Electrocatalytic oxidation of methanol at platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes

The electrocatalytic oxidation of methanol at the platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes (Eu-Fe film) was investigated for the first time by cyclic voltammetry.Compared with the bare platinum electrode,the results showed that the modified electrode had excellent electrocatalytic activity for the oxidation of methanol;the oxidation peak potential shifted more negatively and the peak current increased about twenty times.The electrooxidation of methanol at the modified elect...

Synthesis, Crystal Structure and Spectroscopic Properties of Cyanide-bridged Complex [RuⅡ（ttpy）（CN）3MnⅢ（salen）]

Tricyanide building block K[Ru(ttpy)(CN)3] and [MnⅢ(salen)](ClO4) have been used to design and synthesize a heterobimetallic one-dimensional(1D) zigzag chain complex 1,[RuⅡ(ttpy)(CN)3 MnⅢ(salen)](ttpy = 4′-(p-tolyl)-2,2′:6′,2″-terpyridine, salen = N,N?-ethylenebis-(salicylideneaminato)dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in orthorhombic Pbca space group and the asymmetric unit of 1 contains one[-NC-RuⅡ(ttpy)(CN)(m-CN)-Mn Ⅲ-(salen)-] molecule. In the structure of 1, each [Ru Ⅱ(ttpy)(CN)3]-connects two [MnⅢ(salen)]+ with two cyanide groups in a cis-conformation, and in turn each[MnⅢ(salen)]+ unit links two [RuⅡ(ttpy)(CN)3]-building blocks in a trans-conformation, resulting in a 1D [-NC-RuⅡ-CN-MnⅢ-]n chain. Furthermore, the electronic absorption spectra and luminescence spectroscopy of complex 1 have also been studied.

Designed Syntheses and Crystal Structures of Two Cis-cyanide Bridged Trinuclear Complexes

Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.

Cyanide-bridged One-dimensional Heterobimetallic Complex cis-[Fe^Ⅱ(phen)2(CN)2Mn^Ⅲ(salen)](PF6):Synthesis,Crystal Structure and Magnetic Properties

Dicyanide building block cis-Fe（phen）2（CN）2 and [MnⅢ（salen）]（ClO4） have been used to design and synthesize a cyanide-bridged complex, resulting in a heterobimetallic one-dimensional（1D） zigzag chain complex 1, [cis-Fe（phen）2（CN）2Mn（salen）]（PF6）（phen =1,10-phenanthroline, salen=N,N-ethylenebis-（salicylideneaminato） dianion）. Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in the monoclinic P2（1/c） space group and the asymmetric unit contains one [-NC-Fe（phen）2（μ-CN）-MnⅢ-（salen）-]＋ cation and one PF6- anion. In the cationic structure of 1, each FeⅡ（phen）2（CN）2 connects two [MnⅢ（salen）]＋ with two cyanide groups in a cis-conformation, and in turn each [MnⅢ（salen）]＋ unit links two FeⅡ（phen）2（CN）2 building blocks in a trans-conformation, resulting in a 1D [-NC-FeⅡ-CN-MnⅢ-]n chain. Furthermore, the electronic absorption spectra and electrochemical and magnetic properties of complex 1 have also been studied.

The Assembly and Molecular Structure of a Novel One-dimensionalCyanide-bridged [Ni(pn)_2Ni(CN)_4]_n·nH_2 O Complex

The synthesis, structure and characterization of a new one-dimensional cyanide-bridgedcomplex [Ni(pn)_2Ni(CN)4]n'nH2O (where pn = 1,2-diaminopropane) are described. The structure ofthis complex consists of a one-dimensional polymeric chain-Ni(pn)2-NC-Ni(CN)2-CN-Ni(pn)2- inwhich the Ni(II) centers are linked by two CN groups.

