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257_13 | Palantir Metropolis (formerly known as Palantir Finance) was software for data integration, information management and quantitative analytics. The software connects to commercial, proprietary and public data sets and discovers trends, relationships and anomalies, including predictive analytics. Aided by 120 "forward-deployed engineers" of Palantir during 2009, Peter Cavicchia III of JPMorgan used Metropolis to monitor employee communications and alert the insider threat team when an employee showed any signs of potential disgruntlement: the insider alert team would further scrutinize the employee and possibly conduct physical surveillance after hours with bank security personnel. The Metropolis team used emails, download activity, browser histories, and GPS locations from JPMorgan owned smartphones and their transcripts of digitally recorded phone conversations to search, aggregate, sort, and analyze this information for any specific keywords, phrases, and patterns of behavior. In |
257_14 | 2013, Cavicchia may have shared this information with Frank Bisignano who had become the CEO of First Data Corporation. |
257_15 | Palantir Apollo
Palantir Apollo is a continuous delivery system that manages and deploys Palantir Gotham and Foundry. Apollo was built out of the need for customers to use multiple public and private cloud platforms as part of their infrastructure. Apollo orchestrates updates to configurations and software in the Foundry and Gotham platforms using a micro-service architecture. This product allows Palantir to provide software as a service (SaaS) rather than to operate as a consulting company.
Palantir Foundry
Palantir Foundry was used by NHS England in dealing with the COVID-19 pandemic in England to analyse the operation of the vaccination programme. A campaign was started against the company in June 2021 by Foxglove, a tech-justice nonprofit, because "Their background has generally been in contracts where people are harmed, not healed." Clive Lewis MP, supporting the campaign said Palantir had an "appalling track record." |
257_16 | Other
The company has been involved in a number of business and consumer products, designing in part or in whole. For example, in 2014, they premiered Insightics, which according to the Wall Street Journal "extracts customer spending and demographic information from merchants’ credit-card records." It was created in tandem with credit processing company First Data.
Customers
Corporate use
Palantir Metropolis is used by hedge funds, banks, and financial services firms.
Palantir Foundry clients include Merck KGaA, Airbus and Ferrari.
Palantir partner Information Warfare Monitor used Palantir software to uncover both the Ghostnet and the Shadow Network. |
257_17 | U.S. civil entities
Palantir's software is used by the Recovery Accountability and Transparency Board to detect and investigate fraud and abuse in the American Recovery and Reinvestment Act. Specifically, the Recovery Operations Center (ROC) used Palantir to integrate transactional data with open-source and private data sets that describe the entities receiving stimulus funds. Other clients as of 2019 included Polaris Project, the Centers for Disease Control and Prevention, the National Center for Missing and Exploited Children, the National Institutes of Health, Team Rubicon, and the United Nations World Food Programme.
In October 2020, Palantir began helping the federal government set up a system that will track the manufacture, distribution and administration of COVID-19 vaccines across the country. |
257_18 | U.S. military, intelligence, and police
Palantir Gotham is used by counter-terrorism analysts at offices in the United States Intelligence Community and United States Department of Defense, fraud investigators at the Recovery Accountability and Transparency Board, and cyber analysts at Information Warfare Monitor (responsible for the GhostNet and the Shadow Network investigation).
Other clients as of 2013 included DHS, NSA, FBI, CDC, the Marine Corps, the Air Force, Special Operations Command, West Point, the Joint IED Defeat Organization and Allies. However, at the time the United States Army continued to use its own data analysis tool. Also, according to TechCrunch, "The U.S. spy agencies also employed Palantir to connect databases across departments. Before this, most of the databases used by the CIA and FBI were siloed, forcing users to search each database individually. Now everything is linked together using Palantir." |
257_19 | U.S. military intelligence used the Palantir product to improve their ability to predict locations of improvised explosive devices in its war in Afghanistan. A small number of practitioners reported it to be more useful than the United States Army's program of record, the Distributed Common Ground System (DCGS-A). California Congressman Duncan D. Hunter complained of United States Department of Defense obstacles to its wider use in 2012.
Palantir has also been reported to be working with various U.S. police departments, for example accepting a contract in 2013 to help the Northern California Regional Intelligence Center build a controversial license plates database for California. In 2012 New Orleans Police Department partnered with Palantir to create a predictive policing program. |
257_20 | In 2014, US Immigration and Customs Enforcement (ICE) awarded Palantir a $41 million contract to build and maintain a new intelligence system called Investigative Case Management (ICM) to track personal and criminal records of legal and illegal immigrants. This application has originally been conceived by ICE's office of Homeland Security Investigations (HSI), allowing its users access to intelligence platforms maintained by other federal and private law enforcement entities. The system reached its "final operation capacity" under the Trump administration in September 2017.
Palantir took over the Pentagon's Project Maven contract in 2019 after Google decided not to continue developing AI unmanned drones used for bombings and intelligence.
International Atomic Energy Agency
Palantir was used by the International Atomic Energy Agency (IAEA) to verify if Iran was in compliance with the 2015 agreement. |
257_21 | Europe
The firm has contracts relating to patient data from the British National Health Service. It was awarded an emergency, no-competition contract to mine COVID-19 patient data in 2019. In 2020 this was valued at more than £23.5 million and was extended for two more years. The firm was encouraged by Liam Fox "to expand their software business" in Britain.
The Danish POL-INTEL predictive policing project has been operational since 2017 and is based on the Gotham system. According to the AP the Danish system "uses a mapping system to build a so-called heat map identifying areas with higher crime rates." The Gotham system has also been used by German state police in Hesse and Europol. |
257_22 | The Norwegian Customs is using Palantir Gotham to screen passengers and vehicles for control. Known inputs are prefiled freight documents, passenger lists, the national Currency Exchange database (tracks all cross-border currency exchanges), the Norwegian Welfare Administrations employer- and employee-registry, the Norwegian stock holder registry and 30 public databases from InfoTorg. InfoTorg provides access to more than 30 databases, including the Norwegian National Citizen registry, European Business Register, the Norwegian DMV vehicle registry, various credit databases etc. These databases are supplemented by the Norwegian Customs Departments own intelligence reports, including results of previous controls. The system is also augmented by data from public sources such as social media.
Partnerships and contracts |
257_23 | International Business Machines
On February 8, 2021, Palantir and IBM announced a new partnership that would use IBM's hybrid cloud data platform alongside Palantir's operations platform for building applications. The product, Palantir for IBM Cloud Pak for Data, is expected to simplify the process of building and deploying AI-integrated applications with IBM Watson. It will help businesses/users interpret and use large datasets without needing a strong technical background. Palantir for IBM Cloud Pak for Data will be available for general use in March 2021.
Amazon (AWS)
On March 5, 2021, Palantir announced its partnership with Amazon AWS. Palantir's ERP Suite is now optimized to run on Amazon Web Services. One of the first notable successes of the ERP suite was with BP, which was able to save about $50 million in working capital within two weeks of onboarding the system. |
257_24 | Babylon Health
Palantir took a stake in Babylon Health in June 2021. Ali Parsa told the Financial Times that "nobody" has brought some of the tech that Palantir owns "into the realm of biology and health care."
Controversies
Algorithm development
I2 Inc sued Palantir in Federal Court alleging fraud, conspiracy, and copyright infringement over Palantir's algorithm. Shyam Sankar, Palantir's director of business development, used a private eye company as the cutout for obtaining I2's code. I2 settled out of court for $10 million in 2011. |
257_25 | WikiLeaks proposals (2010)
In 2010, Hunton & Williams LLP allegedly asked Berico Technologies, Palantir, and HBGary Federal to draft a response plan to "the WikiLeaks Threat." In early 2011 Anonymous publicly released HBGary-internal documents, including the plan. The plan proposed that Palantir software would "serve as the foundation for all the data collection, integration, analysis, and production efforts." The plan also included slides, allegedly authored by HBGary CEO Aaron Barr, which suggested "[spreading] disinformation" and "disrupting" Glenn Greenwald’s support for WikiLeaks.
