists all seem to quit as soon as they get their hands on these Lawbot Suit Parts I've been collecting.
Keep in t-t-touch, Toons!
Crazy Winky Cheezyswirl said on December 2, 2014 at 2:04 PM
Brrrr.. I want a scarf now just thinking about it.
Master Dynamite said on December 2, 2014 at 2:04 PM
S.I.L.L.I? Really? I give it a 10...out of 100. Jk, the next month should be interesting.
Ooowoo said on December 2, 2014 at 2:11 PM
I hope that Lil Oldman can cast a spell to keep the blizzard. It is what makes the Brrrgh a good place.
Cool Pinky said on December 2, 2014 at 2:13 PM
I know how cold it is at the Brrrgh! Its freezing there. I know because I'm working on toontasks there. If we get a blizzard, it will be pretty fun though! K-K-Keep in touch, Professor Flake!
Udon said on December 2, 2014 at 2:17 PM
Snow can't be THAT bad, Professor.
Mr. Toon said on December 2, 2014 at 2:36 PM
Must be a very cold way in the brrrgh, don't worry, sweaty pete has some heat you may need.
Mailmare Seasonals said on December 2, 2014 at 2:43 PM
I kinda want to find the machine and put a timer on it, but i'm lazy to find it, as well as to get a hot coco.
Little Foot said on December 2, 2014 at 2:48 PM
Where my family lives, it's been almost below freezing at night, and in the day, it's between 18-19 and 25 degrees. Yeah, it's cold enough and we did get some snow, but not a whole lot. We'd like a few inches though.
Bright Paws said on December 2, 2014 at 3:06 PM
I don't blame u for being cold. I was once in a real blizzard. It. Was. Freezing.
Princess Lily said on December 2, 2014 at 3:42 PM
Surlee's? I read those notes from the 26th and- nevermind. Good luck with the cold weathers there! I just moved on over to DDL, but I'll be sure to still send you guys so hot cocoa!
Aunt Daffy said on December 2, 2014 at 3:44 PM
"Mark my words, one of these days we're going to regret letting that thing create an eternal blizzard." I smell something fishy...
Mister J.C. (Justice Cat) laff 104 said on December 2, 2014 at 4:03 PM
Brrrr.... you said it just helping Professer Flake with his temperature sensors for lawbot parts is chilly around this time of year. I better go get my coat before me next CJ.....
Loopy Z.Z. said on December 2, 2014 at 4:14 PM
It is very c-c-cold! I am also working on my tasks there!
Paddlefish said on December 2, 2014 at 4:58 PM
I was wondering what made it so c-c-cold at the Brrrgh!
Macks said on December 2, 2014 at 5:50 PM
G-g-greetings from the brrrgh. Day can't count, still on the lil oldman task, 10-20 bldgs, and i'm freezing my gloves off. Macks the blue pig out!!
Sir Slapstick said on December 2, 2014 at 6:14 PM
My-My... it is cold there, indeed. In fact, that was the very place I'd been scrambling before.. the shut-down.. *Shudder* Well, we shouldn't dwell on the past, now should we? I wish you luck and a pair of good gloves.
dynoflip said on December 2, 2014 at 6:15 PM
this is going to be a brrgh of a time!!
Ryan said on December 2, 2014 at 6:22 PM
i think you guys or guy is doing great keep up and your awesome for making tootown
john jacob jingleheimer schmidt said on December 2, 2014 at 7:13 PM
None of the post the TTR team makes are random... So what is this post leading up too? Food for thought.
Lady Lemonquack said on December 3, 2014 at 12:32 AM
Wuh? I thought brrgh was always cold. Lawl.
Spiritkit said on December 3, 2014 at 5:27 AM
Brrrr! I c-c-could really go for a toasty pair of winter b-b-boots and a nice s-s-scarf! Hmm... m-m-maybe even some Hot-Cocoa! I'll m-m-make sure I k-k-keep in touch, P-P-Professor!
Dude said on December 3, 2014 at 6:59 AM
could it be a blizzard?cogs could learn to paint themselves white and wed never know what is going on. either that, or all of toontown will be frozen! gee, now im cold
Big Ned said on December 3, 2014 at 8:08 AM
Ugh, I agree with you, Professor. I have to close my eyes if I don't want snow in my eyes.
Rickey Rat said on December 3, 2014 at 10:33 AM
Oh NO! This could freeze all Toontown by Christmas! oh wait.... that might not be too bad....
Greg said on December 3, 2014 at 1:16 PM
I didn't quit! I came back to your building after defeating the CJ for my first time ever in Toontown Rewritten. ;D I chatted with you and you gave me a task to see Shep Ahoy. I promise I'll visit you again after finishing my Bossbot Suit! :)
Lunch said on December 3, 2014 at 1:17 PM
Glad IM not there. I'm nice and cozy in Daisy Gardens
cool domino fuzzy foot said on December 3, 2014 at 1:36 PM
Hmm I wonder if we will have a white Christmas this year in toontown. I'm just getting cold thinking about it.
Strawberry Cake said on December 3, 2014 at 2:17 PM
Oh dear... I've moved to Donald's Dreamland, but I'll be sure to send hot cocoa and warm blankets your way, Professor!
Locomotive said on December 3, 2014 at 2:23 PM
Anyone up for hot cocoa after defeating cogs in the blizzard? I know I am!
Crazy dog said on December 3, 2014 at 3:55 PM
Wow an eternal blizzard.
super winky said on December 3, 2014 at 4:05 PM
hello, im very excited for this
Rocky Blue said on December 3, 2014 at 4:05 PM
Noo! I logged off on The Brrrgh!
CuteSunnyBunny said on December 3, 2014 at 4:11 PM
Looks like I need to grab my coat, because I'll be at the Brrrgh for a while! I'm probably going to make snow toons, and toon angels!
Rosie said on December 3, 2014 at 4:56 PM
Im getting chills reading this post. And coincidentally, I just finished my lawbot suit today!
Whiskers said on December 3, 2014 at 5:43 PM
