The influence of products and by-products obtained by drinking water electrolysis on microorganisms

It is the aim of this work to underline the chemical character of disinfection processes and to present the results of treatment experiments for artificially and electrochemically added chemicals focusing on chlorine components and hydrogen peroxide obtained on IrO₂/RuO₂ anodes. A discontinuous cell with rotating anode placed 4 mm above an IrO₂ expanded mesh cathode of same diameter was used for the generation of electrolysis products. The thermostated experiments were carried out at a temperature of 20 °C and in constant current mode. Artificial solutions prepared using sodium salts and deionised water were electrolysed. Samples were analysed using the DPD (N, N-diethyl-p-phenylendiamine) method. Escherichia coli K-12, Bacillus subtilis DSM 2277 and Saccharomyces cerevisiae Kolin were used as test-microorganisms. Morphological changes were studied using transmission electron microscopy. The results show that electrolysed water had a higher lethal efficiency than Ca(OCl)₂ of the same measured active chlorine concentration. During the killing period mainly inner cell parts of the microorganisms react chemically with the disinfectants. In sufficiently high concentrations and reaction times, the cell material continues to react. Cell walls or membranes can break-through as electron microscopy pictures show. Electrolysed water had a higher lethal efficiency on microorganisms. This behaviour demonstrates the existence of additional by-products.     

GdF3∶Eu3+/NaGdF4∶Eu3+纳米晶的水热合成及发光性质

采用水热法,以聚乙二醇(400)为分散剂,以NaOH和HNO3溶液调节初始溶液pH值,合成GdF3∶Eu3+和NaGdF4∶Eu3+纳米晶。XRD和SEM结果表明:在酸性溶液(pH=3,5)、中性溶液(pH=7)和碱性溶液(pH=9)中,分别获得具有正交结构的GdF3∶Eu3+纳米晶,GdF3∶Eu3+和NaGdF4∶Eu3+混合晶,六方结构NaGdF4∶Eu3+棒状微米晶。根据Scherrer公式估算pH=3和pH=5时制备纳米晶的一次性粒径分别为49和28 nm。样品的发射光谱结果表明:特征发射峰来自于5D2、5D1、5D0到7FJ跃迁。在主晶相为GdF3样品中,主发射峰来自于Eu3+的5D0→7F1的磁偶极跃迁;晶相为NaGdF4样品的主发射峰来自于Eu3+的5D0→7F2电偶极跃迁。5D0→7F1和5D0→7F2跃迁发射相对强度比值显示:Eu3+在NaGdF4晶体中的格位对称性下降。激发光谱显示出Gd3+和Eu3+具有较好的能量传递。     

Effect of Tb3+ concentration in the visible emission of terbium-doped gadolinium oxysulfide microspheres

Experimental data obtained from optical characterization of Gd₂O₂S:Tb³⁺ microspheres were compared with a rate-equation model in order to understand and simulate the emission intensity and color tonality as a function of Tb³⁺ concentration. The microparticles were prepared by hydrothermal synthesis and characterized by TEM and XRD to confirm spherical microparticles with a hexagonal lattice. Furthermore, fluorescent spectroscopy and rate equation model revealed that the direct energy transfer between Gd³⁺→Tb³⁺ ions and the migration of the excitation energy between Tb³⁺ play an important role in the luminescence intensity, while the color tonality is mainly governed by the non-radiative relaxation processes between Tb³⁺ at low concentrations. Finally, our results suggest that the rate equation model provides an efficient alternative to estimate theoretically the maximum doping concentration in oxysulfides before they present quenching of luminescence.     

Determination of rare earth impurities in high purity uranium by isotope dilution analysis

Summary An isotope dilution method for the determination of rare earth impurities in uranium has been developed and Ce, Nd, Sm, Eu and Gd have been determined in uranium oxide samples. The method involves isotopic dilution with enriched isotopes of the rare earths being measured, followed by the separation of rare earths from uranium. A mass spectrometer with thermionic source was used to determine the relative isotopic abundances in each of these rare earths. All these five elements were analysed selectively by preferential evaporation technique. Trace concentrations down to parts per billion range can be measured with good sensitivity and accuracy.

