化学振荡的间接扰动法测定磷酸苯酯

根据磷酸苯酯在碱性磷酸酶的催化作用下水解生成的苯酚对化学振荡体系(溴酸钠-硫酸-苹果酸-大环铜配合物)产生的干扰作用,首次建立一种分析测定磷酸苯酯二钠二水(DPPD)的新方法.其分析结果表明:当磷酸苯酯二钠二水的浓度在2.0×10-6~6.0×10-4mol.L-1范围内时,其浓度对数与振荡体系的振幅的改变值△A呈良好的线性关系,相关系数为0.996 49.     

HBED、EHPG分子内氢键与光谱性质

在pH 7.4、0.1 mol·L-1 Hepes条件下,由Tb3+荧光测得Tb-EHPG条件稳定常数log K为13.95±0.13;EHPG与金属离子结合后分子内O…H-O型氢键断裂而导致荧光被淬灭；HBED与金属离子结合后分子内N…H-O型氢键断裂而导致荧光增强,荧光变化均与结合的金属离子的原子量成反比.由此总结了稀土离子与HBED,EHPG结合的规律.并用荧光方法推断了脱铁伴清蛋白N-,C-端结合部位酪氨酸残基的分子内氢键类型.     

New crystal structure of molecular complex 1-piperidine carboxylate-piperidinium-H<Subscript>2</Subscript>O studied by X-ray single crystal diffraction

Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

二硫基二苯并噻唑的绿色合成

以2-巯基苯并噻唑(M)为原料,于水相(含少量丙酮)体系中,在过氧化氢的氧化下发生反应,高产率获得二硫基二苯并噻唑(DM)。     

纳米面状磷酸锰的制备和表征

本文通过沉淀法制备了纳米面状的磷酸锰,并对其结构进行了X-射线粉末衍射(XRD)、透射电镜(TEM)、选区电子衍射(SAED)表征,讨论了温度和反应容器对产物的影响,结果表明在室温条件下能制备出纯的磷酸锰。     

氢原子n=4能级的斯塔克效应

利用微扰论,精确求解了氢原子在无外场时n=4的16重简并态能级波函数;并对处在电场中的氢原子n=4能级斯塔克效应进行了计算和分析.     

Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.     

Potential release of hydrogen fluoride from domestic coal in endemic fluorosis area in Guizhou,China

Almost half of the total rural area of Guizhou Province and many regions within the 11 adjacent provinces in southwestern China have a long history(at least 70 years) of endemic fluorosis,including dental fluorosis and osteofluorosis along with its associated deformities and disabilities.Over decades of research,this specific type of endemic fluorosis has been defined as coal-burning fluorosis,which is distinct from drinking-water fluorosis.It is generally acknowledged that indoor burning and combustion of high-fluorine coal leads to food contamination,and fluorine then enters the human body.However,the exact chemical form of fluorine during its release and transfer to the body is still unknown.In the present study,21 domestic coal samples from outcrop and semi-outcrop coal collected in five villages with fluorosis were analyzed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).The total mass fraction of sulfur in the samples ranged from 0.24%-5.58% and total fluorine content ranged 90.2-149.2 mg/kg.H3O+,H2SO4+ and HSO4-were detected in the samples by TOF-SIMS,which indicated that sulfuric acid hydrate(H2SO4.H2O) was present in the samples.F-was detected in all of these,which suggested the samples contain ionic fluorine compounds.Under certain circumstances,such as heating or burning,the prevalence and coexistence of the acid(H2SO4.H2O) and base(F-) would lead to a neutralization reaction producing volatile hydrogen fluoride(HF,bp = 19.5℃).This would be the chemical form of fluorine released from the coal.Further studies using HF and SO2 test tubes on headspace gas over coal samples heated to 200℃ in the laboratory and on headspace gas over stoves or chimney tops at rural residences confirmed the release of HF.     

噻吩二胺基三嗪衍生物的合成及其与全氟链苯甲酸形成的复合物的液晶行为研究

 以Kumada偶联反应为关键步骤首次合成了未见文献报道的2,4-二胺基-6-(4,5-二癸基噻吩)-1,3,5-三嗪 (T),并制备了在多重氢键作用下T与全氟链苯甲酸(A)形成的超分子液晶复合物.红外光谱(IR)与偏光显微镜(POM)研究表明T与A形成的等摩尔复合物可呈现液晶柱相,其原因可能是T与A通过氢键形成的二聚超分子的中心极性区域由于氢键的存在其极性得到加强,以及全氟链的引入提高了分子内的极性对比,利于微观相分离及分子进行有序自组装.     

曹妃甸海域磷酸盐容量控制

首先,建立曹妃甸海域潮流和污染物输运数学模型,并用实测资料对模型进行验证;然后,应用验证好的数学模型,计算六种典型水文条件(洪季大、中、小潮,枯季大、中、小潮)下该海域8个河流排污口和曹妃甸围填区混合区半径上的磷酸盐浓度,并与功能区要求的水质标准进行比较分析;最后,计算出磷酸盐的允许排放量和削减率.结果表明:磷酸盐超标的枯季为陡河和沙河,洪季为双龙河和围填区,应加强对这些河流相应季节磷酸盐排放量的控制.