新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

设计合成了2个新型水溶性中氮茚季铵盐化合物4a{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基)肼基]酰乙基-1-吡啶鎓盐}和4b{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基)肼基]酰乙基-1-(2-甲基吡啶)鎓盐},采用红外光谱、核磁共振、质谱和元素分析对其进行了结构表征,并研究了它们的光谱性质.选取Cu2+,Zn2+,Ca2+,Cr3+,Co2+,Al3+,Mn2+,Ni2+,Ba2+,Hg2+,Fe3+,Cd2+,Mg2+,Pb2+,Li+和Ag+等16种常见金属离子,对2个化合物进行了离子识别实验.结果表明,化合物4a和4b在一定浓度范围内对铜离子均具有良好的选择性识别能力,受常见离子干扰小.由于空间位阻的影响,化合物4a具有比4b更高的灵敏性.     

Thermophysical property characterization of aqueous amino acid salt solutions containing α-aminobutyric acid

In this study, density, electrical conductivity, refractive index and viscosity of aqueous potassium and sodium salt solutions of α-aminobutyric acid were presented. Measurements were done over the temperature range (303.15 to 343.15) K and atmospheric pressure for salt compositions from x₁ = 0.009 to 0.062. A modified Graber et al. equation was used to correlate the density, electrical conductivity, and refractive index with temperature and composition leading to average absolute deviations (AAD) between the predicted and calculated values of 0.04%, 0.7%, and 0.01%, respectively. The viscosity data were represented as a function of temperature and composition via Vogel–Tamman–Fulcher (VTF) type equation at an AAD of 0.6%.     

熔盐电解法制备镨钕钆合金的研究

本工艺采用熔融氟化锂-氟化镨钕-氟化钆熔盐三元体系为电解质,通过电解氧化钆与氧化镨钕混合物的方法,制备了成分稳定的镨钕钆合金,同时就电解质组元、温度、阴极电流密度、加料速度对电解过程的影响进行了试验研究。结果表明:在试验条件下可以生产钆含量(10~15)%±0.5%(质量分数)的镨钕钆合金,金属直收率大于98%,电流效率大于78%;产品含碳小于0.05%,含铁小于0.3%,含Ca,W均小于0.01%,同时具有成本低、工艺稳定、产品质量好等优点。     

油/水界面张力的影响因素及无机盐对油水铺展的影响

讨论不同有机相与水形成的油/水界面处水/气、油/气及油/水3个界面张力的影响因素及相对大小。重点讨论了加入无机盐对作用于透镜状油滴上的3个界面张力的影响,总结出基本的规律并进行了实验验证。     

Interaction of Plasma Proteins with Tri‐quaternary Ammonium Salt Cationic Surfactant Studied by QCM‐D

A tri‐quaternary ammonium salt cationic surfactant was synthesized. Its structure was confirmed by using Fourier‐transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and X‐ray photoelectron spectroscopy analyses. Three model surfaces, including Au‐CH₃, Au‐OH and Au‐COOH, were fabricated. Adsorptions of surfactant on the three model surfaces and subsequent plasma proteins adsorption were investigated by quartz crystal microbalance with dissipation (QCM‐D). The mass of surfactant on the Au‐COOH surface was the largest, followed by that on the Au‐CH₃ surface, and that on the Au‐OH surface. These results suggested that the main driving force of surfactant immobilization was electrostatic interaction followed by hydrophobic interaction. Based on the results obtained, we concluded that the protein mass adsorbed on Au‐CH₃‐ S , Au‐OH‐ S , and Au‐COOH‐ S surfaces depended on the protein size and orientation. The mass and thickness of S on the Au‐COOH surface is the largest and the protein adsorption capacity of Au‐COOH‐ S surface is inferior to that of Au‐CH₃‐ S . The Au‐COOH‐ S surface could inhibit lysozyme adsorption, maintain the adsorption balance of bovine serum albumin, and induce fibrinogen‐binding protein adsorption.     

亲电二氟甲基试剂S⁃(二氟甲基)硫𬭩盐对1,1⁃偕二氰基烯烃的二氟甲基化: 二氟甲基取代全碳中心的有效构建

An efficient approach for difluoromethylation of dicyanoalkylidenes by electrophilic S-（difluoromethyl）sulfonium salt under organic base was described. A wide range of structurally and functionally diverse dicyanoalkylidenes was readily transferred into corresponding desirable difluoromethylated compounds bearing difluoromethylated all-carbon-substituted centers in good to excellent yields under standard reaction conditions.     