Palantir CEO Karp ended all ties to HBGary and issued a statement apologizing to "progressive organizations… and Greenwald … for any involvement that we may have had in these matters." Palantir placed an employee on leave pending a review by a third-party law firm. The employee was later reinstated. |
257_26 | Racial discrimination lawsuit (2016)
On September 26, 2016, the Office of Federal Contract Compliance Programs of the U.S. Department of Labor filed a lawsuit against Palantir alleging that the company discriminated against Asian job applicants on the basis of their race. According to the lawsuit, the company "routinely eliminated" Asian applicants during the hiring process, even when they were "as qualified as white applicants" for the same jobs. Palantir settled the suit in April 2017 for $1.7 million while not admitting wrongdoing. |
257_27 | British Parliament inquiry (2018)
During questioning in front of the Digital, Culture, Media and Sport Select Committee, Christopher Wylie, the former research director of Cambridge Analytica, said that several meetings had taken place between Palantir and Cambridge Analytica, and that Alexander Nix, the chief executive of SCL, had facilitated their use of Aleksandr Kogan's data which had been obtained from his app "thisisyourdigitallife" by mining personal surveys. Kogan later established Global Science Research to share the data with Cambridge Analytica and others. Wylie confirmed that both employees from Cambridge Analytica and Palantir used Kogan's Global Science Research data together in the same offices. |
257_28 | ICE Partnership (since 2014)
Palantir has come under criticism due to its partnership developing software for U.S. Immigration and Customs Enforcement. Palantir has responded that its software is not used to facilitate deportations. In a statement provided to the New York Times, the firm implied that because its contract was with HSI, a division of ICE focused on investigating criminal activities, it played no role in deportations. However, documents obtained by The Intercept show that this is not the case. According to these documents, Palantir's ICM software is considered 'mission critical' to ICE. Other groups critical of Palantir include the Brennan Center for Justice, National Immigration Project, the Immigrant Defense Project, the Tech Workers Coalition and Mijente. In one internal ICE report Mijente acquired, it was revealed that Palantir's software was critical in an operation to arrest the parents of undocumented migrant children. |
257_29 | On September 28, 2020, Amnesty International released a report criticizing Palantir failure to conduct human rights due diligence around its contracts with ICE. Concerns around Palantir's rights record were being scrutinized for contributing to human rights violations of asylum-seekers and migrants.
"HHS Protect Now" and privacy concerns (since 2020)
The ongoing COVID-19 pandemic has prompted tech companies to respond to growing demand for citizen information from governments in order to conduct contact tracing and to analyze patient data. Consequently, data collection companies, such as Palantir, have been contracted to partake in pandemic data collection practices. Palantir's participation in "HHS Protect Now", a program launched by the United States Department of Health and Human Services to track the spread of the coronavirus, has attracted criticism from American lawmakers. |
257_30 | Palantir's participation in COVID-19 response projects re-ignited debates over its controversial involvement in tracking undocumented immigrants, especially its alleged effects on digital inequality and potential restrictions on online freedoms. Critics allege that confidential data acquired by HHS could be exploited by other federal agencies in unregulated and potentially harmful ways. Alternative proposals request greater transparency in the process to determine whether any of the data aggregated would be shared with the US Immigration and Customs Enforcement to single out undocumented immigrants.
Project Maven (since 2018)
After Google had issues with employees walking out concerning the new contract in partnership with the Pentagon, Project Maven, a secret artificial intelligence program aimed at the unmanned operation of aerial vehicles, was taken up by Palantir. Critics warn that the technology could lead to autonomous weapons that decide who to strike without human input. |
257_31 | See also
Government by algorithm
References
External links
2003 establishments in California
Analytics companies
Big data companies
Business software companies
Companies based in Denver
American companies established in 2003
Data brokers
Criminal investigation
Software companies based in Colorado
Software companies of the United States
Government by algorithm
Software companies established in 2003
Companies listed on the New York Stock Exchange
Direct stock offerings |
258_0 | Rammellzee (stylized RAMM:ΣLL:ZΣΣ, pronounced "Ram: Ell: Zee"; December 15, 1960 – June 28, 2010) was a visual artist, gothic futurist "graffiti writer", painter, performance artist, art theoretician, sculptor and a hip hop musician from New York City, who has been cited as "instrumental in introducing elements of the avant-garde into hip-hop culture". Since 2021, Rammellzee's work is exclusively represented by Jeffrey Deitch.
Early life
Rammellzee was born on December 15, 1960 in Far Rockaway, Queens to an African-American mother and Italian father who worked as a transit detective. He grew up in the Carlton Manor Projects near the Far Rockaway–Mott Avenue A train terminal station. His graffiti work started to show up in the 1970s on New York City's subway cars and stations, specifically on the A-train since it was his local train. |
258_1 | Rammellzee studied dentistry at the Clara Barton High School for Health Professions, was a model for Wilhelmina (under the name Mcrammellzee), and briefly studied jewelry design at the Fashion Institute of Technology (FIT).
Career
Discovered by a larger audience through the 1982 cult movie Wild Style by Charlie Ahearn, Rammellzee's earlier fame in graffiti circles was established when he painted New York subway trains with DONDI, OU3, and Ink 76, and doctor Revolt under his aliases Hyte, Hytestyr, EG (Evolution Griller the Master Killer), Sharissk Boo, Razz, and Maestro on the A, CC, 2 and 5 subway lines. Rammellzee was an occasional member of the Death Comet Crew, with Stuart Argabright, Michael Diekmann and Shinichi Shimokawa. He also formed the crew Tag Master Killers, consisting of A-One, Delta2, Kool Koor and Toxic. |
258_2 | Rammellzee became a friend and collaborator of artist Jean-Michel Basquiat. In 1982, Rammellzee and Toxic accompanied Basquiat to Los Angeles while he prepared for his show at the Gagosian Gallery. They called themselves the Hollywood Africans as a social and political statement to counter the stereotypical portrayals of African Americans in Hollywood. The trio are depicted in Basquiat's paintings Hollywood Africans in front of the Chinese Theater with Footprints of Movie Stars (1983) and Hollywood Africans (1983). |
258_3 | Rammellzee was an original hip hop artist who introduced specific vocal styles which date back to the early 1980s. His 12-inch single "Beat Bop," in collaboration with rapper K-Rob and with cover art by Basquiat, is considered by some to be the most valuable (meaning collectible) hip-hop record of all time. "Beat Bop" was also featured in the film Style Wars. Rammellzee makes a cameo appearance near the end of Jim Jarmusch's 1984 film Stranger Than Paradise. Rammellzee's influence can be heard in artists such as Beastie Boys and Cypress Hill. In 1988, Rammellzee and his band Gettovetts recorded the album Missionaries Moving, with producer Bill Laswell, a frequent collaborator. Laswell also paired Rammellzee with writer William Burroughs on the 1989 album, Seven Souls, and featured him on several albums recorded by his revolving super-group, Praxis. |
258_4 | He also wrote an opera "The Requiem of Gothic Futurism" in 1985, "offered to send the U.S. military some of the intelligence he had gathered for national defense," and "tried to promote his ideas by producing a comic book and a board game."
Rammellzee was the first artist to collaborate with the streetwear brand Supreme, making hand-painted trucker hats at their first store in 1994.
In 2003, Rammellzee released his debut album, This Is What You Made Me, and performed at the Knitting Factory in New York with the newly reformed Death Comet Crew. Subsequently, Troubleman Unlimited re-released recordings made by DCC between 1982 and 1984. Their single for Exterior St was featured on the compilation Anti-NY with Ike Yard, Sexual Harassment, and Vivien Goldman, among others. In 2004, Rammellzee released his second album Bi-Conicals of the Rammellzee, produced by Gamma Records. |
258_5 | Gothic Futurism
Rammellzee's graffiti and art work are based on his theory of Gothic Futurism, which describes the battle between letters and their symbolic warfare against any standardizations enforced by the rules of the alphabet. His treatise, Ionic treatise Gothic Futurism assassin knowledges of the remanipulated square point's one to 720° to 1440°, details an anarchic plan by which to revise the role and deployment of language in society.Rammellzee performed in self-designed masks and costumes of different characters which represented the "mathematical equation" that is Rammellzee. On the basis of his Gothic Futurism approach, he described his artistic work as the logical extension into a new phase which he calls Ikonoklast Panzerism. This artistic work has been shown in art galleries throughout the US and Europe. His Letter Racers, and other Noise includes artistic works by individuals mostly identified with their musical contributions. |
258_6 | Afrofuturism
Rammellzee's work is considered to contribute to the canon of Afrofuturism, primarily through his repeated use of language as a technology. One of the central themes of Afrofuturist content is the use of language as a technology to transcend the Digital Divide. Conversely, Rammellzee had stated that "there is no such thing as Afro Futurism" and considered his work to be more part of a larger European monastic tradition than any part of an Afrofuturist tradition.
