Cyanogen Bromide
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Recent Advances in Cyanamide Chemistry: Synthesis and Applications
molecules Review Recent Advances in Cyanamide Chemistry: Synthesis and Applications M. R. Ranga Prabhath, Luke Williams, Shreesha V. Bhat and Pallavi Sharma * School of Chemistry, Joseph Banks Laboratories, University of Lincoln, Lincoln LN6 7DL, UK; [email protected] (M.R.R.P.); [email protected] (L.W.); [email protected] (S.V.B.) * Correspondence: [email protected]; Tel.: +44-015-2288-6885 Academic Editor: Margaret A. Brimble Received: 9 March 2017; Accepted: 7 April 2017; Published: 12 April 2017 Abstract: The application of alkyl and aryl substituted cyanamides in synthetic chemistry has diversified multi-fold in recent years. In this review, we discuss recent advances (since 2012) in the chemistry of cyanamides and detail their application in cycloaddition chemistry, aminocyanation reactions, as well as electrophilic cyanide-transfer agents and their unique radical and coordination chemistry. Keywords: cyanamide; synthesis; aminocyanation; cycloaddition; electrophilic cyanation; radical reaction; coordination chemistry 1. Introduction Cyanamide enjoys a rich chemical history, which can be traced to its unique and chemically promiscuous nitrogen-carbon-nitrogen (NCN) connectivity. The chemistry of the nitrile-substituted amino-group of the ‘cyanamide-moiety’ is dominated by an unusual duality of a nucleophilic sp3-amino nitrogen and an electrophilic nitrile unit. The reported use of unsubstituted cyanamide (NH2CN) and metal cyanamides (MNCN, where M = metal) date back as far as the late 19th century, where the likes of calcium cyanamide (CaNCN) was used as a fertilizer, and later as source of ammonia and nitric acid, which fueled the industrial production of metal cyanamides. In contrast, the reported use of the corresponding substituted organic cyanamides (RNHCN or RR’NCN) gathered pace only in more recent years. -
United States Patent 19 11 Patent Number: 5,360,712 Olm Et Al
D US005360712A United States Patent 19 11 Patent Number: 5,360,712 Olm et al. 45 Date of Patent: Nov. 1, 1994 54 INTERNALLY DOPED SILVER HALIDE 4,981,781 1/1991 McDugle et al. ................... 430/605 EMULSIONS AND PROCESSES FOR THER 5,037,732 8/1991 McDugle et al. ................... 430/567 ARA 5,132,203 7/1992 Bell et al. ............. ... 430/567 PREP TION 5,268,264 12/1993 Marchetti et al. .................. 430/605 75) Inventors: McDugle;Myra T. Olm, Sherrin Webster; A. Puckett, Woodrow both G.of FOREIGN PATENT DOCUMENTS Rochester; Traci Y. Kuromoto, West 513748A1 11/1992 European Pat. Off. ... GO3C 7/392 Henrietta; Raymond S. Eachus, Rochester; Eric L. Bell, Wesbter; OTHER PUBLICATIONS Robert D. Wilson, Rochester, all of Research Disclosure, vol. 176, Dec. 1978, Item 17643, N.Y. Section I, subsection A. Research Disclosure, vol. 308, Dec. 1989, Item 308119, 73) Assignee: Eastman Kodak Company, Section, I, subsection D. Rochester, N.Y. 21 Appl. No.: 91,148 Primary Examiner-Janet C. Baxter J. v. V. 19 Attorney, Agent, or Firm-Carl O. Thomas 51) Int. Cl................................................. GC/ A process is disclosed of preparing a radiation sensitive 52 U.S.C. .................................... 430/567; 430/569; silver halide emulsion comprising reacting silver and 430/604; 430/605 halide ions in a dispersing medium in the presence of a 58 Field of Search ................ 430/567, 569, 604, 605 metal hexacoordination or tetracoordination complex (56) References Cited having at least one organic ligand containing a least one carbon-to-carbon bond, at least one carbon-to-hydro U.S. -
Determination of the Activation Parameters of Reaction Between [Fe(CN6] and K[Co(HEDTA)NO2]." (2009)
