毛细管区带电泳法测定3种香豆素的离解常数

采用毛细管区带电泳法(CZE)测定瑞香苷(DN)、瑞香素(DP)和7-羟基香豆素(7-HC)的离解常数(p Ka).通过测试不同酸度条件下各香豆素的迁移时间,以香豆素在电泳中有效淌度和运行液中OH-浓度的关系,推导了毛细管区带电泳-紫外分光光度(CZE-UV)法测定3种香豆素离解常数(p Ka)的线性模型,并建立了这3种香豆素的p Ka测定方法.测得3种香豆素的p Ka值分别是7.43(7-HC)、6.91(DN)和6.86(DP).同时也采用传统方法 -紫外分光光度法对这些物质的p Ka进行测定以验证CZE的可靠性,两种测定结果相一致,说明CZE-UV法用于3种香豆素的离解常数的测定,快速、简便、结果可靠.     

NTO球形化粒子的结构与形貌

3-硝基-1,2,4-三唑-5-酮(NTO)是一种能量接近RDX,感度接近TATB的高能低感炸药[1-3],美国将其作为混合炸药研制计划的主要成分[4]。但合成反应过程直接得到的NTO呈典型的棒状结构,其长径比约为3:1,对冲击波刺激敏感,且成型性能较差,在铸装炸药中会导致装药时的粘度增高,不利于浇     

有机酸性磷酸酯油水分配系数和电离常数的测定及其取代基效应研究

用铁盐分光光度法测定了 1 0个有机酸性磷酸酯的油水分配系数 ,并考察了其取代基效应 (诱导极性效应与空间效应 )。同时报道了有机酸性磷酸酯电离常数 p Ka的测定及 p Ka取代基效应 ,并首次观察到 p Ka测定误差与待测样品浓度之间的关系。     

紫外分光光度法测定硒氧化过程中二氧化硒

利用5-硝基-2,1,3-苯并苤硒脑对紫外光的吸收特性,用紫外分光光度计测定硒氧化过程中硒(Ⅳ)含量。研究了硒(Ⅳ)与4-硝基邻苯二胺(NPDA)生成5-硝基-2,1,3-苯并苤硒脑的衍生反应条件,验证了测定结果的准确性。结果表明:衍生反应适宜条件为pH2,反应温度60℃,反应时间10 min,NPDA试剂用量为硒(Ⅳ)的168倍。在0.002~0.02 g/L硒(Ⅳ)范围内,硒(Ⅳ)浓度与衍生产物5-硝基-2,1,3-苯并苤硒脑的吸光度线性关系良好。用该法测定硒氧化过程中二氧化硒含量,RSD为0.52%。硒(Ⅳ)的平均加标回收率为98.12%。本文建立的紫外分光光度法为硒含量较大的体系中硒(Ⅳ)定量分析提供了准确、便捷的测定方法,对于其它价态硒(Ⅵ价、Ⅱ价、0价)测定有借鉴作用。     

用紫外分光光度法和电位滴定法测定几种植物激素的电离常数

分别采用紫外分光光度法和电位滴定法测定了脱落酸、3-吲哚乙酸、赤霉素、水杨酸等几种植物激素的电离常数,对比分析了两种测试方法的原理、测试步骤和数据处理方法.结果表明,采用两种方法测定的四种样品的电离常数与文献报道值一致,且测量结果的重现性较好;这表明紫外分光光度法和电位滴定法可方便地用于测定有机化合物的电离常数.     

分光光度法测定指示剂解离常数的实验教学改进与实践*

设计了一种不需测定指示剂浓度,只需测定指示剂吸光度即可计算获得指示剂解离常数的实验教学方法。实验通过调节溶液pH,使指示剂呈现不同颜色,通过分光光度法测定了溴百里酚蓝指示剂的解离平衡常数pKa=7.24,并与文献值pKa=7.30进行了对比,结果基本一致。通过该实验学生不仅能理解指示剂的化学解离平衡,还能更好地掌握紫外-可见分光光度计的工作原理及操作方法。本实验教学将化学分析原理与仪器分析测定进行了有机结合,提出了一种采用分光光度法实现高效、简单的测定指示剂解离常数的方法,不仅增强了学生的动手能力,而且培养了学生的创新能力,提高了学生的学习兴趣。     