The theory of Gothic Futurism attempts to deconstruct the English language as it is currently conceived. The battle between letters seen in the Ionic treatise deploys language as a technology to fight the oppressive nature of the alphabet. The introduction of a new mythology in the treatise suggests that Rammellzee's language can serve as a force of liberation, thereby lessening the Digital Divide. |
258_7 | In addition, Rammellzee's Letter Racers are intended to pit each individual letter in galactic battles against each other, symbolically challenging the accepted standards and functionality of the 26-letter alphabet.
Rammellzee's description of the Letter Racers is as follows:
"Humans...in the 14th Century the monks ornamented and illustrated the
manuscripts of letters. In the 21st and 22nd century the letters of the alphabet
through competition are now armamented for letter racing and galactic battles. This was made possible by a secret equation known as THE RAMM:ELL:ZEE."
Rammellzee is celebrated in Big Audio Dynamite's song, 'Come On Every Beat Box'.
In 2010 Buckethead released a tribute song called, 'Rammellzee: Hero of the Abyss'. |
258_8 | Personal life
Rammellzee was married to Carmela Zagari Rammellzee. He died in New York City on June 28, 2010, at the age of 49, having suffered from the exposure to glue, paint fumes, resin and other toxins through his work and from liver problems. The official cause of death was listed as heart disease.
Name
He legally changed his name to Rammellzee in 1979 and friends who knew his birth name were unwilling to reveal it, in accordance with his wishes. He sometimes went by the shortened name of "Ramm". He has stated that his name is derived from RAM plus M for Magnitude, Sigma (Σ) the first summation operator, first L – longitude, second L – latitude, Z – z-bar, Σ, Σ – summation. He has credited Jamel-Z, a mentor from the Nation of Gods and Earths he met in 1977, with inspiration for his name. |
258_9 | Battle Station
Rammellzee's live/work loft studio space on 46 Laight Street in the TriBeCa neighborhood, which he shared with his wife Carmela, was named Battlestation. It was a popular place in the 1980s and 1990s for artists to visit, because Rammellzee's artwork and costumes created a unique atmosphere. After 9/11, the building was sold in order to build luxury condos and this forced Rammellzzee and Carmela to move to a smaller place in Battery Park City, and relocate his 20 years worth of artwork into a storage unit. Some of this stored work was included in the 2011 art exhibition, Art in the Streets at Museum of Contemporary Art Los Angeles. In May 2018, Red Bull Arts New York opened its exhibition RAMMΣLLZΣΣ: Racing for Thunder, billed in its press release as "the largest survey to date of one of the most influential yet overlooked artists of the 20th century." |
258_10 | Exhibitions
2021 - Writing the Future: Basquiat and the Hip-Hop Generation - Museum of Fine Arts, Boston - Group
2018 - RAMMΣLLZΣΣ: A Roll of Dice - Lazinc Gallery - London - England - Solo
2018 - Rammellzee - Racing for Thunder - Red Bull Arts - New-York - United States - Solo
2018 - Le musée du street Art et du Graffiti - L'Aérosol - Maquis-art Hall of Fame - Paris - Group
2016 - La Velocità delle immagini (Collection Speerstra) - Institut Suisse de Rome - Italy
2016 - Graffiti Art - Tableau de légende (Collection Gallizia) - Institut culturel Bernard Magrez - Bordeaux - France - Group
2016 - Pressionnism, graffiti masterpieces on canvas (Collection Gallizia) - Fort Canning Museum - Singapour - France - Group
2015 - Pressionnisme, de Bando à Basquiat (Collection Gallizia) - Pinacothèque de Paris - France - Group
2014 - City as Canvas: Graffiti Art (Collection Martin Wong) - Museum of the City of New York - NY - United States - Group |
258_11 | 2013 - The Shadows Took Shape - The Studio Museum in Harlem - New York City -NY - United States - Group
2013 - Urban Art Biennale 2013 - Urban Art Biennale - Völklingen - Germany - Group
2013 - Graffiti, Thanks a Lot - Fun Gallery (Curateur Patti Astor) - New-York - United States - Group
2013 - Tekens aan de Wand: Ferenc Gögös/Graffiti Art - Museum Tongerlohuys - Roosendaal - Netherlands - Group
2013 - White Petals Surround Your Yellow Heart - Institute of Contemporary Art - University of Pennsylvania - Philadelphia - United States - Group
2013 - Last of the Hollywood Africans: Toxic - Londonewcastle Project Space - London - England - Group
2013 - Abstract Mash-Up II: A Group Exhibition - Crown Point Press Gallery - San Francisco - United States - Group
2012 - Radical Presence: Black Performance In Contemporary Art - Contemporary Arts Museum Houston - Houston - United States - Group |
258_12 | 2012 - God Save the Queen: Punk in the Netherlands 1977-1984 - Centraal Museum - Utrecht - Netherlands - Group
2012 - Brucennial 2012 - Harder. Betterer. Fasterer - United States - Group
2012 - Strongerer - Brucennial - New York City - United States - Group
2012 - Letter Racers - The Museum of Modern Art - NY - United States - Solo
2012 - Letter Racers - The Suzanne Geiss Company - NY - United States - Solo
2012 - The Rammellzee Galaxseum - Children's Museum of Art - New York - United States - Solo
2011 - Perfect Man II - White Columns - New York City - NY - United States - Group
2011 - Graffiti - New York 80's - Galerie Jérôme de Noirmont - Paris - France - Group
2012 - Speerstra Fondation (Collection Speerstra) - Apples - Switzerland - Group
2012 - Art in the Streets - The Geffen Contemporary at MOCA - Los Angeles - CA - Group - solo
2011 - L'Art du Graffiti : 40 ans de Pressionnisme (Curateur A.D. Gallizia) - Grimaldi Forum - Monaco - France - Group & solo |
258_13 | 2011 - The Aerosol Experience - Zieglerzwei - Zurich - Switzerland - Group
2011 - The Rudolf and Ute Scharpff Collection - Kunstmuseum Stuttgart - Germany - Solo
2010 - Street and Studio - Von Basquiat bis Séripop - Kunsthalle Wien (Museumsquartier) - Vienna - Austria - Group
2010 - Un musée à ciel ouvert (Collections Gallizia-Emerige) - Bâche Wagram - Paris - France - Group
2010 - Printin - The Museum of Modern Art - NY - United States - Group
2010 - Rammellzee: The Equation - Suzanne Geiss's Gallery - New York - United States - Solo
2009 - Gothic Futurism - Galerie Renée Ziegler - Zurich - Switzerland - Solo
2009 - Subcultural Capital - Anonymous Gallery - New York City - NY - United States - Group
2009—The New Yorkers - V1 Gallery - Copenhagen - Denmark - Group
2009 - Ramm:Ell:Zee - Galerie Ziegler SA - Zurich - Switzerland - Solo
2009 - Tag au Grand Palais (Collections Gallizia) - Grand Palais - Paris - France - Group |
258_14 | 2007 - Futuro del Futurismo - Gamec -Galleria d'Arte Moderna e Contemporanea di Bergamo - Italy - Group
2007 - Graffiti Stories (Collection Speerstra) - Abbaye d'Auberive et Musée Paul Valéry, Sète - France - Group
2007 -L'art modeste sous les bombes (Collection Speerstra) - Musee International des Arts Modestes - Sete - France - Group
2006 - Music is a Better Noise - MoMA PS1, New York City - NY - Group
2006 - Sound Zero - Kunst Meran - Meran - Italy - Group