Syntheses, Structures, Electrochemistry and Magnetic Properties of Two Trinuclear Cyanide-bridged Clusters Based on Tricyanometalate Building Block

The reaction of tricyanometallate precursor, Bu_4N[Fe(Tp)(CN)_3] and(Bu_4N)[(pzTp)Fe(CN)_3](Tp = tris(pyrazolyl)hydroborate, pzTp = tetrakis(pyrazolyl)borate) with Ni(ClO_4).26 H_2O in the presence of the monodentate N-methylimidazole ligand afforded two new cyano-bridged heterobimetallic {Fe2 Ni} trinuclear clusters, {[Fe(Tp)(CN)_3]_2[Ni(Mim)_4]}·8 H_2O(1) and {[Fe(pzTp)(CN)_3]_2[Ni(Mim)_4]}·2 CH_3OH·2H_2O(2). The molecular structure was determined by single-crystal X-ray diffraction. In the two compounds, the FeIII ions were coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp(or pzTp) anions, whereas, the NiII ions were surrounded by two cyanide nitrogen atoms and four nitrogen atoms from four monodentate N-methylimidazole ligands, and they were bridged by tricyanometalate building block to form similar {Fe2Ni} trinuclear clusters. Cyclic voltammetry(CV) measurements indicated that compound 1 exhibited two quasireversible iron-centered reduction processes at –0.71 and –0.17 V and one quasireversible nickel-centered oxidation process at 0.92 V, while compound 2 showed two quasireversible iron-centered reduction processes at –0.66 and –0.09 V and one quasireversible nickel-centered oxidation process at 0.88 V. Magnetic measurements showed that compounds 1 and 2 exhibited strong intrachain ferromagnetic interaction between the low-spin Fe~Ⅲ(S = 1/2) and high-spin Ni~Ⅱ(S = 1) ions.

Synthesis,Crystal Structure and MMCT Property of a New Mixed-valence Cyanide-bridged Binuclear Complex

A new mixed-valence cyanide-bridged complex, Br3Fe（p-NC）RuBr（dppm）2 （dppm = bis（diphenylphosphino）methane）, was obtained through the reaction between trans-（dppm）2C1- RuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer （MMCT） and this complex is Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.

Interaction mechanism of cyanide with pyrite during the cyanidation of pyrite and the decyanation of pyrite cyanide residues by chemical oxidation

The toxic cyanides in cyanide residues produced from cyanidation process for gold extraction are harmful to the environment.Pyrite is one of the main minerals existing in cyanide residues.In this work,the interaction of cyanide with pyrite and the decyanation of pyrite cyanide residue were analyzed.Results revealed that high pH value,high cyanide concentration,and high pyrite dosage promoted the interaction of cyanide with pyrite.The cyanidation of pyrite was pseudo-second-order with respect to cyanide.The decyanation of pyrite cyanide residue by Na_(2)SO_(3)/air oxidation was performed.The cyanide removal efficiency was 83.9% after 1 h of reaction time under the optimal conditions of pH value of 11.2,SO_(3)^(2-) dosage of 22 mg·g^(-1),and air flow rate of 1.46 L·min^(-1).X-ray photoelectron spectroscopy analysis of the pyrite samples showed the formation of Fe(Ⅲ)and FeSO_(4) during the cyanidation process.The cyanide that adsorbed on the pyrite surface after cyanidation mainly existed in the forms of free cyanide(CN^(-))and ferrocyanide(Fe(CN)_(6)^(4-)),which were effectively removed by Na_(2)SO_(3)/air oxidation.During the decyanation process,air intake promoted pyrite oxidation and weakened cyanide adsorption on the pyrite surface.This study has practical significance for gold enterprises aiming to mitigate the environmental impact related to cyanide residues.

Alkylene-functionality in bridged and fused nitrogen-rich poly-cyclic energetic materials:Synthesis,structural diversity and energetic properties

From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exhibits several advantages in the regulation of energetic properties,the nonaromatic heterocycles,assembling nitramino explosophores with simple alkyl bridges,still have prevailed in benchmark materials.The methylene bridge plays a pivotal role in the constructions of the classic nonaromatic heterocycle-based energetic compounds,e.g.,hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),whereas ethylene bridge is the core moiety of state-of-the-art explosive 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20).In this context,it is of great interest to employ simple and practical bridges to assemble aromatic and nonaromatic nitrogen-rich heterocycles,thereby expanding the structural diversity of energetic materials,e.g.,bridged and fused nitrogen-rich poly-heterocycles.Furthermore,alkyl-bridged poly-heterocycles highlight the potential for the open chain type of energetic materials.In this review,the development of alkyl bridges in linking nitrogen-rich heterocycles is presented,and the perspective of the newly constructed energetic backbones is summarized for the future design of advanced energetic materials.