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Bestimmung von Verunreinigungen an Seltenen Erden in hochreinem Uran durch Isotopenverdünnungsanalyse

Zusammenfassung Eine Isotopenverdünnungsmethode wurde ausgearbeitet zur Bestimmung von Ce, Nd, Sm, Eu und Gd in Uranoxidproben. Das Verfahren umfaßt isotopische Verdünnung mit angereicherten Isotopen der zu bestimmenden Elemente und nachfolgende Abtrennung der Seltenen Erden von Uran. Die relativen Isotopenhäufigkeiten wurden mit Hilfe eines Massenspektrometers mit thermischer Ionenquelle bestimmt. Alle fünf Elemente wurden durch selektive Verdampfung analysiert. Spurenkonzentrationen bis herab zum ppb-Bereich konnten mit guter Empfindlichkeit und Genauigkeit erfaßt werden.

     

N-Arylation of azoles with low basicity by 1,4-dimethoxybenzene during undivided electrolysis

The reactions of 1,4-dimethoxybenzene with 4-nitropyrazole, 3,4-dinitro-5-methylpyrazole, 1,2,4-triazole, 3-nitro-1,2,4-triazole, and tetrazole were studied during undivided amperostatic electrolysis on a Pt electrode in MeCN, CH₂Cl₂, and MeOH. The main reaction products were 2-azolyl-1,4-dimethoxybenzenes and (or) 1,4-diazolyl-1,4-dimethoxycyclohexa-2,5-dienes. In all cases except 1,2,4-triazole, N-arylation occurs only in the presence of the Alk₄N⁺ salts of azoles or 2,4,6-trimethylpyridine as a base. The mechanism of the reactions is discussed.     

Capillary electrophoresis-based assessment of nanobody affinity and purity

Drug purity and affinity are essential attributes during development and production of therapeutic proteins. In this work, capillary electrophoresis (CE) was used to determine both the affinity and composition of the biotechnologically produced “nanobody” EGa1, the binding fragment of a heavy-chain-only antibody. EGa1 is an antagonist of the epidermal growth factor receptor (EGFR), which is overexpressed on the surface of tumor cells. Using a background electrolyte (BGE) of 50 mM sodium phosphate (pH 8.0) in combination with a polybrene-poly(vinylsulfonic acid) capillary coating, CE analysis of EGa1 showed the presence of at least three components. Affinity of the EGa1 components towards the extracellular domain of EGFR was assessed by adding different concentrations (0–12 nM) of the receptor to the BGE while measuring the effective electrophoretic mobility of the respective EGa1 components. Binding curves obtained by plotting electrophoretic mobility shifts as a function of receptor concentration, yielded dissociation constants (K_d) of 1.65, 1.67, and 1.75 nM for the three components, respectively; these values were comparable to the K_d of 2.1 nM obtained for the bulk EGa1 product using a cellular assay. CE with mass spectrometry (MS) detection using a BGE of 25 mM ammonium acetate (pH 8.0) revealed that the EGa1 sample comprised of significant amounts of deamidated, bisdeamidated and N-terminal pyroglutamic acid products. CE–MS using a BGE of 100 mM acetic acid (pH 2.8) in combination with a polybrene–dextran sulfate–polybrene capillary coating demonstrated the additional presence of minor products related to incomplete removal of the signal peptide from the produced nanobody. Combining the results obtained from affinity CE and CE–MS, it is concluded that the EGa1 nanobody product is heterogeneous, comprising highly-related proteins that exhibit very similar affinity towards EGFR.     

On the phase CrTe3

A new phase CrTe₃ was discovered and its existence was confirmed by differential thermal analysis and X-ray investigations. Symmetry and lattice parameters as well as the temperature of its peritectic decomposition were determined.