2005 - Bi-Conicals of Rammellzee Tour - Venice Biennale - Italy - Solo
2004 - Smile away the parties and champagne - Zeen keuze uit de collectie - Gemeentemuseum Helmond - Boscotondohal, Helmond - Netherlands - Group
2002 - Americas Remixed - Careof – Fabbrica del Vapore - Milan - Italy - Group
2002 -Cowboys en kroegtijgers - Gemeentemuseum Helmond - Boscotondohal - Helmond - Netherlands - Group
2002 - Americas - Fabbrica del Vapore - Milan - Italy - Group |
258_15 | 2001 - Oostduitse meisjes en andere stukken - Gemeentemuseum Helmond - Boscotondohal - Helmond - Netherlands - Group
1998 - Smile away the parties and champagne - Gemeentemuseum Helmond - Boscotondohal, Helmond - Netherlands - Group
1994 - Rammellzee vs Gen U One (Gen Atem) - Exercises in Self Presentation - Eigen + Art - New York City - United States - Group
1992 - Coming from the Subway (Collection Speerstra) - Groninger Museum - Netherlands - Group
1991 - American Graffiti: A Survey - Liverpool Gallery - Brussels - Group
1991 - Graffiti Art : Artistes américains et français 1981/1991 (Collection Speerstra) - Musée des monuments Français Paris - Group
1990 - Rammellzee - Galerie B5/Speerstra Gallery - Monaco - France - Solo
1989 - Hip Hop 'til You Drop - Whitney Museum of American Art - New York - United States - Group
1988 - Comic Iconoclasm - Cornerhouse - Manchester - England - Group
1987 - The Equation - Lidia Carrieri Gallery - Rome - Italy - Solo |
258_16 | 1986 - Retrospective (Collection Speerstra) - Gemeente museum - Helmond - Netherlands - Group
1985 - 18° Bienal de Sao Paulo - Bienal de Sao Paulo - São Paulo - Brasil - Group
1985 - Ikonoklast Panzerim - Galerie Renée Ziegler - Zurich - Switzerland - Group
1985 - Between Science and Fiction - Bienal de Sao Paulo - Brasil - Group
1984 - Rapid Enamel The Art of Graffiti - The Renaissance Society at The University of Chicago - Group
1984 - Ein anderes klima - a different climate (II) - Kunsthalle Düsseldorf - Dusseldorf - Germany - Group
1984 - Graffiti - Groninger Museum - Groningen - Netherlands - Group
1984 - New York Graffiti (Collection Speerstra) - Louisiana Museum - Humlebaek - Denmark - Group
1984 - Artists from New-York in Monte-Carlo - Speerstra Gallery - Monaco - France - Group
1983 - Post-Graffiti - Sydney Janis Gallery - New-York - United States - Group
1983 - Graffiti, Thanks a Lot - Fun Gallery (Patti Astor) -Group |
258_17 | 1983 - Museum Boymans - Van Beuningen - Rotterdam - Netherlands - Group
1982 - New York - Institute of Contemporary Arts - London - England - Group |
258_18 | Collections
Rammellzee's work is held in the following public collection:
Museum of Modern Art, New York: one 12-inch vinyl record (Beat Bop) and a series of ten drawings titled Alphabet, undated
Museum of Graffiti, Miami
Discography
Studio albums
Singles & EPs
References
External links
Artist biography at Magical-Secrets.com
Excerpts from Rammellzee's thesis Iconic Treatise Gothic Futurism
Interview with Rammellzee
Video Interview with Guerilla Art
Red Bull Music and Culture Video Profile "RAMMELLZEE: It's Not Who But What"
Art gallery |
258_19 | 1960 births
2010 deaths
American graffiti artists
Rappers from New York City
20th-century American painters
American male painters
American people of Italian descent
21st-century American painters
Artists from New York City
Mass media theorists
People from Far Rockaway, Queens
Postmodern artists
20th-century American printmakers
African-American contemporary artists
American contemporary painters
African-American male models
African-American painters
African-American printmakers
20th-century African-American male singers
21st-century African-American artists |
259_0 | Metal-ligand cooperativity (MLC) is a mode of reactivity in which a metal and ligand of a complex are both involved in the bond breaking or bond formation of a substrate during the course of a reaction. This ligand is an actor ligand rather than a spectator, and the reaction is generally only deemed to contain MLC if the actor ligand is doing more than leaving to provide an open coordination site. MLC is also referred to as "metal-ligand bifunctional catalysis." Note that MLC is not to be confused with cooperative binding. |
259_1 | The earliest reported metal-ligand cooperativity was from the Fujiwara group in the 1950s, in which they reported formation of stilbene from styrene and arenes using a palladium chloride catalyst. Shvo's catalyst was developed for one of the earliest uses of ketone hydrogenation by an outer-sphere mechanism. Noyori has developed many chiral catalysts for asymmetric hydrogenation. Transfer hydrogenation, one of the most commonly used applications of MLC, is employed broadly in industry for large scale Noyori-type reductions.
Modes of Metal-Ligand Cooperativity
There are a variety of modes in which this cooperativity has been demonstrated. Four primary modes are generally accepted under MLC: the ligand can (1) act with Lewis acidity, (2) act with Lewis basicity, (3) play a role in aromatization and dearomatization, or (4) be redox non-innocent. |
259_2 | The ligand can act as a Lewis acid and accept electrons from an incoming substrate as it binds to the metal, as in employed in dehydrogenation catalysis. Conversely, the ligand can be Lewis basic and bind the substrate; this Lewis basicity is most frequently seen in hydrogenation catalysis.
The aromatization and dearomatization of a ligand can serve to facilitate a reaction. As shown in the figure, a ligand can be dearomatized by a base and thus activated toward cleaving a C-H or H-H bond and be subsequently rearomatized during substrate bond cleavage. NHC ligands and other pincer ligands are frequently employed in this mode of MLC. In some reports, with bidentate ligands, ligand dearomatization is not observed when the complex is treated with base but rather a complex with a formal metal-carbon bond is observed (that then acts as a Lewis basic ligand). |
259_3 | The ligand can also be redox non-innocent to facilitate reactions that the metal would otherwise be unable to activate. The ligand can act as an electron reservoir, which is enabled when ligands contain frontier orbitals of suitable energy to participate in the redox event themselves, and can accept or donate electrons during the course of the reaction, allowing the metal to modulate its oxidation state. This allows metals which normally only participate in one electron regimes to be used in two electron regimes with a redox non-innocent ligand to store electrons during the reaction. Dithiolate ligands have been used extensively as one electron redox active ligands in metal complexes. For example, dithiolates have been demonstrated to allow for the selective and reversible reduction of ethylene in the presence H2, CO, and H2S. This has applications in the purification of ethylene gas streams, in which ethylene can be reduced electrochemically by a dithiolate, selectively removed from |
259_4 | the impurities in the stream, and then reversibly desaturated. |
259_5 | Electrochemical metal-ligand cooperativity in redox reactions allows for ease of tuning the potential of the ligands to avoid off-target reactivity.
