Question of the mechanism of the formation of 5-hydrazino-tetrazole from 5-diazomethylazotetrazole in acidic media

The heating of the hydrate of 5-diazomethylazotetrazole in an aqueous medium led to the isolation, for the first time, of 5-hydroxymethylazotetrazole — the proposed intermediate product in the isolation of 5-hydrazinotetrazole from 5-diazomethylazotetrazole in acidic media. It was established that 5-hydrazinotetrazole is not formed when 5-hydroxymethylazotetrazole is treated with hydrochloric acid under different conditions. In this connection, an improved reaction mechanism, not including 5-hydroxymethylazotetrazole as an intermediate compound, was proposed. It was shown that not all of the 5-diazomethylazotetrazole enters into the reaction with water. The proposition was expressed that the product which did not enter into the reaction is the Z-isomer.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1351–1353, October, 1992.     

火灾探测器滤光片校准方法

以紫外可见近红外分光光度计为计量标准器建立火灾探测器滤光片校准方法。火焰探测器紫外滤光片校准选择波长范围150~300 nm进行光谱扫描,测量滤光片在紫外区域的透射比;红外滤光片校准选择波长范围800~1 100 nm进行光谱扫描,测量滤光片在红外区域的透射比。线型光束感烟火灾探测器滤光片校准波长扫描范围设置为700~1 100 nm,取850~950 nm透射比平均值计算减光值。火焰探测器紫外滤光片校准结果为220,240,260,280 nm波长下的透射比,红外滤光片校准结果为850,900,950,1 000 nm波长下的透射比,不作合格性判定。线型光束感烟火灾探测器滤光片减光值标称值为0.4,0.9 d B时,误差不超过±0.1 d B;减光值标称值为10.0 d B时,误差不超过±1.0 d B。     

Study of the Effect of an Antifoaming Agent on the Evaporation of the Components During the Stirring of a Coating Dispersion Containing a Volatile Agent

The main objective of this work was to evaluate the evaporation of coating liquids containing a volatile component (ethanol) and an aqueous polymer dispersion under well‐controlled circumstances. The influence of different concentrations of a polydimethylsiloxane type antifoaming agent was studied. In consequence of to its low interfacial tension, it can form a layer on the surface of a liquid, and the effect of this was studied by determination of the quantity of the stirred liquid that was evaporated. The effects of different operational factors were compared by means of factorial designs. It was conluded that the presence of ethanol in the liquid changed not only the extents of the effects of the factors, but also their relative importance as concerns the evaporation process. The highest difference in effect of a given factor was detected for the stirring rate, while the lowest difference was observed for the duration of stirring. A high concentration of Dimeticon decreased the extent of evaporation, but not significantly. Thus, the alterations in the effects of the operational factors were not very substantial either. It may be stated that this antifoaming agent does not result in a relevant change in the evaporation in these systems containing ethanol as a volatile component. Accordingly, primarily the operational parameters must be considered during the formulation of these compositions. This information helps towards the design of an appropriate stirring device, because our results indicate that open systems are not adequate and it is known that hermetically closed tanks make atomization impossible. Hence, determination of the critical control points of coatings with a liquid containing a volatile component cannot be avoided because the vapour of such materials can be very dangerous.     

Control of amino acid transport in the mammary gland of the pregnant mouse

The regulation of the uptake of the amino acid analog alpha-aminoisobutyric acid was studied in diced mammary glands from pregnant mice. Stimulation of uptake by insulin was not prevented by inhibitors of protein synthesis; protein synthesis inhibitors decreased uptake by 20%; this response occurred more promptly in insulin-treated tissues. Elimination of extracellular amino acids led to a substantial increase in transport which was not abolished by inhibitors of protein synthesis. These results indicate that insulin does not increase amino acid transport in this system by altering synthesis and degradation of transport protein. They are consistent with a model in which the activity of the existing amino acid transport protein in subject to negative feedback regulation from the intracellular amino acid pool.     