M-Man I-I-Its R-Really C-Cold I-I-I-In T-The B-B-B-Brrrgh!
Gummie Bare said on December 3, 2014 at 6:33 PM
Stay warmed toons! with your coats and jackets
smokey said on December 4, 2014 at 5:35 AM
I hope we can keep the blizzard going, I love the wintery look! Gosh! I love the snow!
Super Popcorn Thunderdoodle said on December 4, 2014 at 7:45 AM
Ooh, a bit of foreshadowing I presume?
Raven said on December 4, 2014 at 8:39 AM
I just finished the Lil Oldman Task! Im on the Brrrgh now! Thats funny! the day it was posted! :D yay
May said on December 4, 2014 at 9:59 AM
Brr.... I have a suspicion..... what if that thingy makes the whole town a Winter Freezingland? Just a hunch..... maybe....
doom said on December 4, 2014 at 11:03 AM
i love toontown rewritten
idoom2 said on December 4, 2014 at 11:04 AM
i love tootown rewritten
Bandit said on December 4, 2014 at 11:27 AM
Cool. :)
Cricket said on December 4, 2014 at 2:20 PM
Angel said on December 4, 2014 at 6:40 PM
Doctor Surlee is awesome. The Brrgh is always winter for some reason :D.
Professor Flake is awesome. The Brrgh is always winter for some reason lol.
Pickle said on December 4, 2014 at 8:53 PM
Come on you are making me have chills! And there is something fishy happening at the lawbot hq... the cogs seem to group up!
Storm said on December 4, 2014 at 11:31 PM
The brrrgh has been colder than normal this winter!
Cool Toon said on December 5, 2014 at 3:37 AM
Uhhhhh....... Its really really cold in ttr now. Hope we find the machine soon to stop it!
Gamesmarts194 said on December 5, 2014 at 5:47 AM
Why hate the snow? Yeah, a little too much snow is pretty bad, but I've seen (and experienced worse). I'd go out in 20 F weather in jeans and a light jacket.
Pandora said on December 5, 2014 at 6:50 AM
awesome :D i just got into the brrrg too! Things are working out for me~ ^^
Captain Curly Gumdropswirl said on December 5, 2014 at 8:29 AM
It's cold as a billion of popsicles!
chrissy123 said on December 5, 2014 at 10:38 AM
brrrrr...im really cold
Master Orville WeaselGadget said on December 5, 2014 at 6:34 PM
S.I.L.L.I team? Kool!
Radioactive said on December 5, 2014 at 7:28 PM
- shivers - I sh-should now. I have to do tasks in that playground. It is pr-pretty cold. But if I work hard enough Lil Oldman will give me trap!
Domino said on December 5, 2014 at 9:10 PM
i think they've had enough coldness... P.S. I actually know how it feels to be THAT cold
Tom said on December 6, 2014 at 1:41 AM
Gosh that will stop me from going to the brrrgh now for a bit Can I have a scarf?!?!?!
Bar-B-Que said on December 6, 2014 at 5:43 AM
Love the thought and effort put into this game and the newly updated story line of Toontown! Toons of the world unite!
Polar Wolf said on December 6, 2014 at 7:04 AM
My squirt gags are frozen solid! Hahaha :)
charlie said on December 6, 2014 at 7:09 AM
what is going on with that? I feel something exciting yet weird is going to be going on in the brrrgh!
Cool Domino Fuzzyfoot said on December 6, 2014 at 9:18 AM
I think you guys need to make a fire type gag to keep us warm this winter.
Reed said on December 6, 2014 at 9:40 AM
Sounds C-c-cold!
Doge said on December 6, 2014 at 10:17 AM
Keep up the good research Professor! We want all the information that we can get. Just do your best! See you next month.
Mr Toon Man said on December 6, 2014 at 10:17 AM
Man... I wonder what the cogs plan on doing to us for Christmas!! Keep an eye out Toons! Toons Of The World, UNITE!!
Prince Ned Purplemuffin said on December 6, 2014 at 11:30 AM
Hope you can get this "air conditioner" to stop, and continue your research, Professor Flake! We need all of this info we can get from our Professors, for it will benefit Toontown Rewritten! You just gave me an update, actually, for I thought it just normally snowed. Thank you, and good luck!!!
Sunny Buddy said on December 6, 2014 at 1:28 PM
No worries! I'll send you a scarf and a lifetime supply of hot cocoa and you'll be warm in no time!!
said on December 6, 2014 at 1:41 PM
I'm doing tasks in the Brrrgh now, and it IS pretty cold, but I like it that way. I'll never ever imagine the Brrrgh without snow. Too sad. To me, snow is what the Brrrgh's all about. If someone took the blizzards and snow away, it would be nothing to me. So PLEASE don't stop the snow machine. Please. - Louie :)
Dark Tiger said on December 6, 2014 at 1:50 PM
Interesting! I Wonder What Will happen... Hmmm...
Destrie said on December 6, 2014 at 2:37 PM
Whoa! You don't say?! I was in the Brrrgh the other day and it was pouring with snow, Professor!
Shuffle said on December 6, 2014 at 2:40 PM
What about Donald's Dreamland? Will it be in forever darkness? Or will he even wake up?
Cool Fangs Petal Pretzel said on December 6, 2014 at 2:44 PM
Man, I wish I had the Super-Duper Air Conditioner!
Waffles said on December 7, 2014 at 8:11 AM
Brrrr.... Does anyone have handwarmers? Im freezing here!
Crazy Candy said on December 7, 2014 at 3:25 PM
I need to wear my Brrgh winter clothing for this!
Grace said on December 7, 2014 at 7:21 PM
Yeah. Lawbots are boring. But blizzards aren't! I know it is cold I have been there too. It is lots of fun!
Estates are a BLAST!
McQuack - December 11, 2014 at 2:00 PM
Gardening is a GO!
Professor Ivy - December 6, 2014 at 2:30 PM
Professor Flake - December 2, 2014 at 2:00 PM
The Thankful Thanksgiving Sale
Sir Max - November 28, 2014 at 12:00 AM
Our Pleasure to Return
??? - November 26, 2014 at 4:35 PM