There are a number of other ligand modes of reactivity which are sometimes classified under MLC. This includes reactions in which the ligand accepts or loses a proton, though not directly from or to the substrate. Ligands can also be used to form stabilizing H-bonds, which can be applied in molecular recognition catalysis. Ligands can also be designed to be photoresponsive, with applications in molecular switches. Ligands may also be considered to be involved in MLC while acting only in the second coordination sphere (not directly bound to the metal) but acting as a proton shuttle. Frustrated Lewis pairs, in which an ion pair of the type [R3B-H]−[H-Ar3]+ transfer a hydride and proton are also sometimes classified under MLC. |
259_6 | Mechanism of Hydrogenations with Metal-Ligand Cooperativity |
259_7 | MLC is most frequently used in hydrogenations, with many applications in asymmetric catalysis and in process scale production of chemicals. In a hydrogenation, there is a transfer of a hydride and a hydrogen to a substrate. Typical substrates include aldehydes, ketones, and imines. As this is a common use for MLC, it is instructive in understanding the mechanism of metal-ligand cooperativity. MLC occurs through an outer sphere mechanism. An outer sphere mechanism does not necessitate that the metal undergo oxidative addition or reductive elimination. Thus, H2 is not added across the metal, but rather across the metal and a ligand; alternatively, the metal complexes are preformed to contain a hydride ligand as well as a ligand with a hydrogen alpha to the metal. Thus, the hydride and hydrogen are adjacent to one another, facilitating the transfer to the substrate; this transfer occurs without the substrate ever binding to the metal itself. Though amine is by far the most used ligand in |
259_8 | cooperativity, other actor ligands include alkoxides and thiols. |
259_9 | In contrast, in an inner sphere mechanism, the substrate will be inserted into the metal and reaction with hydrogen will then afford the hydrogenated product. This mechanism does not employ MLC. The differentiation between an outer sphere mechanism relying on MLC and an inner sphere mechanism is exemplified by cobalt hydrogenation with an amine pincer ligand. In the outer sphere mechanism, the hydrogen on the pincer ligand is added into the ketone along with a hydride ligand on the metal. It is worth noting that there is debate over the concertedness of the transition state of this outer sphere hydrogenation step, and different reactions and catalysts may be either concerted or stepwise, and in some scenarios there may be multiple pathways at play. In comparison to the ketone hydrogenation, an olefin undergoes an inner sphere mechanism under the same reaction conditions, in which the olefin inserts directly into the metal. These mechanistic differences between the ketone and olefin |
259_10 | are corroborated by the observation that the ketone hydrogenation will not occur with an N-Me pincer ligand, and the olefin hydrogenation will proceed with the N-Me ligand, suggesting the ketone requires the presence of the N-H bond while the olefin does not. |
259_11 | Common Ligands |
259_12 | MLC is most broadly used with M-NH systems. Nyori and others have developed an extensive library of diamine ligands which serve in hydrogenation reactions, following the general outer sphere mechanism illustrated above. These systems are typically ruthenium complexes containing phosphine ligands as the spectator ligands. Many of these diphosphine ligands, such as BINAP, contain arene rings and impart chirality from atropisomerism; the rigidity of the phosphene ligands can impart chirality on prochiral substrates with high fidelity, allowing for asymmetric hydrogenation. Reactivity of metal complexes used in MLC can be tuned greatly by the use of different diphosphine spectator ligands. |
259_13 | M-OH metal ligand systems have application in MLC. Shvo's catalyst was one of the earliest complexes developed for ketone and aldehyde reductions to alcohols. The ruthenium complex (1), upon heating, dissociates into a 18 electron complex (2) and a 16 electron complex (3), the former of which is catalytically active. The hydroxy group on the cyclopentadienyl is the actor ligand, donating a hydrogen in an outer sphere mechanism. Bäckvall has developed use for Shvo's catalyst in the dynamic kinetic resolution of alcohols with lipases. |
259_14 | Bergman and coworkers developed a sulfur ligand for activation of H-H as well as Si-H bonds. A titanium sulfide complex binds H2 across the titanium and sulfur, yielding a hydride and thiol ligand. A similar mode of reactivity is seen with H-Si bonds, in which the sulfide forms a bond with the silicon, and the titanium accepts the hydride. The use of sulfur ligands in MHC has continued to expand since Bergman's early work in the field. Iridium and rhenium complexes with bridging sulfides have been demonstrated to heterolytically cleave H2.
Metal boron complexes have also been demonstrated to be useful in activating H2. These ligands are less developed for the purpose of MLC, and commonly suffer from off target alkyl and aryl migration from the boron ligand to other ligands or substrates which disrupts the catalytic cycle
References
Hydrogenation |
260_0 | The cuisine of Philadelphia was shaped largely by the city's mixture of ethnicities, available foodstuffs and history. Certain foods have become associated with the city.
Invented in Philadelphia in the 1930s, the cheesesteak is the most well known, and soft pretzels have long been a major part of Philadelphia culture.
The late 19th and early 20th centuries saw the creation of two Philadelphia landmarks, the Reading Terminal Market and Italian Market. After a dismal restaurant scene during the post-war era of the 20th century, the 1970s brought a restaurant renaissance that has continued into the 21st century.
Many foods and drinks associated with Philadelphia can also commonly be linked with the Pennsylvania Dutch cuisine and Italian-American cuisine. |
260_1 | Innovations
Philadelphia's large immigrant population has contributed to a large mixture of tastes to mingle and develop. Many types of foods have been created in or near Philadelphia or have strong associations with the city. In the 20th century, Philadelphia's foods included the cheesesteak, stromboli, hoagie, soft pretzel, water ice and soda.
The cheesesteak is a sandwich traditionally made with sliced beef and melted cheese on an Italian roll. In the 1930s, the phenomenon as a steak sandwich began when hot dog vendor brothers Pat Olivieri and Harry Olivieri put grilled beef on a hot dog bun and gave it to a taxi driver. Later, after Pat and Harry had started selling the sandwich on Italian rolls, the cheesesteak was affixed in the local culture when one of their cooks put melted cheese on the sandwich. |
260_2 | Originally, the cheese was melted in a separate container to accommodate their large clientele who followed kosher rules (thereby not mixing dairy and meat). Today, cheese choices in Philadelphia eateries are virtually limited to American, Provolone, or Cheez Whiz. The latter is especially popular in those places that prominently carry it.
The hoagie is another sandwich that is said to have been invented in Philadelphia, undoubtedly of origin in Italian-American cuisine. It has been asserted that Italians working at the World War I era shipyard in Philadelphia, known as Hog Island where emergency shipping was produced for the war effort, introduced the sandwich, by putting various sliced meats, cheeses, and lettuce between two slices of Italian bread. This became known as the "Hog Island" sandwich; hence, the "hoagie".
Declared the official sandwich of Philadelphia in 1992, the hoagie is a sandwich made of meat and cheese with lettuce, tomatoes, and onions on an Italian roll. |
260_3 | Another Italian roll sandwich popularized in Philadelphia by Italian immigrants is the roast pork Italian, or Italian roast pork sandwich, a variation of the Italian street food dish known as porchetta. The sandwich consists of sliced roast pork with broccoli rabe or spinach and provolone cheese.
Philadelphia Pepper Pot, a soup of tripe, meat, vegetables, is claimed to have been created during the American Revolutionary War and named after the home city of its creator.
Snapper soup, a thick brown turtle soup served with sherry, is a Philadelphia delicacy, generally found in area bars and seafood restaurants. In many places, it is served with oyster crackers (such as OTC Crackers, OTC being an abbreviation for "Original Trenton Cracker") and horseradish. |
260_4 | The snack item commonly associated with Philadelphia, but not invented there, is the soft pretzel. The soft pretzel dates back to 7th-century France and was brought over to the Philadelphia area by the Pennsylvania Dutch. Pretzels were sold in Philadelphia by numerous vendors on street corners. Federal Pretzel Baking Company defined the soft pretzel for most Philadelphians during the 1900s by first applying mass production and distribution to a distinctive baked flavored family recipe.
Another snack associated with Philadelphia is Irish potato candy. The candies have a coconut cream inside (generally made from some blend of coconut, confectioner's sugar, vanilla, and cream or cream cheese) and are rolled in cinnamon on the outside, resulting in an appearance reminiscent of small potatoes. The treats are about the size of a large marble and are especially popular around St. Patrick's Day. |
260_5 | Oh Ryan's of Boothwyn, Pennsylvania, claims to be the largest distributor of Irish Potatoes, shipping about 80,000 pounds to major chains and smaller candy stores, mostly in the Philadelphia area.