Contribution to the chemistry of the Belousov-Zhabotinsky reaction. Products of the Ferriin-Bromomalonic acid and the Ferriin-Malonic acid reactions

In the present mechanistic schemes of the ferroin-catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction the oxidation of the organic substrates (bromomalonic or malonic acid) by ferriin (the oxidized form of the catalyst) plays an important role. As the organic products of these reactions were not yet identified experimentally, they were studied here by an HPLC technique. It was found that the main organic oxidation product of bromomalonic acid is bromo-ethene-tricarboxylic acid (BrEETRA), the same compound that is formed when bromomalonic acid is oxidized by Ce4+ (another catalyst of the BZ reaction). Formation of BrEETRA is explained here by a new mechanism that is more realistic than the one suggested earlier. To find any oxidation product of malonic acid in the ferriin-malonic acid reaction was not successful, however. Neither ethane-tetracarboxylic acid (ETA) nor malonyl malonate (MAMA), the usual products of the Ce4+- malonic acid reaction, nor any other organic acid, not even CO2, was found as a product of the reaction. We propose that malonic acid is not oxidized in the ferriin-malonic acid reaction, and it plays only the role of a complex forming catalyst in a process where Fe3+ oxidizes mostly its phenantroline ligand.     

Application of the QuEChERS method for the analysis of pyrethrins and pyrethroids in fish tissues

The application of the quick easy cheap effective rugged and safe (QuEChERS) method has generally been used in the preparation of produce samples (e.g., lettuce and oranges) for pesticide analysis. In the present study, the QuEChERS method was successfully applied to the determination of the natural pyrethrins (cinerin I and II, jasmolin I and II, and pyrethrin I and II), as well as two pyrethroid insecticides, cypermethrin and deltamethrin, in fin and non-fin fish products. Analysis of these compounds was performed using gas chromatography–mass spectrometry. Although cypermethrin is not and has not been registered for pest control use in aquaculture operations in Canada, cypermethrin was detected in domestically produced salmon. Cypermethrin was detected in seven of the 18 Canadian farmed salmon samples (39%), although it was not detected in any wild domestic salmon (n = 3). Cypermethrin concentrations ranged from 0.3 to 6.5 ng/g in the positive samples. It was not, however, observed in any imported fish product or any other domestically produced fish product.     

Capacitance Characterization of the Effect of pH Value on the Self—assembled Monolayers of Octadecanethiol

In this paper,the membrane capacitance(Cm),which was obtained from the ecectrochemical impedance spectroscopy(EIS) method,was used to characterize the effect of pH value on the self-assembled monolayers(SAMs) of octadecanethiol(18SH) for the first time.The results not only strongly proved that inorganic ions could penetrate the SAMs of 18SH,but also ascertained that SAMs of 18SH were not an absolute of free of ion-penetration.Verifying the existence of pin-holes in the octadecanethiol SAMs was the main contribution of this paper,which coincided with the former conjecture very well.     

An Attempt at the Preparation of Macrocyclic Polymer

Syntheses of cyclic oligomer and polymer were attempted with magnesiacyclohexane as the initiator in HMPA. The oligomer of α-methylstyrene, initiated by magnesiacyclohexane, was treated with dimethyldichlorosilane in order to obtain a stable cyclic oligomer. The products were investigated by GPC, IR, NMR, and elemental analysis. It was found that magnesia-cyclohexane could not be activated enough by HMPA, and that the magnesium-carbon bond was not stable in HMPA, and that the chain transfer reaction might occur repeatedly during the polymerization. Consequently, the yield of cyclic oligomer was so low that cyclic compounds could not be discriminated from the linear oligomer.     

On the Effect of the Strength of Acid Sites in Heterogeneous Catalysts on the Activity in the Skeletal Isomerization of n-Butane

The catalytic activity of three groups of acid catalysts different in the nature and strength of acid sites in the skeletal isomerization of n-butane was studied. It was found that the strength of the sites did not correlate with the rate of the reaction.     

Ecotoxicity of the Adipate Plasticizers: Influence of the Structure of the Alcohol Substituent

A significant increase in the production of plastic materials and the expansion of their areas of application contributed to the accumulation of a large amount of waste of polymeric materials. Most of the polymer composition is made up of plasticizers. Phthalate plasticizers have been recognized as potentially hazardous to humans and the environment due to the long period of their biodegradation and the formation of persistent toxic metabolites. It is known that the industrial plasticizer dioctyl adipate is characterized by reduced toxicity and a short biodegradation period. The paper describes the synthesis of a number of new asymmetric esters based on adipic acid and ethoxylated butanol by azeotropic esterification. The receipt of the products was confirmed by IR spectra. The physicochemical properties of the synthesized compounds were investigated. The glass transition temperatures of PVC composites plasticized with alkyl butoxyethyl adipates were determined using DSC analysis. The ecological safety of esters was assessed by the phytotesting method. Samples of adipates were tested for fungal resistance, and the process of their biodegradation in soil was also studied. It is shown that the synthesized esters have good plasticizing properties and are environmentally safe. When utilized under natural conditions, they can serve as a potential source of carbon for soil microorganisms and do not form stable toxic metabolites; therefore, they are not able to accumulate in nature; when the plasticizers under study are disposed of in the soil, toxic substances do not enter.     