East Tennessee State University Digital Commons @ East Tennessee State University Electronic Theses and Dissertations Student Works 12-2009 Determination of the Activation Parameters of -4 Reaction Between [Fe(CN6] and K[Co(HEDTA)NO2]. Sammy Eni Eni East Tennessee State University Follow this and additional works at: https://dc.etsu.edu/etd Part of the Organic Chemistry Commons Recommended Citation -4 Eni Eni, Sammy, "Determination of the Activation Parameters of Reaction Between [Fe(CN6] and K[Co(HEDTA)NO2]." (2009). Electronic Theses and Dissertations. Paper 1798. https://dc.etsu.edu/etd/1798 This Thesis - Open Access is brought to you for free and open access by the Student Works at Digital Commons @ East Tennessee State University. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ East Tennessee State University. For more information, please contact [email protected]. -4 The Determination of the Activation Parameters of Reaction Between [Fe(CN)6] and K[Co(HEDTA)NO2] ________________________________ A thesis presented to the faculty of the Department of Chemistry East Tennessee State University in Partial Fulfillment of the requirements for the degree Master of Science in Chemistry ________________________________ by Sammy Eni Eni December 2009 ________________________________ Dr. Jeffrey Wardeska, Chair Dr. Ningfeng Zhao Dr. Yu-Lin Jiang -4 Keywords: Activation parameters, [Fe(CN)6] , K[Co(HEDTA)NO2]. ABSTRACT -4 Determination of the Activation Parameters of Reaction Between [Fe(CN)6] and K[Co(HEDTA)NO2] by Sammy Eni Eni -4 The kinetics of the oxidation of [Fe(CN)6] by K[Co(HEDTA)NO2] was studied in order to get the mechanism and the activation parameters of the reaction. -
Reversibility of Ferri-/Ferrocyanide Redox During Operando Soft X-Ray Spectroscopy
Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Risch, Marcel, Kelsey A. Stoerzinger, Tom Z. Regier, Derek Peak, Sayed Youssef Sayed, and Yang Shao-Horn. “Reversibility of Ferri-/ Ferrocyanide Redox During Operando Soft X-Ray Spectroscopy.” The Journal of Physical Chemistry C 119, no. 33 (August 20, 2015): 18903–18910. As Published http://dx.doi.org/10.1021/acs.jpcc.5b04609 Publisher American Chemical Society (ACS) Version Author's final manuscript Citable link http://hdl.handle.net/1721.1/109590 Terms of Use Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. Reversibility of Ferri-Ferrocyanide Redox During Operando Soft X-Ray Spectroscopy ┴ Marcel Risch,†* Kelsey A. Stoerzinger,§ Tom Z. Regier,‡ Derek Peak,º Sayed Youssef Sayed,† Yang Shao-Horn†§||* †Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA 02139 §Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA 02139 ||Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA 02139 ‡Canadian Light Source, Inc., Saskatoon, SK, Canada S7N 2V3 ºDepartment of Soil Sciences, University of Saskatchewan, Saskatoon, SK, Canada S7N 5A8 KEYWORDS. Electrochemistry; In-situ; redox shuttle; iron cyanide; X-ray absorption; radiolysis; radiation damage. ABSTRACT The ferri-ferrocyanide redox couple is ubiquitous in many fields of physical chemistry. We studied its photochemical response to intense synchrotron radiation by in-situ X-Ray absorption spectroscopy. -
Investigation of Novel Nanoparticles of Gallium Ferricyanide and Gallium Lawsonate As Potential Anticancer Agents, and Nanoparti
Investigation of Novel Nanoparticles of Gallium Ferricyanide and Gallium Lawsonate as Potential Anticancer Agents, and Nanoparticles of Novel Bismuth Tetrathiotungstate as Promising CT Contrast Agent A Thesis submitted to Kent State University In partial fulfillment of the requirements for the degree of Master of Science Liu Yang August 2014 Thesis written by Liu Yang B.S. Kent State University, 2013 M.S. Kent State University, 2014 Approved by ___________________________________, Advisor, Committee member Dr. Songping Huang ___________________________________, Committee member Dr. Scott Bunge ___________________________________, Committee member Dr. Mietek Jaroniec Accepted by ___________________________________, Chair, Department of Chemistry Dr. Michael Tubergen ___________________________________, Dean, College of Arts and Sciences Dr. James L. Blank ii Table of Contents List of Figures..…………………………………………………………………........vii Acknowledgements ……………………………………………………………….….xi Chapter 1: Summary, Materials and Methods …..……………………………………1 1.1 Materials ………………………………………………………………….3 1.1.1 carboxymethyl reduced polysaccharide (CMRD) preparation….3 1.2 Methods …………………………………………………………………4 1.2.1 Atomic absorption spectroscopy (AA) …………………………4 1.2.2 Acid base treating method ……………………………………...4 1.2.3 Cell viability study ……………………………………………...5 i) MTT assay…………………………………………………..5 ii) Trypan blue assay ………………………………………….6 1.2.4 Dialysis …………………………………………………………6 1.2.5 Elementary analysis …………………………………………….7 1.2.6 Lyophilization …………………………………………………..7 iii 1.2.7 -
