Crystal structure of copper sulfate and thiocyanate complexes with 5-bromo-and 5-nitrosalicylaldehyde thiosemicarbazones

The crystal structures of (5-bromosalicylidenethiosemicarbazido)aquacopper(II) sulfato(5-bromosalicylidenethiosemicarbazido)aquacuprate(II) tetrahydrate (I), (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) sulfate (II), and catena(μ-thiocyanato)(5-nitrosalicylidenethiosemicarbazido)copper(II) (III) were determined. In structure I, the independent part of the unit cell contains four water molecules of crystallization and the cation-anion complex [Cu(H₂O)(L)][Cu(H₂O)(L)(SO₄)] containing two nonequivalent copper complexes (A and B). In these, the metal atom coordinates monodeprotonated 5-bromosalicylaldehyde thiosemicarbazone (HL) and water molecules, and in anion B also a sulfate ion. In complex ions A and B, sulfur, azomethine nitrogen, and phenolic oxygen of the salicylidene thiosemicarbazone fragment, and also water molecule form a distorted planar square around the metal atom. The axial vertex of the pyramid in anion B is occupied by the oxygen atom of the monodentate sulfate anion. In structure II, the independent part of the unit cell contains the (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) complex cation and the sulfate anion. The coordination polyhedron of the central atom is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and dimethyl sulfoxide oxygen. The axial position is occupied by the methanol oxygen atom. In structure III, the copper atom coordinates 5-nitrosalicylaldehyde thiosemicarbazone and the thiocyanate ion, which combines complexes into infinite polymer chains along the [010] direction. The copper coordination polyhedron in III is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and nitrogen of thiocyanate ion, the axial vertex is occupied by sulfur of thiocyanate ion of the neighboring complex.     

Synthesis and photoreactivity of some 5-alkylidene- and 5-alkylidenamine-2,5-dihydroisoxazoles

5-Alkylidene-2,5-dihydroisoxazoles and 5-alkylidenamine-2,5-dihydroisoxazoles were easily prepared from the corresponding 5-chloro-2-methylisoxazolium triflate and an enolizable compound or alkylamine. Their photochemical reactivity leads to photoisomers that in some cases constitute new heterocycles systems. The photorearrangement involves either triplet or singlet state depending on substituents and experimental conditions.     

表面活性剂对Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应作用的研究

我们曾研究了离子型-非离子型混合表面活性剂对Ag²⁺-5-Cl-PADAB和Cu²⁺-5-Cl-PADAB等显色反应的作用。本文研究了阴离子、阳离子、非离子及阴-非混合表面活性剂对一系列Me-5-Br-DEPAP及Me-5-Cl-PADAB显色反应的作用,试图寻求表面活性剂对显色体系增敏作用及协同增敏作用的原因,并对其作用机理作一初步探讨。     

Methylation of 3-methyl- and 3-phenyl-4-arylhydrazonoisoxazol-5-ones with methyl iodide and dimethyl sulfate

Methylation of 3-methyl-4-arylhydrazonoisoxazol-5-ones with methyl iodide affords both 2,3-dimethyl-4-arylazoisoxazol-5-ones and 3-methyl-4-(N-methylarylhydrazono)isoxazol-5-ones but with dimethyl sulfate only the former products are formed. 3-Phenyl-4-arylhydrazonoisoxazol-5-ones behave in a similar way on methylation with methyl iodide and dimethyl sulfate.     

A Raman spectral study of hydrated vanadium sulfate (VSO5) phases

Raman spectra were measured for various hydrated VSO₅ materials. Spectral differences were noted and interpreted for α-VSO₅, VSO₅ · H₂O possessing vanadium atoms bonded to H₂O molecules in the interlayers, and other hydrated phases which involve broken VOS linkages.     

Action of phosphorus pentasulfide on 5-acetamidothiohydantoins and 4-bromo-5-acetamidopyrazoles

New condensed systems — (5,4-thiazolo)imidazoline-2-thione and pyrazolo[5,4-d]thiazoles -are formed by reaction of phosphorus pentasulfide with 5-acetamidothiohydantoins and 4-bromo-5-acetamido derivatives of pyrazole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 932–934, July, 1974.     