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Über die PhaseCrTe ₃

Zusammenfassung Eine neue Phase CrTe₃ wurde entdeckt und ihre Existenz wurde mittels differential-thermoanalytischer und röntgenographischer Untersuchungen sichergestellt. Es wurden Symmetrie und Gitterparameter sowie auch die Temperatur des peritektischen Zerfalls bestimmt.

     

Thermodynamic parameters for the transfer of ions from water to propylene carbonate

There are large discrepancies between various recorded values for the free energy of transfer of the alkali metal cations from water to propylene carbonate. Using the known enthalpies of transfer given byKrishnan andfriedman, and the entropy correlation introduced byAbraham, these discrepancies are resolved in favour of the values obtained byCourtot-Coupez et al. and those due (indirectly) toGritzner. This enables, for the first time, a reasonably reliable set of free energies, entropies, and enthalpies of transfer to be constructed.

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Thermodynamische Parameter für die Übertragung von Ionen von Wasser in Propylencarbonat

Zusammenfassung Die verschiedenen veröffentlichten Werte für die freie Enthalpie der Übertragung von Alkalimetallkationen von Wasser in Propylencarbonat zeigen große Unstimmingkeiten. Diese Unstimmigkeiten können zugunsten der Werte vonCourtot-Coupez et al. und der (indirekten) vonGritzner behoben werden, wenn man die bekannten Werte für die Übertragungsenthalpie vonKrishnan undFriedman, und die vonAbraham eingeführte Entropiekorrelation benützt. Es ist nun zum ersten Mal möglich, relativ zuverlässige Werte für die freie Energie, Entropie und Enthalpie auszuarbeiten.

     

N-Dimethoxyphenylation of highly basic pyrazoles during undivided electrolysis

The reactions of pyrazole, 3,5-dimethylpyrazole, and its 4-nitro derivatives with 1,4-dimethoxybenzene during undivided amperostatic electrolysis in MeCN (CH₂Cl₂) were studied. The basicity of the medium, which depends on the solvent nature, the nature and concentration of pyrazole and the acid-base properties of additives, and the amount of electricity passed determine the yield and relative content of the target products, viz., 1,4-dimethoxy-2-(pyrazol-1-yl)benzenes (1) and 1,4-dimethoxy-1,4-di(pyrazol-1-yl)cyclohexa-2,5-dienes (2). The process occurs mainly through the interaction of the nonionized solvato complex of pyrazole with the 1,4-dimethoxybenzene radical cation and affords radical intermediates structurally similar to compounds 1 and 2. The key stage of the process determining the 1 : 2 ratio is the rearrangement of the intermediately produced 1,4-dimethoxy-1-(pyrazol-1-yl)arenonium cation to the 1-(pyrazol-1-yl)-2,5-dimethoxyarenonium cation.     

Conformational analysis by LIS. II. 2-and 3-alkyl substituted 1-indanones

The preferred conformations of the alkyl groups relative to the cyclopentenone ring of 2-ethyl-, 2-benzyl-, 2-isopropyl-, and 3-isopropyl-1-indanone were determined by means of the lanthanide-induced-shift technique (LIS). Two different models were used in the calculation of LIS. Coupling data-where available-were compatible with the conformations derived from LIS data. O. Hofer, Mh. Chem.109, 405 (1978).     

Removal of proteinaceous soils using hydroxyl radicals generated by the electrolysis of hydrogen peroxide

We have developed here for the first time a novel method to generate hydroxyl radicals, *OH, by applying slightly negative electric potentials (-0.2--0.8 V vs Ag/AgCl) to the surface of a metal (or metal oxide) that is in contact with hydrogen peroxide solution containing a supporting electrolyte. Namely, *OH radicals were generated at the surface by the electrolysis of hydrogen peroxide according to the equation, H2O2+e- --> *OH+OH-. This method was used to clean a stainless steel fouled with a model protein, beta-lactoglobulin. The *OHs generated at the surface were effective in removing beta-lactoglobulin that had been irreversibly adsorbed, by several minutes of treatment at room temperature (22+/-2 degrees C). The removal rates measured for various concentrations of H2O2 and supporting electrolyte and different potentials were determined exclusively by the electric current.     