MSDS Material Safety Data Sheet
For RICCA, SpectroPure, Red Bird, and Solutions Plus Brands Emergency Contact(24 hr) -- CHEMTREC® Domestic: 800-424-9300 International: 703-527-3887 ZOBELL'S SOLUTION, APHA ORP Solution, and other ORP Standards MSDS Material Safety Data Sheet Section 1: Chemical Product and Company Identification Catalog Number: 5464.5, 9880, OX-905, PX-918, R5464510, S0932A, SZ117300 Product Identity: ZOBELL'S SOLUTION, APHA ORP Solution, and other ORP Standards Manufacturer's Name: Emergency Contact(24 hr) -- CHEMTREC® RICCA CHEMICAL COMPANY LLC Domestic: 800-424-9300 International: 703-527-3887 CAGE Code: 4TCW6, 0V553, 4XZQ2 Address: Telephone Number For Information: 448 West Fork Dr 817-461-5601 Arlington, TX 76012 Date Prepared: 11/9/98 Revision: 9 Last Revised: 01/24/2014 Date Printed: 03/25/2015 1:19:09 pm Section 2. Composition/Information on Ingredients Component CAS Registry # Concentration ACGIH TLV OSHA PEL < 0.2% (w/v) Not Available Not Available Potassium Ferricyanide 13746-66-2 Not Available Not Available < 0.5% (w/v) Not Available Not Available Potassium Ferrocyanide Trihydrate 14459-95-1 1 (as Fe) mg/m3 Not Available < 1% (w/v) Not Available Not Available Potassium Chloride 7447-40-7 Not Available Not Available Balance Not Available Not Available Water, Deionized 7732-18-5 Not Available Not Available Section 3: Hazard Identification Emergency Overview: Does not present any significant health hazards. Wash areas of contact with water. Target Organs: eyes, skin Eye Contact: May cause slight irritation. Inhalation: Not likely to be hazardous by inhalation. Skin Contact: May cause slight irritation. Ingestion: May cause nausea, vomiting, diarrhea and cramps. -
The Light Triggered Dissolution of Gold Wires Using Potassium Ferrocyanide T Solutions Enables Cumulative Illumination Sensing ⁎ Weida D
Sensors & Actuators: B. Chemical 282 (2019) 52–59 Contents lists available at ScienceDirect Sensors and Actuators B: Chemical journal homepage: www.elsevier.com/locate/snb The light triggered dissolution of gold wires using potassium ferrocyanide T solutions enables cumulative illumination sensing ⁎ Weida D. Chena, Seung-Kyun Kangb, Wendelin J. Starka, John A. Rogersc,d,e, Robert N. Grassa, a Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland b Department of Bio and Brain Engineering, KAIST, 291 Daehak-ro, Yuseong-gu, Daejeon 334141, Republic of Korea c Departments of Materials Science and Engineering, Biomedical Engineering, Neurological Surgery, Chemistry, Mechanical Engineering, Electrical Engineering and Computer Science, Northwestern University, Evanston, IL 60208, USA d Center for Bio-Integrated Electronics, Northwestern University, Evanston, IL 60208, USA e Simpson Querrey Institute for Nano/Biotechnology, Northwestern University, Evanston, IL 60208, USA ARTICLE INFO ABSTRACT Keywords: Electronic systems with on-demand dissolution or destruction capabilities offer unusual opportunities in hard- Photochemistry ware-oriented security devices, advanced military spying and controlled biological treatment. Here, the dis- Cyanide solution chemistry of gold, generally known as inert metal, in potassium ferricyanide and potassium ferrocya- Sensor nide solutions has been investigated upon light exposure. While a pure aqueous solution of potassium Conductors ferricyanide–K3[Fe(CN)6] does not dissolve gold, an aqueous solution of potassium ferrocyanide–K4[Fe(CN)6] Diffusion limitation irradiated with ambient light is able to completely dissolve a gold electrode within several minutes. Photo Devices activation and dissolution kinetics were assessed at different initial pH values, light irradiation intensities and ferrocyanide concentrations. -
Cyanogera Bromide and Cyanogen. by AUGUSTUSEDWARD DIXON and JOHNTAYLOR