Study of the change in the properties of Mn-bentonite by aging

In this paper the structure and properties of fresh manganese(II)-bentonite was compared with that of an old substance. It was concluded that the oxidation state of Mn changed. This did not cause many changes in the scanning electron microscope (SEM) and in the X-ray diffraction (XRD) studies; caused minor changes in the Mn concentration (determined by XRF) and thermoanalytical and electron spectroscopy analysis (ESCA). The change in the oxidation state of manganese was indicated by the colors of the samples, the difference in the surface sites, titration curves, redox potentials, adsorption, and catalytic activity of the fresh and the old Mn-bentonite. Potentiometric titration data were evaluated by a surface complexation model using the FITEQL3.2 computer program. Stability constants of edge charge reactions and the number of aluminol, silanol, and edge sites were calculated. Potentiometric titration data of commercial and freshly made MnO2 were also evaluated; the calculated constants and site numbers were compared with that of found in literature. Catalytic and adsorption activity of the samples were also investigated. It was found that fresh Mn-bentonite does not adsorb valine, while the old one and MnO2 does. Fresh Mn-bentonite does not catalyze the decomposition of H2O2, while the old one, as well as MnO2 does.     

Importance of the Treatment Field for the Application of Vascular Photodynamic Therapy to Inhibit Intimal Hyperplasia

Intimal hyperplasia (IH) plays a dominant role in the development of restenosis. In previous studies, photodynamic therapy (PDT) prevented IH induced by segmental balloon injury of the rat carotid. The critical elements required to control IH effectively with this technique are not fully understood. This study assessed the importance of the treatment field by studying the repair process of injured vessels, in which the PDT-treatment field did not target the entire injured area. The entire rat common carotid artery was balloon-injured to induce IH, whereas only the cervical segment below the bifurcation was subjected to PDT by external light irradiation after administration of the photosensitizer chloroaluminum sulfonated phthalocyanine. Light irradiation of injured arteries without photosensitizer served as control for PDT, and PDT of uninjured arteries was included as a control group for the balloon injury. Histologic characterization of the repair process was sequentially assessed. Balloon-injured arteries without PDT displayed rapid IH development with a peak at 2 weeks. Photodynamic therapy of balloon-injured arteries resulted in complete local depletion of medial smooth muscle cells (SMC), which was associated with a lack of IH until 2 weeks. However, at 4 and 16 weeks there was significant IH in PDT-treated arteries despite a lack of medial SMC repopulation. A wave of IH progression over the acellular media was observed in these arteries, migrating from the injured non-PDT-treated area. The PDT of uninjured arteries did not result in IH and was also associated with a persistent acellular media. Delayed IH development after PDT of injured vessels can result from IH progression from an injured site not included in the treatment field. This also indicated that the source of cells developing the intimal hyperplasia lesion can originate from an area remote from the lesion. Together with previous results and the determination that PDT itself does not induce IH, it can be reasoned that inclusion of the whole injured artery or a section of an uninjured margin in the treatment field is essential for effective PDT prevention of IH.     

C-glycosylation reactions of sulfur-substituted glycosyl donors: evidence against the role of neighboring-group participation

Nucleophilic substitution reactions of C-4 sulfur-substituted tetrahydropyran acetals revealed that neighboring-group participation does not control product formation. Spectroscopic evidence for the formation of an intermediate sulfonium ion is provided, as are data from nucleophilic substitution reactions demonstrating that products are formed from oxocarbenium ion intermediates. The selectivity was not sensitive to solvent or to which Lewis acid was employed. The identity of the heteroatom at the C-4 position also did not significantly impact diastereoselectivity. Consequently, neighboring-group participation was not responsible for the formation of either the major or the minor products. These studies implicate a Curtin-Hammett kinetic scenario in which the formation of a low-energy intermediate does not necessitate its involvement in the product-forming pathway.     