Clinical Case Report of Acute Heart Injury and Acute Rhabdomyolysis Due to Cyanide Poisoning

Cyanide poisoning is one of the most dangerous poisonings, and it can be absorbed into the body through the mouth, inhalation and through the skin. A 32-year-old female patient was admitted to our poison control center because of high fever, severe vomiting, and seizures. Physical examination found that the patient was drowsy, had a high fever of 40 degrees Celsius, pulse of 140 beats/minute, and increased tendon and bone reflexes. Exploiting the patient’s information, it was discovered that the patient bought Cyanide to drink with the intention of committing suicide. The patient was quickly treated with gastric lavage and activated charcoal. Echocardiography recorded EF: 35%, reduced movement of the entire myocardium. CK blood test: 4562 U/L. The patient’s condition rapidly deteriorated and the patient was made ECMO, IHD and CVVHDF. After 3 days of treatment, the patient’s condition did not improve, so the family asked for the patient to go home. This article aims to describe the rapidly progressing and severe damage to the heart and muscles of patients with cyanide poisoning.

Making bridges between preclinical and clinical insights into age-related cognitive decline

With people living longer,the societal impact of age-related cognitive decline is becoming more pronounced(Crimmins,2015).Thus,it is increasingly important to comprehend the cognitive shifts linked to aging-whether they are physiological or pathological.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

Fe extraction from high-silicon and aluminum cyanide tailings by pretreatment of water leaching before magnetic separation

Pretreatment of high content of Si- and Al-containing cyanide tailings by water leaching to remove some impurities, such as the major impurities minerals of Si and A1, as well as its effect on Fe extraction in the water leaching process was investigated. The effects of different parameters on iron recovery were studied, and the reaction parameters were proposed as follows： sodium carbonate content of 30%, water leaching at 60 ~C for 5 min, liquid/solid ratio of 15：1, and exciting current of 2 A. Under these optimal conditions, magnetic concentrate containing 59.11% total iron and a total iron recovery rate of 76.12% was obtained. In addition, the microstructure and phase transformation of the process of water leaching were studied by X-ray powder diffraction technique （XRD）, Electronic image of backscattering （BEI）, X-ray fluorescence （XRF）, and energy dispersive spectrometry （EDS）. The results indicate that the soluble compound impurities generated in the roasting process are washed out, and the dissoluble substances enter into nonmagnetic materials by water leaching, realizing the effective separation of impurities and Fe.

TDDFT Study on Different Sensing Mechanisms of Similar Cyanide Sensors Based on Michael Addition Reaction

The solvents and substituents of two similar fluorescent sensors for cyanide, 7-diethylamino- 3-formylcoumarin （sensor a） and 7-diethylamino-3-（2-nitrovinyl）coumarin （sensor b）, are proposed to account for their distinct sensing mechanisms and experimental phenomena. The time-dependent density functional theory has been applied to investigate the ground states and the first singlet excited electronic states of the sensor as well as their possible Michael reaction products with cyanide, with a view to monitoring their geometries and photophysieal properties. The theoretical study indicates that the protic water solvent could lead to final Michael addition product of sensor a in the ground state, while the aprotic acetonitrile solvent could lead to carbanion as the final product of sensor b. Furthermore, the Michael reaction product of sensor a has been proved to have a torsion structure in its first singlet excited state. Correspondingly, sensor b also has a torsion structure around the nitrovinyl moiety in its first singlet excited state, while not in its carbanion structure. This could explain the observed strong fluorescence for sensor a and the quenching fluorescence for the sensor b upon the addition of the cyanide anions in the relevant sensing mechanisms.