五味子中木脂素类成分的高效液相色谱-电喷雾质谱研究

采用液相色谱-电喷雾质谱联用(HPLC-ESI-MSⁿ)技术, 对北五味子与南五味子中木脂素类成分进行了系统研究. 通过HPLC-ESI-MS技术, 获得了相应化合物的保留时间、紫外光谱和分子量等信息, 利用电喷雾多级串联质谱技术(ESI-MSⁿ), 获得了相应化合物的结构信息. 研究结果表明, 北五味子与南五味子的主要木脂素成分除5个共有成分外其它成分差异较大, 并且其共有成分含量差别较大. 在此基础上, 建立了简便、快速的北五味子与南五味子药材分析鉴定的新方法.     

C-Glucosylflavonoid biosynthesis from 2-hydroxynaringenin by Desmodium uncinatum (Jacq.) (Fabaceae)

[2′,3′,5′,6′-²H₄]-2-Hydroxynaringenin is synthesised and incubated with commercially available UDP-glucose and the crude protein extract from Desmoduim uncinatum leaves. The organic extract produces isotopically labelled [2′,3′,5′,6′-²H₄]-vitexin and [2′,3′,5′,6′-²H₄]-isovitexin. Repeating the experiment with denatured protein or replacing the 2-hydroxynaringenin with [2′,3′,5′,6′-²H₄]-apigenin or [2′,3′,5′,6′-²H₄]-naringenin results in no observable incorporation. 2-Hydroxynaringenin is therefore the substrate for C-glucosylflavonoid biosynthesis in D. uncinatum.     

Automatic twin vessel recrystallizer. Effective purification of acetaminophen by successive automatic recrystallization and absolute determination of purity by DSC

I describe an interchangeable twin vessel (J, N) automatic glass recrystallizer that eliminates the time-consuming recovery and recycling of crystals for repeated recrystallization. The sample goes in the dissolution vessel J containing a magnetic stir-bar K; J is clamped to the upper joint H of recrystallizer body D. Empty crystallization vessel N is clamped to the lower joint M. Pure solvent is delivered to the dissolution vessel and the crystallization vessel via the head of the condenser A. Crystallization vessel is heated (P). The dissolution reservoir is stirred and heated by the solvent vapor (F). Continuous outflow of filtrate E out of J keeps N at a stable boiling temperature. This results in efficient dissolution, evaporation and separation of pure crystals Q. Pure solvent in the dissolution reservoir is recovered by suction. Empty dissolution and crystallization vessels are detached. Stirrer magnet is transferred to the crystallization vessel and the role of the vessels are then reversed. Evacuating mother liquor out of the upper twin vessel, the apparatus unit is ready for the next automatic recrystallization by refilling twin vessels with pure solvent. We show successive automatic recrystallization of acetaminophen from diethyl ether obtaining acetaminophen of higher melting temperatures than USP and JP reference standards by 8× automatic recrystallization, 96% yield at each stage. Also, I demonstrate a novel approach to the determination of absolute purity by combining the successive automatic recrystallization with differential scanning calorimetry (DSC) measurement requiring no reference standards. This involves the measurement of the criterial melting temperature T₀ corresponding to the 100% pure material and quantitative ΔT in DSC based on the van’t Hoff law of melting point depression. The purity of six commercial acetaminophen samples and reference standards and an eight times recrystallized product evaluated were 98.8 mol%, 97.9 mol%, 99.1 mol%, 98.3 mol%, 98.4 mol%, 98.5 mol% and 99.3 mol% respectively.     

Die Kristallstruktur der Verbindung Li3Zn0,5GeO4

The crystal structure of the compound Li₃Zn_0.5GeO₄ has been determined and refined by means of three-dimensionalFourier syntheses and least squares. Li₃Zn_0.5GeO₄ crystallizes orthorhombic with space groupD _2h ¹⁶ -Pmnb (No. 62) and the lattice parametersa=6.29,b=10.74 andc=5.17 Å. The crystal structure consists of isolated [GeO₄] tetrahedra, which are linked together by [(Li,Zn)O₄] tetrahedra analogous to Li₃PO₄(h). An additional eight-fold position is partly occupied by two lithium atoms. The occupancy of this position may vary according to the observed range of composition, which lies between Li_3.8Zn_0.1GeO₄ and Li_2.6Zn_0.7GeO₄.