View Article Online / Journal Homepage / Table of Contents for this issue 974 DIXON AND TAYLOR: GI.- Cyanogera Bromide and Cyanogen. By AUGUSTUSEDWARD DIXON and JOHNTAYLOR. CYANOGENbromide, in cold aqueous solution, or in the presence of such dilute acids as do not of themselves chemically decompose it, shows no evidence of suffering ionic dissociation. The dilute aqueous solution has the same odour as the solid compound; even after long keeping it yields with silver nitrate no turbidity; it is neutral to litmus, and the pungent vapour fails to give the guaiacum and copper sulphate reaction for hydrogen cyanide ; moreover, the solution is a very feeble conductor of electricity. Although the mixture produced by treating cyanogen bromide with alkali hydroxide contains but alkali bromide and alkali cyanate, Chattaway and Wadmore are of opinion (T., 1902, 81, 199) that hypobromite must first be formed, and then reduced. That cyanate is not directly formed in the reaction with alkali hydroxide is proved from the following facts: (1) Alkali cyanate is not reduced to cyanide by hydriodic acid, ferrous sulphate and alkali, sulphurous acid, alkali sulphite, or even by treatment with aluminium and alkali hydroxide. Further, it has no action on carbamide, either alone or in presence of alkali, (2) If cyanogen bromide is treated with alkali iodide, followed -by alkali, the mixture contains cyanide, but no cyanate, and, when acidified, yields free iodine. (3) If it is treated with ferrous sulphate, and subsequently with alkali and ferric salt, the mixture on acidification gives Prussian- blue, but contains no cyanate. Published on 01 January 1913. -
Reverse-Phase High-Performance Liquid Chromatography of Hydrophobic Proteins and Fragments Thereof’
ANALYTICAL BIOCHEMISTRY 131,99-107 (1983) Reverse-Phase High-Performance Liquid Chromatography of Hydrophobic Proteins and Fragments Thereof’ GEORGE E.TARR*'~ ANDJOHN W.CRABB-~~ *Department of Biological Chemistry, University of Michigan, Ann Arbor, Michigan 48109, and lDepartment of Ophthalmology, University of Washington, Seattle, Washington 98195 Received January 31, 1983 Reverse-phase high-performance liquid chromatography (HPLC) resolution and recovery of cytochrome P-450 and bovine rhodopsin, both integral membrane proteins, and large peptides derived from P-450 LMI were enhanced by utilizing ternary solvents. Surprisingly, most test materials eluted later in the gradient when using mixtures of acetonitrile and propanol in the mobile phase compared to using either solvent alone. Of the supports tested, the best recovery of hydrophobic cytochrome P-450 LMI was experienced on the less retentive CN-bonded phase. Two alternate solvents for HPLC of polypeptides are proposed: (1) 0.02-o. 1 M hexafluoroacetone/ NH3, pH 7.2 for highly acidic peptides; and (2) 6 M formic acid/O.13 M trimethylamine, pH 1.5, vs 4 M formic acid/O.09 M trimethylamine in propanol for relatively insoluble peptides. Anomalous side reactions between formic acid and peptides can cause HPLC peak broadening, increased retention, and decreased resolution. These deleterious effects are thought to be due in part to formyl esterilication of serine and threonine residues and appear to be reversible by aminoethanol treatment. High-performance liquid chromatography, tides (3-7) and hydrophobic, membrane-as- particularly reverse-phase chromatography, sociated polypeptides (8- 14), methods for such has supplanted the more classical methods of fractionations are not yet well established. -
Long-Term Ferrocyanide Application Via Deicing Salts Promotes the Establishment of Actinomycetales Assimilating Ferrocyanide-Derived Carbon in Soil
bs_bs_banner Long-term ferrocyanide application via deicing salts promotes the establishment of Actinomycetales assimilating ferrocyanide-derived carbon in soil Silvia Gschwendtner,1 Tim Mansfeldt,2 soils, belonging mostly to Actinomycetales Susanne Kublik,1 Evangelia Touliari,1 (Kineosporia, Mycobacterium, Micromonosporaceae). Franz Buegger3 and Michael Schloter1,* In the soil without pre-exposition, bacteria belonging 1Research Unit Environmental Genomics, Helmholtz to Acidobacteria (Gp3, Gp4, Gp6), Gemmatimonade- Zentrum Munchen,€ German Research Center for tes (Gemmatimonas)andGammaproteobacteria Environmental Health (GmbH), Ingolstadter€ Landstraße 1, (Thermomonas, Xanthomonadaceae)usedferro- Neuherberg 85764, Germany. cyanide as C source but not the present Actinomyc- 2Department Geowissenschaften, Bodengeographie/ etales. This indicated that (i) various bacteria are able Bodenkunde, Universitat€ zu Koln,€ Albertus-Magnus- to assimilate ferrocyanide-derived C and (ii) long-term Platz, Koln€ 50923, Germany. exposition to ferrocyanide applied with deicing salts 3Institute of Biochemical Plant Pathology, Helmholtz leads to Actinomycetales