Application of ferrate(VI) in the treatment of industrial wastes containing metal-complexed cyanides : A green treatment

Ferrate（VI） was employed for the oxidation of cyanide （CN） and simultaneous removal of copper or nickel in the mixed/complexed systems of CN-Cu, CN-Ni, or CN-Cu-Ni. The degradation of CN （1.00 mmol/L） and removal of Cu （0.095 mmol/L） were investigated as a function of Fe（Ⅵ） doses from 0.3-2.00 mmol/L at pH 10.0. It was found that Fe（Ⅵ） could readily oxidize CN and the reduction of Fe（Ⅵ） into Fe（Ⅲ） might serve efficiently for the removal of free copper ions. The increase in Fe（Ⅵ） dose apparently favoured the CN oxidation as well as Cu removal. Moreover, the pH dependence study （pH 10.0-13.0） revealed that the oxidation of CN was almost unaffected in the studied pH range （10.0-13.0）, however, the maximum removal efficiency of Cu was obtained at pH 13.0. Similarly, treatment was carded out for CN-Ni system having the initial Ni concentration of 0.170 mmol/L and CN concentration of 1.00 mmol with Fe（Ⅵ） dose 2.00 mmol at various pH values （10.0-12.0）. Results showed a partial oxidation of CN and partial removal of Ni. It can be observed that Fe（Ⅵ） can partially degrade the CN-Ni complex in this pH range. Further, Fe（Ⅵ） was applied for the treatment of simulated industrial waste/effluent waters treatment containing CN, Cu, and Ni.

Treatment of copper-rich gold ore by cyanide leaching, ammonia pretreatment and ammoniacal cyanide leaching

The treatment of a copper sulphide-bearing gold ore by direct cyanide leaching, ammonia pretreatment and ammoniacal cyanide leaching was investigated. Dissolution behaviour of gold and copper in these leaching systems was demonstrated. Severe interference by the copper containing sulphides with cyanide leaching of gold is observed at p（NaCN）〈5 g/L. This is consistent with speciation calculations. Ammonia pretreatment is shown to readily eliminate the copper interference, allowing almost complete extraction of gold with concomitantly low reagent consumption in subsequent cyanide leaching. In ammoniacal cyanide system, Box-Behnken experimental design shows the main and interaction effects of NH3, NaCN and Pb（NO3）2. The concentrations of NH3 and NaCN are statistically confirmed to be significant factors affecting extraction of gold while the effect of Pb（NO3）2 is limited. Increasing the concentration of NH3 improves the selectivity and extent of gold extraction and reduces the cyanide consumption. The contribution of reagent interactions to gold extraction is statistically insignificant. These findings highlight that ammonia pretreatment and ammonia-cyanide leaching are promising approaches for the treatment of gold ores with high copper sulphide content.

Highly active double metal cyanide complexes: Effect of central metal and ligand on reaction of epoxide/CO2

Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.

Granular activated carbons from palm nut shells for gold di-cyanide adsorption

Granular activated carbons were produced from palm nut shells by physical activation with steam. The proximate analysis of palm nut shells was investigated by thermogravimetric analysis, and the adsorption capacity of the activated carbons, produced as a result of shell pyrolysis at 600℃ followed by steam activation at 900℃ in varying activation times, was evaluated using nitrogen adsorption at 77 K. Applicability of the activated carbons for gold dicyanide adsorption was also investigated. Increasing the activation hold time with the attendant increase in the degree of carbon burn-off results in a progressive increase in the surface area of the activated carbons, reaching a value of 903.1 m2/g after activation for 6 h. The volumes of total pores, mieropores, and mesopores in the activated carbons also increase progressively with the increasing degree of carbon burn-off, resulting from increasing the activation hold time. The gold di-cyanide adsorption of the activated carbons increases with the rise of pore volume of the activated carbons. The gold di-cyanide adsorption of palm nut shell activated carbon obtained after 6-h activation at 900℃ is superior to that of a commercial activated carbon used for gold di-cyanide adsorption.