Production of 5′-mononucleotides using immobilized 5′-phosphodiesterase and 5′-amp deaminase

The preparations and properties of 5′-phosphodiesterase and 5′-AMP-deaminase immobilized on porous ceramics by covalent binding and the production of 5′mononucleotides from RNA using these immobilized enzymes are described. Comparison tests for the properties of both immobilized and native enzymes were carried out. It was found that the pH optima of these immobilized enzymes were shifted toward the acidic side, and their practically operable pH regions were much more broadened. In such acidic pH regions, these immobilized enzymes also showed more excellent heat stabilities. These special characteristics of the immobilized enzymes were quite satisfactory for eliminating possible microbial contamination during the long-term operation of these immobilized enzyme systems. In continuous-column operations, more than 85% hydrolysis of RNA and complete conversion of 5′-AMP to 5′-IMP were maintained for more than 23 days when a 4% RNA solution was charged as the substrate.     

ZAPO-5和MnAPO-5分子筛大单晶的生长

磷酸锌铝(ZAPO-5)和磷酸锰铝(MnAPO-5)分予筛是新型分子筛^[1],由文献^[1]可知UCC得到了粉末状的ZAPO-5和MnAPO-5分子筛,得到的ZAPO-5不仅是粉末状而且是不纯的,本文报道了ZAPO-5和MnAPO-5纯相大单晶的合成。     

Electron paramagnetic resonance and spectroscopic characteristics of electrogenerated mixed-valent systems [(eta 5-C5Me5)M(mu-L)M(eta 5-C5Me5)]+ (M = Rh, Ir; L = 2,5-diiminopyrazines) in relation to the radicals [(eta 5-C5Me5)ClM(mu-L)MCl(eta 5-C5Me5)]+ and [(eta 5-C5Me5)M(mu-L)MCl(eta 5-C5Me5)]2+

Electrochemical reduction of the dinuclear [(eta 5-C5Me5)ClM(mu-L)MCl(eta 5-C5Me5)]2+ ions (M = Rh, Ir; L = 2,5-bis(1-phenyliminoethyl)pyrazine (bpip) and 2,5-bis[1-(2,6-dimethylphenyl)iminoethyl]pyrazine (bxip)) proceeds via the paramagnetic intermediates [(eta 5-C5Me5)ClM(mu-L)MCl(eta 5-C5Me5)]+ (L = bpip) or [(eta 5-C5Me5)M(mu-L)MCl(eta 5-C5Me5)]2+ (L = bxip) and [(eta 5-C5Me5)M(mu-L)M(eta 5-C5Me5)]+. Whereas the first is clearly a radical species with a small g anisotropy, the chloride-free cations are distinguished by structured intervalence charge transfer (IVCT) bands in the near-infrared region and by rhombic electron paramagnetic resonance features between g = 1.9 and g = 2.3, which suggests considerable metal participation at the singly occupied MO. Alternatives for the d configuration assignment and for the role of the bisbidentate-conjugated bridging ligands will be discussed. The main difference between bpip and bxip systems is the destabilization of the chloride-containing forms through the bxip ligand for reasons of steric interference.     

Sulfangolids, macrolide sulfate esters from Sorangium cellulosum

Sulfangolids are the first sulfate ester containing secondary metabolites from myxobacteria. The metabolites 1-4 and the structurally related kulkenon (5) were isolated from different strains of the species Sorangium cellulosum. In the course of isolation all metabolites proved to be rather sensitive due to their conjugated double bond systems and the strong acidic nature of the sulfate ester in sulfangolids. The relative configuration of sulfangolid C (3) was assigned by extensive 1D and 2D NMR analysis and molecular modelling. In addition, the biosynthesis of 3 was studied by feeding experiments.     