Reaction of small molecules O2, NO,CO, and the Naldini salt (PPh3)2MnBr2: Characterized by infrared spectroscopy,elemental analysis,and single-crystal X-ray diffraction

Addition of 2 equiv. of PPh₃ to MnBr₂ in tetrahydrofuran (THF) solution under N₂ atmosphere results in the formation of Naldini salt (PPh₃)₂MnBr₂ ( 1 ). Reaction of Complex 1 and O₂, NO, and CO (with reducing agent) leads to Complex (OPPh₃)₂MnBr₂ ( 2 ), (PPh₃)₂Mn(NO)Br₂ ( 3 ), and (PPh₃)₂Mn(CO)₃Br ( 4 ), respectively. Both Complexes 2 and 4 crystallize in the triclinic space group P-1 with a = 9.94 Å, b = 10.11 Å, c = 10.53 Å; α = 65.42°, β = 63.16°, and γ = 89.22° of 2 and a = 10.23 Å, b = 12.26 Å, c = 14.44 Å and α = 97.03°, β = 104.34°, and γ = 106.33° of 4 . The isoelectronic replacement of 3CO with 2NO yields the {Mn(NO)₂}⁸ species (PPh₃)₂Mn(NO)₂Br ( 5 ). The single crystal of 5 is in the monoclinic space group C2/c with a = 23.17 Å, b = 9.62 Å, c = 15.92 Å, and β = 114.91°. In the THF solution, Complex 5 serves as an NO source in the presence of NO trapping, Co(TPP), Co(TPP) = 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II).     

Dielectric relaxation and ion transport in silver–boro-tellurite glasses

Glass systems of composition xAg₂SO₄–20Ag₂O–(80?x) [0.50 B₂O₃–0.50 TeO₂], where x = 5, 10, 15, 20, 25 and 30 mol% have been prepared by melt-quenching technique. Frequency- and temperature-dependent conductivity measurements have been carried out in the frequency range 10 Hz to 10 MHz and at a temperature range of 303–353 K, respectively. DC conductivities exhibit Arrhenius behavior over the entire temperature range with a single activation barrier. Addition of Ag₂SO₄ expands the glass network and, consequently, conductivity increases. This suggests that the structure and network expansion are the key parameters for enhancing conductivity. Impedance spectra of these glasses show a single semicircle, indicating one type of conduction. AC conductivity behavior of the glasses was analyzed using both single power law and Kolhrauh–William–Watts (KWW) stretched exponential relaxation function. The power law exponent (s) is temperature-dependent, while the stretched exponent (β) is insensitive to temperature. Scaling behavior has also been carried out using reduced plots of conductivity with frequency, which suggests the ion transport mechanism remains unaffected by temperature and composition.     

Nachruf Prof. Hübner

Abstract

Representative water samples were collected from different oases in the western desert of Egypt to examine characteristics of Egyptian groundwater. Chemical data recognized two basic groundwater types; alkali bicarbonate and alkali chloride, where sodium has the highest concentration. For each region the median SD, δ¹⁸ 0 and ionic strength of water calculated from their chemical analyses are recorded and plotted.

Generally, the results of isotopic content measurements of the groundwaters from the different oases in the western desert indicate the fossile origin of these waters. The values of δD and δ¹⁸ 0 of the western desert oases' waters are characteristic of old paleowaters from the Nubian sand aquifer. Modern sparse rainfall data suggest that any precipitation will exhibit moderate to large positive isotopic content enrichments and cannot be a source for these waters. They have been in no connection with the Nile water, moreover the change in isotopic composition is due to evaporation which is now ineffective at deeper levels.     

Determination of δ2H and δ18O in saline oil-associated waters: the question of simple vacuum distillation of water samples prior to isotopic analyses

The paper deals with analytical and procedural aspects of δ¹⁸O and δ²H determination in saline oil-associated waters. The main objective of the study was to show experimentally the qualitative and quantitative applicability of the simple vacuum distillation of saline oil-associated waters while routine procedures of water isotopic analyses are applied. Additionally, two standard off-line techniques of δ²H determination in water – the zinc and the chromium method – have been compared. Each time a typical isotope salt effect has been tracked on the Dead Sea water. The results clearly show that application of the simple vacuum distillation improve the accuracy and reproducibility of δ²H determinations, especially in chromium off-line technique which appeared to be more sensitive to water salinity. The simple vacuum distillation does not improve the quality of δ¹⁸O determinations in the range of water salinities studied. Its application to high concentrated brines (for example, Dead Sea water) decreases the time of equilibration but still propagate the isotopic error connected with low water activity (in the case of ¹⁸O/¹⁶O ratio) and the incomplete water extraction from the remaining salts (in the case of ²H/¹H ratio); in consequence, its time-consuming application seems to be baseless.