Water ice, known as Italian ice in other Northeastern US cities, is similarly associated with Philadelphia, brought to Philadelphia by Italian immigrants. Water ice likely derives from semi-frozen desserts originating in Italy, specifically granita. |
260_6 | The Philadelphia metropolitan area (including Delaware Valley, South Jersey, Southeastern Pennsylvania) is the only region of the United States to refer to the dessert as "water ice"; in other areas, such as New York City, water ice is called "Italian ice". However, despite the overlap and near synonymity between the two terms, water ice has been described as a specific type of Italian ice originating in Philadelphia, or a "variation on the more broadly-accepted Italian ice." Certain stands like South Philadelphia's "Pop's" or "Italiano's" became similar products later franchised into new markets like "Rita's Water Ice".
As with New York City and Chicago, Philadelphia has its own regional variant of hot dog known as the Texas Tommy, originating right outside Philadelphia in Pottstown, Pennsylvania before spreading throughout the Delaware Valley region and South Jersey. The Texas Tommy hot dog is defined by its use of cheese (usually cheddar cheese) and bacon as toppings. |
260_7 | Some variations of the Texas Tommy use other forms of cheese, replacing the cheddar with the Cheez-Whiz found on cheesesteaks. The bacon and cheese are often wrapped around the hot dog, and the hot dog may be cooked using a variety of methods, such as deep frying, barbecuing, or grilling. Condiments such as mustard, ketchup, or relish may be used in addition to the bacon and cheese.
Chili is also sometimes added to the Texas Tommy, making the dish resemble more closely a Texas Wiener or chili dog with bacon and cheese.
Some types of soda that rose to popularity in Philadelphia include Hires Root Beer, Franks Beverages' unique Black Cherry Wishniak or Vanilla Cream, and Levis Champ Cherry.
Restaurants and markets |
260_8 | In early Philadelphia history the city's eating scene was dominated by taverns. By 1752, Philadelphia had 120 licensed taverns and numerous illegal taverns. The taverns ranged for all types of people and class from illegal grog shops on the waterfront that sailors frequented to the upper class taverns that members of city government enjoyed.
Taverns such as the London Coffee House, the Blue Anchor, Tun Tavern and John Biddle's Indian King were regular meeting places for the political and business leaders of the city. The City Tavern is a replica of a historic 18th-century building located at 138 South 2nd Street and is part of Independence National Historical Park. The tavern offers authentic 18th-century recipes, served in seven period dining rooms, three wine cellar rooms and an outdoor garden.
McGillin's Olde Ale House, located on Drury Street in Center City, is the oldest continuously operated tavern in the city, and has become a well-knownplace for celeb-spotting. |
260_9 | Popular restaurants during the early 19th century included the United States Hotel and Parkinson's on Chestnut Street and Joseph Head Mansion's House on Spruce Street. One of the most significant restaurateurs and caterers at this time was M. Latouche, an expert in French cuisine, whose restaurant offered expensive food and choice wine.
Toward the end of the 19th century, the large number of Italian immigrants in South Philadelphia led to the creation of the Italian Market. The market, which runs along part of south 9th Street, includes numerous types of food vendors along with other shops, although today it is mostly made up of non-Italian merchants. |
260_10 | Another market, the Reading Terminal Market, opened in 1892. Created to replace the markets displaced by the construction of the Reading Terminal on Market Street in Center City, Reading Terminal Market has over 80 merchants and is a popular tourist attraction. In 1902, Joseph Horn and Frank Hardart opened the first automat in the U.S. at 818 Chestnut Street, now a retail store. The original Automat is now part of the Smithsonian Institution.
In the 1950s and 1960s, the restaurant scene was in decline. The city saw a large emigration into the suburbs, and fine dining could be found mainly in private clubs and dinner parties. |
260_11 | But as the city started to rebound in the 1970s, Philadelphia saw a restaurant renaissance. For instance, in 1970 Georges Perrier and Peter Von Starck founded French restaurant Le Panetiere. After a year, the two split, with Von Starck taking the Panetiere name to a different location. Perrier opened Le Bec-Fin at 13th & Spruce Street, then later at 1523 Walnut Street, which quickly became one of Philadelphia's most renowned restaurants. Another popular example is H.A Winston & Co., which evolved into a chain of restaurants located throughout the region.
The years following saw many new fine dining places open, including Four Seasons' Fountain Restaurant in 1983. Along with the up-scale restaurants, numerous ethnic and fast-food restaurants opened throughout the city. |
260_12 | The 1970s also saw the rise of street vendors. The vendors, building off the well-established tradition of chestnut and pretzel vendors, began selling numerous foods, especially hot dogs, cheesesteaks, and breakfast sandwiches. By taking up sidewalk space and possibly business, the vendors annoyed established stores which eventually led to numerous legal battles over ordinances which placed restrictions on vendors.
The issue was surrounded by race and class overtones, but vendors have since become commonplace and even nationally renowned for serving quality food.
A wide variety of eateries now thrive in Philadelphia. The city has a growing reputation for culinary excellence, and many of the city's chefs have been honored with nominations for James Beard Awards |
260_13 | Prolific local restaurateurs like Stephen Starr's STARR Restaurants and Iron Chef Jose Garces's Garces Restaurant Group operate restaurants that coexist with small chef-owned BYOBs. Major dining locations include Rittenhouse Square, Old City, Chinatown, Manayunk, East Passyunk Avenue and Fishtown.
A variety of cuisine popular with Philadelphians today include Italian, Mediterranean, Chinese, Japanese, steakhouses, French, gastropub fare, tapas, diners, delis, and pizzerias.
In September 2006, a smoking ban went into effect for Philadelphia bars and restaurants. The ban, which exempts private clubs, hotels, specialty smoking shops, and waiver-eligible bars that serve little food, had a troubled start and went unenforced until January 2007.
Just a month later Philadelphia City Council passed a ban on trans fat in restaurants, effective September 2, 2007. Other health reforms have been introduced by the Get Healthy Philly Initiative.
Other foods with Philadelphia historical roots |
260_14 | Cheese sauce—gooey, orange, dairy condiment carried by many street vendors. In general, Philadelphians often add cheese sauce to inexpensive food items, such as French fries and pretzels. The vast majority of cheese sauce served on Philadelphia foods is the national brand Cheez Whiz.
Funnel cake—associated with the Pennsylvania Dutch, made by pouring batter into hot cooking oil in a circular pattern and deep frying the overlapping mass until golden-brown; extremely popular in the Philadelphia area.
German butter cake—very rich type of pound cake with a buttery, pudding-like center, not to be confused with the traditional butter cake or the St. Louis version. Also called Philadelphia Butter Cake.
Good & Plenty—popular licorice pastille candy created in 1893.
Herr's—Philadelphia-area snack brand, noted for potato chips and other snack foods
Peanut Chews—popular candy produced in Philadelphia since 1917 |
260_15 | Pork roll—although developed and mostly produced in Trenton (on the border between the Philadelphia and New York spheres of influence) and mostly associated with New Jersey culinary traditions, pork roll is widely available in the Philadelphia area and well-incorporated into Philadelphian cuisine.
Roast pork sandwich—usually served on an Italian roll and often with broccoli rabe instead of spinach and most traditionally with sharp provolone; a staple of South Philadelphia cuisine.
Scrapple—processed meat loaf made of pork scraps and trimmings combined with cornmeal and flour, is a Pennsylvanian breakfast food. |
260_16 | Soda—in the early 19th century, Dr. Philip Syng Physick and John Hart of Philadelphia invented carbonated water in an attempt to simulate water from natural springs. In 1807, Philadelphian pharmacist Townsend Speakman sold fruit juice and carbonated water, inventing the first soft drink. In 1875, Charles Elmer Hires invented root beer by mixing sarsaparilla, sassafras, wild cherry, wintergreen, ginger, and alcohol. He sold it at his drug store in Philadelphia.
Whoopie pie—also associated with the Pennsylvania Dutch, it is made of two round mound-shaped pieces of chocolate cake, or sometimes pumpkin or gingerbread cake, with a sweet, creamy filling or frosting sandwiched between them. Also popular in New England.