Isolation and purification of recombinant human plasminogen Kringle 5 by liquid chromatography and ammonium sulfate salting‐out

In this work, a novel method was established to isolate and purify Human plasminogen Kringle 5 (HPK5) as a histidine‐tagged fusion protein expressed in Escherichia coli BL21 (DE3). This method consisted of sample extraction using a Ni‐chelated Sepharose Fast‐Flow affinity column, ammonium sulfate salting‐out and Sephadex G‐75 size‐exclusion column in turn. The purity analysis by SDS–PAGE, high‐performance size‐exclusion and reversed‐phase chromatographies showed that the obtained recombinant fusion HPK5 was homogeneous and its purity was higher than 96%; the activity analysis by chorioallantoic membrane model of chicken embryos revealed that the purified recombinant HPK5 exhibited an obvious anti‐angiogenic activity under the effective range of 5.0–25.0 µg/mL. Through this procedure, about 19 mg purified recombinant fusion HPK5 can be obtained from 1 L of original fermentation solution. Approximate 32% of the total recombinant fusion HPK5 can be captured and the total yield was approximately 11%. Copyright © 2013 John Wiley & Sons, Ltd.     

Ti-ZSM-5和B-ZSM-5分子筛大单晶的合成

具有ZSM-5结构的含钛和含硼分子筛是催化性能良好的新型杂原子分子筛,可分别作为碳氢化合物的氧化反应^[1]和制备高纯异丁烯的催化剂^[2]。近年来,有关这2种分子筛的合成已见报道^[1~4]。但其合成均采用碱性介质,成核和晶化都比较快,因此未能得到生长完美的杂原子ZSM-5型分子筛大单晶。     

Chemistry of bicyclic [1,3,4]thiadiazole 5-5 systems containing ring-junction nitrogen

This review provides a survey of the advances in the methods of formation and chemical reactivity of bicyclic [1,3,4]thiadiazole 5-5 systems containing ring-junction nitrogen over the period from 1989 to the beginning of 2017.     

The systems NbF5RbF and NbF5CsF

NbF₅ systems (MRb,Cs) are investigated by differential thermal analysis and X ray powder diffraction. Six types of ternary fluorides are found, and lattice parameters calculated for most of them. Comparison with the NbF₅TlF system is carried out.     

MgO-P2O5和CaO-P2O5体系的热力学优化

基于严格评估的相图和热力学实验数据,采用相图计算方法对MgO-P₂O₅和CaO-P₂O₅体系进行热力学优化.液相采用修正的似化学模型进行描述,考虑了对近似处理液相中存在的短程有序.为了描述M₃(PO₄)₂(M = Mg, Ca)组分处的最大短程有序,将PO₄^3-当作液相中P₂O₅的基本组成单元.体系中所有的中间相都看作线性化合物并考虑了晶型转变.获得一套合理、可靠、自洽的模型参数用来描述体系中各相的热力学性质,在实验误差范围内很好地重现了相图、焓、熵和活度实验数据,为炼钢脱磷过程中熔渣体系热力学数据库的建立打下了坚实的基础.     

Addition reactions of thiazol-5(4H)-ones—IV : Synthesis,tautomerism and addition reactions of 2-phenylthiazole-5-thiols

4-Substituted 2-phenylthiazole-5-thiols 3 undergo addition reactions of a different type from those of their oxygen analogues, the oxazol- and thiazol-5(4$\text{H}$)-ones, since they exist in solution entirely in the thioenol tautomeric form. Their addition reactions involve only the exocyclic sulphur atom, and they behave as typical heteroaromatic thiols towards unsaturated systems, giving sulphides. A mesoionic thiazole-5-thiol, however, is shown to possess cycloaddition reactivity, undergoing cycloaddition-extrusion reactions with unsaturated systems comparable with well-established reactions of oxygen analogues.     