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        var
            tempNode = this._arr[key],
            // greaterNode = greaterChild(tempNode);
            lowerNode = lowerChild(tempNode);

        while ( sinkDownComparator(tempNode, lowerNode) && !!lowerNode ) {
            heapSwap(this._arr, tempNode, lowerNode);
            key = tempNode.key;
            tempNode = this._arr[key],
            lowerNode = lowerChild(tempNode);
        }
    },
    // insert in a heap
    insert: function insert (val) {
        // insert
        var newNode = createNode(val, this._insertPos);

        //attach relationships
        this._insertPos = this._arr.push(newNode);
        console.log("insertPos is at "+this._insertPos+" and node Parent pos is: " + nodeParent(this._insertPos-1));
        console.log("New Node");
        console.log(newNode);
        if ( this._insertPos-2 > 0 ) {
            console.log("New Node Parent");
            var newNodeParent = this._arr[nodeParent(this._insertPos-1)];
            console.log(newNodeParent);
            _attachNodes(newNode, newNodeParent);
        }
        // compare and swim  if needed
        this.swimUp(this._insertPos-1);
    },
    _delLastLeaf: function delLastLeaf() {
        // remove it
        _delNodesRelation(this._arr.pop());
        //decerement the insert Position
        this._insertPos -= 1;
    },
    delMin: function delMin() {
        if ( !this.isEmpty() ) {
            // delete the root Minimum Node
            // get last node which is the Max Node in Min Binary Heap at root - O(lgN)
            heapSwap(this._arr, this._arr[1], this._arr[this._insertPos-1]);
            // remove the last leaf - O(1)
            this._delLastLeaf();
            //rebalance the heap by sinking Down from root Index, 1. - O(lgN)
            this.sinkDown(1);
        }
    },
    minHeap: function minHeap() {
        // return minimum of minHeap - O(1)
        return this._arr[1].val;
    },
    seek: function seek (key) {
        // O(1)
        return key<this._insertPos?this._arr[key]:undefined;
    },
    print: function print(log) {
        log(this._arr);
    }
};

// for debugging and testing only
// var log = console.log;

// var dummy = function dummy() {
//     // body...
//     return;
// };

// console.log = (function (status) {
//     if (status) return log;
//     else return dummy;
// })(false);

// var heap = Object.create(minBinaryHeap);
// heap.init();
// heap.insert(100);
// heap.insert(-1000);
// heap.insert(-2000);
// heap.insert(20000);
// heap.insert(780);
// heap.insert(2340);
// heap.print(log);
// console.assert(heap.minHeap()==-2000, "Should equal -2000");
// log("------------------------");
// heap.delMin();
// heap.print(log);
// console.assert(heap.minHeap()==-1000, "Should equal 1000");