Spiced wafers—type of cookie traditionally sold in the autumn. |
260_17 | Stromboli—reported to have originated in 1950 in Essington, just outside Philadelphia. It is a type of turnover made with Italian bread dough filled with various kinds of cheese, Italian charcuterie or vegetables. Panzarotti is a trademark for a type of deep-fried stromboli, particularly associated with Philadelphia's South Jersey suburbs.
Tastykake—most well-known snack brand native to Philadelphia. Since 1914, the Tasty Baking Company has provided the region with its line of pre-packaged baked goods; best-known varieties include Krimpets, cupcakes, Kandy Kakes (wafer-sized chocolate and peanut butter cakes), and Tasty Pies.
Tomato pie—essentially a cheeseless pizza two-feet by three-feet in size, with extra oregano. Tomato pie is normally served cold or at room temperature. It is more often found in the Northeast section of Philadelphia and at bakeries in South Philadelphia with variations found in Trenton, New Jersey and other suburban localities. |
260_18 | Texas Tommy—grilled, split hot dog with bacon and cheese; a common hot dog dish in Philadelphia.
Water ice—a version of Italian ice that is popular in Philadelphia and the Delaware Valley. It is sold to order at specific shops and pre-packaged in grocery stores. |
260_19 | Alcoholic beverages
Beer was brewed by English colonial inhabitants of Philadelphia since the city's founding in 1682, and later by German immigrants that settled the city's countryside. Because of this, the city is strongly identified with both English-style beer (particularly porter, a variety that was virtually synonymous with Philadelphia during the American Revolutionary period) and German-style beer (such as lager), which eclipsed the English style near the end of the 19th century.
In the industry's heyday before Prohibition, more than 90 breweries operated in city limits, with another 100 located in the greater metropolitan area. A neighborhood in the city is still called Brewerytown, owing to the concentration of breweries in the area during this time. The last of the city's most successful brewers, such as the Henry F. Ortlieb Brewing Company and the Christian Schmidt Brewing Company, shut down in the 1980s. |
260_20 | The beer most associated with Philadelphia is Yuengling lager, brewed in nearby Pottsville, Pennsylvania and often referred to as simply "Lager" by Philadelphians and people in the Delaware Valley and South Jersey.
Recently, however, a number of highly regarded micro-breweries and brewpubs appeared in and around the city in the 1990s and 2000s, such as Victory, Yards and PBC, reviving the city's dormant brewing industry. (For more information, see Breweries in Philadelphia.) In 2011, Philadelphia was ranked as one of the 14 best beer cities in the world by Frommer's, and the city's annual beer week is among its most popular food-centric civic events.
Other notable Delaware Valley microbreweries and brewpubs include Iron Hill Breweries and the award-winning Sly Fox Brewery.
The distillation of spirits in Philadelphia has a long history, but the industry has sat idle for several decades. |
260_21 | One of the largest manufacturing complexes in the city, spanning 40 acres, was owned by Publicker Industries, which produced chemicals, industrial alcohols and spirits in South Philadelphia. Its Continental Distilling Company arm produced Old Hickory bourbon, Inver House Scotch and Skol vodka, among many other liquors, before the company abandoned the site in 1986.
The oldest producer of cordials and liqueurs in the U.S., Charles Jacquin et Cie, remains in operation in the city's Kensington neighborhood; the company is best known for its Pravda vodka, Jacquin's family of liqueurs and Original Bartenders Cocktails brand, well as its introduction of Chambord (sold to Brown-Forman in 2006), Creme Yvette, St-Germain and Domaine de Canton to the U.S. market. |
260_22 | More recently, Philadelphia Distilling opened in 2005 in the city's Fishtown neighborhood; it is the first craft distillery to open in Pennsylvania since before Prohibition, and produces Bluecoat American Dry Gin, Vieux Carré Absinthe Supérieure, Penn 1681 vodka, XXX Shine corn whiskey and The Bay, a vodka seasoned with Chesapeake Bay seasoning.
See also
Cuisine of the Pennsylvania Dutch
Cuisine of the Thirteen Colonies
Cuisine of New Jersey
Cuisine of Allentown, Pennsylvania
References |
261_0 | A double layer (DL, also called an electrical double layer, EDL) is a structure that appears on the surface of an object when it is exposed to a fluid. The object might be a solid particle, a gas bubble, a liquid droplet, or a porous body. The DL refers to two parallel layers of charge surrounding the object. The first layer, the surface charge (either positive or negative), consists of ions adsorbed onto the object due to chemical interactions. The second layer is composed of ions attracted to the surface charge via the Coulomb force, electrically screening the first layer. This second layer is loosely associated with the object. It is made of free ions that move in the fluid under the influence of electric attraction and thermal motion rather than being firmly anchored. It is thus called the "diffuse layer". |
261_1 | (-> this description of DL is not right, at least concerning the electrode/electrolyte interface. Here DL refers to charge separation at the interface with the electrode (which typically is a metal) possessing negative charge and the electrolyte positive charge. The two layers (one electronic the other ionic) are separated by some molecular distance. The two layers mentioned in above description are all at the electrolyte side (the Gouy-Chapman model). |
261_2 | Interfacial DLs are most apparent in systems with a large surface area to volume ratio, such as a colloid or porous bodies with particles or pores (respectively) on the scale of micrometres to nanometres. However, DLs are important to other phenomena, such as the electrochemical behaviour of electrodes.
DLs play a fundamental role in many everyday substances. For instance, homogenized milk exists only because fat droplets are covered with a DL that prevents their coagulation into butter. DLs exist in practically all heterogeneous fluid-based systems, such as blood, paint, ink and ceramic and cement slurry.
The DL is closely related to electrokinetic phenomena and electroacoustic phenomena.
Development of the (interfacial) double layer
Helmholtz |
261_3 | When an electronic conductor is brought in contact with a solid or liquid ionic conductor (electrolyte), a common boundary (interface) among the two phases appears. Hermann von Helmholtz was the first to realize that charged electrodes immersed in electrolyte solutions repel the co-ions of the charge while attracting counterions to their surfaces. Two layers of opposite polarity form at the interface between electrode and electrolyte. In 1853 he showed that an electrical double layer (DL) is essentially a molecular dielectric and stores charge electrostatically. Below the electrolyte's decomposition voltage, the stored charge is linearly dependent on the voltage applied.
This early model predicted a constant differential capacitance independent from the charge density depending on the dielectric constant of the electrolyte solvent and the thickness of the double-layer. |
261_4 | This model, with a good foundation for the description of the interface, does not consider important factors including diffusion/mixing of ions in solution, the possibility of adsorption onto the surface, and the interaction between solvent dipole moments and the electrode.
Gouy–Chapman
Louis Georges Gouy in 1910 and David Leonard Chapman in 1913 both observed that capacitance was not a constant and that it depended on the applied potential and the ionic concentration. The "Gouy–Chapman model" made significant improvements by introducing a diffuse model of the DL. In this model, the charge distribution of ions as a function of distance from the metal surface allows Maxwell–Boltzmann statistics to be applied. Thus the electric potential decreases exponentially away from the surface of the fluid bulk. |
261_5 | Stern
The Gouy-Chapman model fails for highly charged DLs. In 1924, Otto Stern suggested combining the Helmholtz model with the Gouy-Chapman model: in Stern's model, some ions adhere to the electrode as suggested by Helmholtz, giving an internal Stern layer, while some form a Gouy-Chapman diffuse layer.