Reactive uptake of N2O5 by aerosol particles containing mixtures of humic acid and ammonium sulfate

The kinetics of reactive uptake of N2O5 on submicron aerosol particles containing humic acid and ammonium sulfate has been investigated as a function of relative humidity (RH) and aerosol composition using a laminar flow reactor coupled with a differential mobility analyzer (DMA) to characterize the aerosol. For single-component humic acid aerosol the uptake coefficient, gamma, was found to increase from 2 to 9 x 10(-4) over the range 25-75% RH. These values are 1-2 orders of magnitude below those typically observed for single-component sulfate aerosols (Phys. Chem. Chem. Phys. 2003, 5, 3453-3463;(1) Atmos. Environ. 2000, 34, 2131-2159(2)). For the mixed aerosols, gamma was found to decrease with increasing humic acid mass fraction and increase with increasing RH. For aerosols containing only 6% humic acid by dry mass, a decrease in reactivity of more than a factor of 2 was observed compared with the case for single-component ammonium sulfate. The concentration of liquid water in the aerosol droplets was calculated using the aerosol inorganic model (for the ammonium sulfate component) and a new combined FTIR-DMA system (for the humic acid component). Analysis of the uptake coefficients using the water concentration data shows that the change in reactivity cannot be explained by the change in water content alone. We suggest that, due to its surfactant properties, the main effect of the humic acid is to reduce the mass accommodation coefficient for N2O5 at the aerosol particle surface. This has implications for the use of particle hygroscopicity data for predictions of the rate of N2O5 hydrolysis.     

果糖脱水制备5-羟甲基糠醛

5-羟甲基糠醛(HMF)是一种重要的生物基材料单体,具有非常广泛的应用价值。果糖等己糖选择性脱水是制备5-羟甲基糠醛的主要方法之一。本文首先从催化剂的角度出发,介绍了近年来不同均相和多相酸性催化剂在该反应中的应用。按照反应溶剂体系进行分类,总结了近年来该领域中不同溶剂体系的研究进展,包括双相溶剂体系、亚/超临界流体溶剂体系和离子液体溶剂体系等。最后,指出了新型多相酸性催化剂以及高效溶剂体系的开发和改进是该领域将来主要的研究方向。     

Conductivity and interfacial behaviour of bis-1,4-dioxapentyl sulfate (IV) and 1,4,7-trioxaoctyl sulfate (IV) based electrolyte for lithium batteries

The electrolytic conductivity and viscosity of lithium perchlorate in bis-1,4-dioxapentyl sulfate (IV) [OS22] and 1,4,7-trioxaoctyl sulfate (IV) [OS32] were determined as a function of salt concentration (0.00005–2 M) and temperature (286–318 K). At 298 K, the highest conductivity (=2.77×10^{–3 –1} cm^–1) was achieved for OS22 based solutions containing 1–2 M LiClO₄. Formation of electrically neutral ion pairs appeared to be the main reason for a continuous decline in the molar conductivity () observed in dilute solutions with increasing salt concentration. Additionally, an increase in the dynamic viscosity () accounted for a decrease in the mobility of charge carriers with increasing length of the oxaalkyl chain in the podand molecules. The temperature dependence of the conductivity and viscosity was found to be of the Arrhenius type for both systems investigated, while the activation energies, E ^# and E ^#, varied in parallel with the degree of interionic aggregation. CVs obtained on a polycrystalline Pt electrode indicated the electrochemical stability of OS22 in the potential range between –0.8 V and 4.7 V versus Li⁺/Li. A linear current density–potential dependence, with the same slope for the anodic and cathodic branches proved the reversibility of lithium electrodeposition and re-dissolution at the Pt/1 M LiClO₄+OS22 interface.     

Importance of the methyl group at C10 of squalene for hopene biosynthesis and novel carbocyclic skeletons with 6/5 + 5/5 + (6) ring system(s)

[reaction: see text] Incubation of (6E,10E,14E,18E)-2,6,10,19,23-pentamethyl-tetracosa-2,6,10,14,18,22-hexaene with Alicyclobacillus acidocaldarius hopene cyclase afforded four products having two types of carbocyclic skeletons, i.e., two hopane products and two products having an unprecedented carbocyclic skeleton of 6/5 + 5/5 +6 pentacyclic and 6/5 + 5/5 tetracyclic ring systems. The former two hopane skeletons were formed from the bioconversion of C15-desmethylsqualene and the latter two skeletons from that of C10-desmethylsqualene.