     

CCl2自由基被无机小分子猝灭的速率常数

对CCl4/Ar混合气体脉冲直流高压放电产生CCl2自由基,用541.52 nm激光将电子基态CCl2激励到A 1B1(0,4,0)振动能级上. 通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1和a 3B1)被O2、N2、NO、 CO2、 CS2、H2O、SO2,和SF6分子猝灭的实验结果.用我们提出的三能级模型分析处理实验数据,获得了CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.     

Synthesis of some new fluorine containing 3-dialkylaminomethyl indoles, 3-indolylglyoxamides and tryptamines

Several new 2-(fluoroaryl)-3-dialkylaminomethylindoles, 3-acetyl-2-(fluoroaryl)-indoles, 2-(fluoroaryl)-3-indolylglyoxamides and corresponding tryptamines have been prepared as possible psychopharmacological agents. 2-(Fluoroaryl)-indoles have been synthesized by theFischer indole synthesis. 2-(Fluoroaryl)-indoles on treatment with oxalyl chloride and subsequent reaction with amines, gave 2-(fluoroaryl)-3-indolylglyoxamides. Some of these indolylglyoxamides were reducted with lithium aluminium hydride, to the corresponding tryptamines. 2-(Fluoroaryl)-indoles when subjected toMannich reaction afforded 3-dialkylaminomethyl-2-(fluoroaryl)-indoles. All these new compounds have been characterized by IR spectral studies.Possible Psychopharmacological Agents, Part XII, Part XI, J. Indian. Chem. Soc.57, 423 (1980).     

Studies on the reaction of salicylidenebenzoic-hydrazide (SBH) with Ce3+, Th4+ and UO2 2+

The stoichiometry and structure of salicylidenebenzoic-hydrazine (SBH) chelates with UO₂(II), Ce(III) and Th(IV) in buffer-ethanol mixtures and in pure ethanol is studied applying conductometric titration, visible spectrophotometry and ir-spectrophotometry. The ir-spectra revealed that coordination takes place through the C=O and C=N groups.Deceased December 1977.     

Studies on the overproduction of indole-containing metabolites by a methanol-utilizing yeast

Production of indole-containing metabolites (“indoles”) from methanol has been studied using a mutant ofHansenula polymorpha resistant to 5-fluorotryptophan. Whereas the wild-type culture produces only a small amount of indoles, the mutant is partially deregulated and overproduces indoles. Indoles production was studied in batch and continuous culture and in a washed-cell system. When the pH was above 4.0, indoles production was growth-associated, in both minimal and complex media, and batch or continuous culture. When the pH was below or equal to 4.0, a low phosphate concentration was found to improve production. In a phosphate-deficient washed-cell suspension system, the addition of an amino acid such as methionine at 5 mM increased specific productivity by more than 60%. Addition of cycloheximide at 50 mg/L decreased residual growth and increased maximum productivity of indoles by more than 60%. When the antibiotic was added at 1000 mg/L, growth was completely inhibited and indoles production continued for about 35 h.     

Synthesis of a tricyclic tetraazatriacetic ligand for gadolinium(III) as potential contrast agent for MRI

A tricyclic tetraazatriacetic compound, which is a rigidified derivative of PCTA12 ligand with a cyclohexylene bridge replacing an ethylene one, was prepared. Two synthetic routes have been investigated, both of them implying a common functionalized triamine intermediate. Whatever the route, four synthetic steps were necessary to obtain the target tricyclic ligand. The more effective one (Route B) led to the desired compound in 19% overall yield from the triamine intermediate. The corresponding gadolinium complex of 1/1 stoichiometry was then prepared in order to evaluate it as potential contrast agent for MRI.