The Stern layer accounts for ions' finite size and consequently an ion's closest approach to the electrode is on the order of the ionic radius. The Stern model has its own limitations, namely that it effectively treats ions as point charges, assumes all significant interactions in the diffuse layer are Coulombic, assumes dielectric permittivity to be constant throughout the double layer, and that fluid viscosity is constant plane. |
261_6 | Grahame
D. C. Grahame modified the Stern model in 1947. He proposed that some ionic or uncharged species can penetrate the Stern layer, although the closest approach to the electrode is normally occupied by solvent molecules. This could occur if ions lose their solvation shell as they approach the electrode. He called ions in direct contact with the electrode "specifically adsorbed ions". This model proposed the existence of three regions. The inner Helmholtz plane (IHP) passes through the centres of the specifically adsorbed ions. The outer Helmholtz plane (OHP) passes through the centres of solvated ions at the distance of their closest approach to the electrode. Finally the diffuse layer is the region beyond the OHP. |
261_7 | Bockris/Devanathan/Müllen (BDM)
In 1963 J. O'M. Bockris, M. A. V. Devanathan and Klaus Müller proposed the BDM model of the double-layer that included the action of the solvent in the interface. They suggested that the attached molecules of the solvent, such as water, would have a fixed alignment to the electrode surface. This first layer of solvent molecules displays a strong orientation to the electric field depending on the charge. This orientation has great influence on the permittivity of the solvent that varies with field strength. The IHP passes through the centers of these molecules. Specifically adsorbed, partially solvated ions appear in this layer. The solvated ions of the electrolyte are outside the IHP. Through the centers of these ions pass the OHP. The diffuse layer is the region beyond the OHP. |
261_8 | Trasatti/Buzzanca
Further research with double layers on ruthenium dioxide films in 1971 by Sergio Trasatti and Giovanni Buzzanca demonstrated that the electrochemical behavior of these electrodes at low voltages with specific adsorbed ions was like that of capacitors. The specific adsorption of the ions in this region of potential could also involve a partial charge transfer between the ion and the electrode. It was the first step towards understanding pseudocapacitance.
Conway
Between 1975 and 1980 Brian Evans Conway conducted extensive fundamental and development work on ruthenium oxide electrochemical capacitors. In 1991 he described the difference between 'Supercapacitor' and 'Battery' behavior in electrochemical energy storage. In 1999 he coined the term supercapacitor to explain the increased capacitance by surface redox reactions with faradaic charge transfer between electrodes and ions. |
261_9 | His "supercapacitor" stored electrical charge partially in the Helmholtz double-layer and partially as the result of faradaic reactions with "pseudocapacitance" charge transfer of electrons and protons between electrode and electrolyte. The working mechanisms of pseudocapacitors are redox reactions, intercalation and electrosorption.
Marcus |
261_10 | The physical and mathematical basics of electron charge transfer absent chemical bonds leading to pseudocapacitance was developed by Rudolph A. Marcus. Marcus Theory explains the rates of electron transfer reactions—the rate at which an electron can move from one chemical species to another. It was originally formulated to address outer sphere electron transfer reactions, in which two chemical species change only in their charge, with an electron jumping. For redox reactions without making or breaking bonds, Marcus theory takes the place of Henry Eyring's transition state theory which was derived for reactions with structural changes. Marcus received the Nobel Prize in Chemistry in 1992 for this theory. |
261_11 | Mathematical description
There are detailed descriptions of the interfacial DL in many books on colloid and interface science and microscale fluid transport. There is also a recent IUPAC technical report on the subject of interfacial double layer and related electrokinetic phenomena. |
261_12 | As stated by Lyklema, "...the reason for the formation of a "relaxed" ("equilibrium") double layer is the non-electric affinity of charge-determining ions for a surface..." This process leads to the buildup of an electric surface charge, expressed usually in C/m2. This surface charge creates an electrostatic field that then affects the ions in the bulk of the liquid. This electrostatic field, in combination with the thermal motion of the ions, creates a counter charge, and thus screens the electric surface charge. The net electric charge in this screening diffuse layer is equal in magnitude to the net surface charge, but has the opposite polarity. As a result, the complete structure is electrically neutral. |
261_13 | The diffuse layer, or at least part of it, can move under the influence of tangential stress. There is a conventionally introduced slipping plane that separates mobile fluid from fluid that remains attached to the surface. Electric potential at this plane is called electrokinetic potential or zeta potential (also denoted as ζ-potential).
The electric potential on the external boundary of the Stern layer versus the bulk electrolyte is referred to as Stern potential. Electric potential difference between the fluid bulk and the surface is called the electric surface potential. |
261_14 | Usually zeta potential is used for estimating the degree of DL charge. A characteristic value of this electric potential in the DL is 25 mV with a maximum value around 100 mV (up to several volts on electrodes). The chemical composition of the sample at which the ζ-potential is 0 is called the point of zero charge or the iso-electric point. It is usually determined by the solution pH value, since protons and hydroxyl ions are the charge-determining ions for most surfaces.
Zeta potential can be measured using electrophoresis, electroacoustic phenomena, streaming potential, and electroosmotic flow.
The characteristic thickness of the DL is the Debye length, κ−1. It is reciprocally proportional to the square root of the ion concentration C. In aqueous solutions it is typically on the scale of a few nanometers and the thickness decreases with increasing concentration of the electrolyte. |
261_15 | The electric field strength inside the DL can be anywhere from zero to over 109 V/m. These steep electric potential gradients are the reason for the importance of the DLs.
The theory for a flat surface and a symmetrical electrolyte is usually referred to as the Gouy-Chapman theory. It yields a simple relationship between electric charge in the diffuse layer σd and the Stern potential Ψd:
There is no general analytical solution for mixed electrolytes, curved surfaces or even spherical particles. There is an asymptotic solution for spherical particles with low charged DLs. In the case when electric potential over DL is less than 25 mV, the so-called Debye-Huckel approximation holds. It yields the following expression for electric potential Ψ in the spherical DL as a function of the distance r from the particle center:
There are several asymptotic models which play important roles in theoretical developments associated with the interfacial DL. |
261_16 | The first one is "thin DL". This model assumes that DL is much thinner than the colloidal particle or capillary radius. This restricts the value of the Debye length and particle radius as following:
This model offers tremendous simplifications for many subsequent applications. Theory of electrophoresis is just one example. The theory of electroacoustic phenomena is another example.
The thin DL model is valid for most aqueous systems because the Debye length is only a few nanometers in such cases. It breaks down only for nano-colloids in solution with ionic strengths close to water.
The opposing "thick DL" model assumes that the Debye length is larger than particle radius:
This model can be useful for some nano-colloids and non-polar fluids, where the Debye length is much larger.
The last model introduces "overlapped DLs". This is important in concentrated dispersions and emulsions when distances between particles become comparable with the Debye length. |
261_17 | Electrical double layers
The electrical double layer (EDL) is the result of the variation of electric potential near a surface, and has a significant influence on the behaviour of colloids and other surfaces in contact with solutions or solid-state fast ion conductors.
The primary difference between a double layer on an electrode and one on an interface is the mechanisms of surface charge formation. With an electrode, it is possible to regulate the surface charge by applying an external electric potential. This application, however, is impossible in colloidal and porous double layers, because for colloidal particles, one does not have access to the interior of the particle to apply a potential difference.
EDLs are analogous to the double layer in plasma.
Differential capacitance
EDLs have an additional parameter defining their characterization: differential capacitance. Differential capacitance, denoted as C, is described by the equation below: |
261_18 | where σ is the surface charge and ψ is the electric surface potential. |
261_19 | Electron transfer in electrical double layer |
261_20 | The formation of electrical double layer (EDL) has been traditionally assumed to be entirely dominated by ion adsorption and redistribution. With considering the fact that the contact electrification between solid-solid is dominated by electron transfer, it is suggested by Wang that the EDL is formed by a two-step process. In the first step, when the molecules in the solution first approach a virgin surface that has no pre-existing surface charges, it may be possible that the atoms/molecules in the solution directly interact with the atoms on the solid surface to form strong overlap of electron clouds. Electron transfer occurs first to make the “neutral” atoms on solid surface become charged, i.e., the formation of ions. In the second step, if there are ions existing in the liquid, such as H+ and OH-, the loosely distributed negative ions in the solution would be attracted to migrate toward the surface bonded ions due to electrostatic interactions, forming an EDL. Both electron |
261_21 | transfer and ion transfer co-exist at liquid-solid interface. |
261_22 | See also
Depletion region (structure of semiconductor junction)
DLVO theory
Electroosmotic pump
Interface and colloid science
Nanofluidics
Poisson-Boltzmann equation
Supercapacitor
References
Further reading
External links
The Electrical Double Layer
Chemical mixtures
Colloidal chemistry
Condensed matter physics
Electrochemistry
Matter
Soft matter |
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