outcompeting other microor- Zentrum Munchen,€ German Research Center for ganisms for the use of ferrocyanide as C source. Environmental Health (GmbH), Ingolstadter€ Landstraße 1, Neuherberg 85764, Germany. Introduction Cyanide is produced by various organisms including Summary bacteria, algae, fungi and higher plants as defence Cyanides are highly toxic and produced by various mechanism or offensive strategy (Møller and Seigler, microorganisms as defence strategy or to increase 1998; Gallagher and Manoil, 2001; Zagrobelny et al., their competitiveness. As degradation is the most 2008) and consequently occurs naturally at low levels in efficient way of detoxification, some microbes devel- the environment. However, it is highly toxic for living oped the capability to use cyanides as carbon and organisms by complexing metalloproteins, e.g. -
Problems 14, 15, 16, 19, 22, 24, and 25 in Dekock and Gray, Pages 411–414. 14. “All Octahedral Complexes of V3+ Have The
Problems 14, 15, 16, 19, 22, 24, and 25 in DeKock and Gray, pages 411–414. 14. “All octahedral complexes of V3+ have the same number of unpaired electrons, no matter what the nature of the ligand. Why is this so?” V3+ has a d2 electron configuration; in an octahedral ligand environment, regardless of the type of ligand interactions, the lowest energy orbitals are the triply degenerate 2 t2g orbitals. A d octahedral metal complex will always have 2 unpaired electrons. For the same reason, octahedral d1, d3, d8, d9, and d10 also only have one possible electronic configuration. 15. “How does the molecular-orbital theory account for the order of ligands in the spectrochemical series.” The spectrochemical series (courtesy of Wikipedia): I− < Br− < S2− < SCN− < Cl− < − − − − 2− − NO3 < N3 < F < OH < C2O4 ≈ H2O < NCS < CH3CN < pyridine < NH3 < − − ethylenediamine < 2,2'-bipyridine < 1,10-phenanthroline < NO2 < PPh3 < CN ≈ CO. This series can be explained by the type of π interactions on the ligands. The ligands with the smallest octahedral splitting will be π-donors (i.e. I-, Br-, etc) who will bond with the t2g orbitals on the metal, raising it in energy, thus decreasing the - t2g eg splitting. Similarly, π-acceptors (i.e. CN , CO, etc) will have the largest octahedral splitting energy as the t2g orbitals on the metal now become bonding and decrease in energy. The ligands in the middle of the series have little π-interaction with the metal and therefore the t2g remain nonbonding. 3- 4- 16. “Explain why Co(CN)6 is extremely stable but Co(CN)6 is not.” 3- 6 6 4- 7 6 1 Co(CN)6 is low spin d , therefore t2g , while Co(CN)6 is low spin d , t2g eg* . -
Cyanogen Bromide; CASRN 506-68-3
Integrated Risk Information System (IRIS) U.S. Environmental Protection Agency Chemical Assessment Summary National Center for Environmental Assessment Cyanogen bromide; CASRN 506-68-3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data, as outlined in the IRIS assessment development process. Sections I (Health Hazard Assessments for Noncarcinogenic Effects) and II (Carcinogenicity Assessment for Lifetime Exposure) present the conclusions that were reached during the assessment development process. Supporting information and explanations of the methods used to derive the values given in IRIS are provided in the guidance documents located on the IRIS website. STATUS OF DATA FOR Cyanogen bromide File First On-Line 09/26/1988 Category (section) Assessment Available? Last Revised Oral RfD (I.A.) yes 09/26/1988* Inhalation RfC (I.B.) not evaluated Carcinogenicity Assessment (II.) not evaluated *A comprehensive review of toxicological studies was completed (2004) - please see section I.A.6 for more information. I. Chronic Health Hazard Assessments for Noncarcinogenic Effects I.A. Reference Dose for Chronic Oral Exposure (RfD) Substance Name — Cyanogen bromide CASRN — 506-68-3 Last Revised — 09/26/1988 The oral Reference Dose (RfD) is based on the assumption that thresholds exist for certain toxic effects such as cellular necrosis. It is expressed in units of mg/kg-day. In general, the RfD is an estimate (with uncertainty spanning perhaps an order of magnitude) of a daily exposure to the human population (including sensitive subgroups) that is likely to be without an appreciable risk 1 Integrated Risk Information System (IRIS) U.S.