Effect of Pre-treatment of α-Ketoglutarate on Cyanide-induced Toxicity and Alterations in Various Physiological Variables in Rodents

Objective To investigate the effects of pre-treatment of α-ketoglutarate （α-KG） on cyanide-induced lethality and changes in various physiological parameters in rodents. Methods The LD50 of potassium cyanide （KCN） given orally （po）, intraperitoneally （ip）, subcutaneously （sc） or intravenously （iv） was determined in male mice, in the presence or absence α-KG given po, ip or iv. α-KG was administered 10, 20 or 40 min prior to KCN at 0.50, 1.0 or 2.0 g/kg by po or ip route, and at 0.10, 0.20 or 0.40 g/kg by iv route. Protection index （PI） was calculated as the ratio of LD50 of KCN in the presence of α-KG （protected animals） and LD50 of KCN in the absence of α-KG （unprotected animals）. In a separate experiment, several physiological variables viz. mean arterial pressure （MAP）, heart rate （HR）, respiratory rate （RR）, neuromuscular transmission （NMT） and rectal temperature （RT） were measured in anesthetized female rats pre-treated （-10 rain） with po （2.0 g/kg） or iv （0.125 g/kg） α-KG and then administered sub-lethal （0.75 LD50） or lethal （2.0, 4.0 or 8.0 LD50） doses of KCN （po）. Results PI of 4.52, 6.40 and 7.60 at -10 min, 3.20, 5.40 and 6.40 at -20 min, and 1.40, 3.20 and 5.40 at -40 min of po administration with α-KG was observed for 0.50, 1.0 and 2.0 g/kg doses, respectively, against KCN given by po route. When KCN was given ip, a PI of 3.38, 4.79 and 5.70 was observed for 0.50, 1.0 and 2.0 g/kg α-KG given ip （-10 min）, respectively. A lower PI of 3.37, 2.83 and 2.38 was observed when KCN given sc was challenged by 2.0 g/kg α-KG given ip at -10, -20 or -40 min, respectively. Similarly, a PI of 3.37, 2.83 and 2.0 was noted when KCN given sc was antagonized by 2.0 g/kg α-KG given po at -10, -20 or -40 rain, respectively. No appreciable protection was observed when lower doses of α-KG （ip or po） challenged KCN given by sc route. Pre-treatment of iv or po administration of α-KG did not afford any protection against KCN given po or iv route. Oral treatment of 0.75 LD50 KCN caused significant decrease in MAP and HR after 15 min, RR after 30 min and NMT after 60 min. There was no effect on RT. No reduction in MAP, HR, RR and RT was observed when rats received 2.0 or 4.0 LD50 KCN after pre-treatment of α-KG （po; 2.0 g/kg）. However, no protection was observed on NMT. Protective efficacy of α-KG was not observed on MAP, HR, RR, and NMT decreased by 8.0 LD50 KCN. Decrease in MAP and NMT caused by 2.0 LD50 KCN （po） was resolved by iv administration of α-KG Conclusions Cyanide antagonism by α-KG is best exhibited when both α-KG and KCN are given by po route. The protective effect of α-KG on cyanide-induced changes in several physiological parameters also indicates a promising role of α-KG as an alternative cyanide antidote.

Efficient destruction of sodium cyanide by thermal decomposition with addition of ferric oxide

Efficient destruction of cyanide by thermal decomposition with ferric oxide addition was proposed. The mechanism of destruction of sodium cyanide with or without ferric oxide addition under various conditions was examined by XRD, DSC-TG, and chemical analysis technologies. In the absence of ferric oxide, sodium cyanide decomposes at 587.4 ℃ in air and 879.2 ℃ in argon atmosphere. In the presence of ferric oxide, about 60% of sodium cyanide decomposes at 350 ℃ for 30 min in argon, while almost all sodium cyanide decomposes within 30 min in air or O2 with mass ratio of ferric oxide to sodium cyanide of 1:1. The increase of ferric oxide addition, temperature, and heating time facilitates the destruction of sodium cyanide. It is believed that with ferric oxide addition, NaCN reacts with Fe2O3 to form Na4Fe(CN)6, Na2CO3, NaNO2 and Fe3O4 in argon. NaCN decomposes into NaCNO, Na4Fe(CN)6, minor NaNO2, and the formed NaCNO and Na4Fe(CN)6 further decompose into Na2CO3, CO2, N2, FeOx, and minor NOx in air or O2.