Comparison of the thermal decomposition behavior for members of the hydroxylamine family

In the present work the thermal stability of some members of the hydroxylamine family was studied using adiabatic calorimetry. The study included aqueous solutions of hydroxylamine free base, hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine-o-sulfonic acid of concentrations typically used in industry. Also, the catalytic effect of metal surfaces of stainless steel, carbon steel, and titanium was studied. From the solutions studied HA is the most reactive with higher maximum temperature, pressure, non-condensable pressure, and lower time to maximum rate. HA maximum heat rate is at least ∼3 times higher than that of the other solutions studied, and the pressure generation rate is ∼13 times higher. All decompositions were catalyzed by stainless steel, but only HA was catalyzed significantly by titanium metal. Solid hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine-o-sulfonic acid exhibited stability up to ∼60 °C. Hydroxylamine 100% was not studied because it is not readily available, is not used industrially, and is known to be unstable at room temperature. A violent reaction was measured for solid hydroxylamine sulfate that generated a heat rate >500 °C/min and pressure rate >5200 psia/min before the sample cell was completely destroyed by the generated pressure.     

光亮剂对银电沉积行为的影响

用电势阶跃法和旋转圆盘电极法 (RDE)以及SEM和XRD测试手段 ,初步研究了光亮剂对氰化体系中银电沉积行为的影响 .研究表明 ,光亮剂的加入并未导致银电沉积成核机理的改变 ,但显著增强了镀液的微观平整效应 ,并且所得镀层的表观光滑程度明显改善 .XRD测试亦同时表明光亮剂的加入并未改变镀层的择优取向     

用改进的基向量法重建光谱反射比

如何从已知物体表面颜色的三刺激值及其照明条件和观察条件准确地重建其光谱反射比,是彩色图像研究领域尚待解决的一个重要课题.本文首先介绍了两种前人提出的方法,即“伪逆矩阵法”和“Wiener方法”,然后,分析了这两种方法的优缺点,指出了共同存在的问题,即所重建的光谱反射系数有可能超出实际可能的范围(0,1),进而提出了一种新的改进的基向量法.最后,文中还给出此改进的算法和上述两种算法的特性模拟仿真.从仿真的结果中可以看出,改进的算法不仅在精度上较上述两种算法更精确,而且能够保证所重建的光谱反射比能够满足其实际可能的范围(0,1).因而,用本文中所给出的改进的基向量法重建物体表面的光谱反射比,较上述两种前人提出的算法更能满足工业实际需要.     

Effect of the nature of solid metal fluorides on the alkylation kinetics of CH-acids in the presence of onium salts

The selective C-alkylation of ethyl 2-methylacetoacetate by prenyl chloride in the presence of solid metal fluorides proceeds at room temperature with yields of from 2.5 to 87.5% depending on the nature of the deprotonating agent. The alkylation rate increases in going from LiF to CsF. A linear correlation was found between the activation free energy for the alkylation reaction and the crystal lattice energy of the solid metal fluorides. Ion exchange was not observed between tetrabutylammonium chloride and solid KF, CsF, and CaF₂ in acetonitrile. The extent of the exchange with KF·2H₂O over 10 h did not exceed 6%. Deprotonation of ethyl 2-methylacetoacetate by the action of the solid metal fluorides was not observed. Loss of the CH-acid is found in the presence of an onium salt, which varies upon, changing the nature of the deprotonating agent: LiF-NaF=KF (30%), RbF (54%), CsF (90%), CaF₂ (35%).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2690–2696, December, 1989.     

基于液相色谱原理的黄曲霉毒素测定仪校准方法

建立黄曲霉毒素测定仪的校准方法。黄曲霉毒素测定仪校准项目主要包括仪器的动态基线漂移、长期基线噪声、线性相关系数、最小检测浓度、定性与定量重复性。选用C18色谱柱,以甲醇为流动相,流量为1.0 mL/min,其长期基线噪声不大于1500 counts/(30 min),动态基线漂移不大于5000 counts/h;当选用甲醇中黄曲霉毒素B1溶液标准物质,以乙腈-甲醇(1∶1)为流动相,仪器最小检测浓度不大于0.03 ng/mL,线性相关系数不小于0.998,定性重复性不大于1.0%,定量重复性不大于3.0%,仪器的计量性能正常。据此对影响仪器主要性能的各个参数进行全面评价,确认各项性能指标控制在合理范围内。该校准方法切实可行,可用于黄曲霉毒素测定仪的校准。     

What is the structure of the patellamides?

The compound with the structure (2) elucidated for patellamide B was synthesized and found to be not identical with that cyclopeptide. A new proposition for the structure of patellamide B is given.