哌拉西林的解离常数测定及其在水溶液中的存在形态

哌拉西林（PIP）是一种广泛使用的广谱β-内酰胺类抗生素,其在环境中滞留可能对水生态产生风险。解离常数可以判断其在环境中的稳定性。本文采用自动电位滴定法,并用3种方法处理滴定数据,测定了PIP在25℃时的解离常数（p Ka）,其中一阶导数法、二阶导数法和二阶导数对pH作图法测得的p Ka值分别为3.19±0.02,3.20±0.09和3.14±0.18,相对标准偏差分别为0.68%,2.7%和5.8%。根据PIP的解离常数,可初步确定中性条件下,PIP以阴离子形式存在。采用液相色谱仪和分光光度计测定了PIP分子在pH 3～11的形态变化,逐渐碱化过程中,在pH 3～7溶液中PIP分子没有形态变化;在pH 9～11溶液中,PIP分子降解程度随pH升高而升高;pH 11时,PIP瞬间降解。将此溶液体系酸化（pH 11～3）过程中,溶液中存在2种可相互转化的降解产物,含量随pH改变。本研究通过PIP和其它抗生素的对比,预测了PIP的水解行为。     

高聚物包覆法抑制NTO酸性腐蚀的XPS实验研究

采用高聚物包覆方法制得了NTO/F2311药柱,用XPS测试了药柱与不锈钢、铝、铜等金属高温接触贮存期间的NTO酸性腐蚀作用.结果表明,NTO/F2311药柱与金属在高温接触贮存期间未发生酸性腐蚀,F2311具有抑制NTO酸性腐蚀的作用;样品表面各种原子的迁移变化不明显,F2311中含氯链段发生取向为药柱深层的迁移,而含氟链段发生取向为药柱表面的迁移;药柱表面组分的迁移存在着的取向性使表面层组分的电子云密度降低以及峰位结合能增大,起到了抑制NTO酸性腐蚀的作用.     

AGNTO的制备和分子结构

通过3-硝基-1,2,4-三唑-5-酮（NTO）与氨基胍重碳酸盐反应制备NTO氨基胍盐,并用X射线衍射、元素分析、红外光谱对其进行了表征.晶体属于单斜晶系,空间群为P21/n.晶体学参数为：a=0.67870(10)nm, b=2.7915(4)nm, c=1.2739(2)nm; β =96.930(10) V=2.3959(6)nm3, Z=12, Dc=1.698 g•cm －3, μ( Mo K )=1.47 cm －1, F(000)=1272.晶体结构经全矩阵最小二乘法修正,最终偏离因子R=0.0352, wR =0.0718.该盐是一种具有广泛应用前景的产气剂材料.     

毛细管电泳-内标法同时测定3种药物的解离常数

本文采用毛细管电泳-内标法对普萘洛尔、阿替洛尔和美托洛尔等3种一元弱碱性药物的解离常数同时进行测定。选取麻黄碱、普鲁卡因和苯海拉明等3种物质为内标物,应用毛细管电泳-内标法及迭代计算法确定内标物的解离常数。测定内标物和分析物在部分和完全质子化条件下的有效电泳淌度,通过单内标体系和多内标体系对3种分析物的解离常数同时进行测定,并对方法的精密度和准确度进行考察。实验结果的相对标准偏差为0.26%~0.96%,测定值与相同条件下单组分测定结果及文献值相差均小于0.1个p Ka单位。该方法不需准确测定缓冲溶液的p H,仅需2次电泳分析即可同时测得3种药物的解离常数,显著缩短了分析时间,适用于高通量的药物评估及筛选。     

Gels from a semifluorinated n-alkane in fluorinated solvents as a probe for intermolecular interactions

Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF₂)₈(CH₂)₁₆H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F₈H₁₆ in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent.     

HCOO在Cu(110)、Ag(110)和Au(110)表面的吸附

采用密度泛函理论(DFT)以及广义梯度近似方法(GGA)计算了甲酸根(HCOO)在Cu(110)、Ag(110)和Au(110)表面的吸附. 计算结果表明, 短桥位是最稳定的吸附位置, 计算的几何参数与以前的实验和计算结果吻合. 吸附热顺序为Cu(110)(-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), 与实验上甲酸根的分解温度相一致. 电子态密度分析表明, 吸附热顺序可以用吸附分子与金属d-带之间的Pauli 排斥来关联, 即排斥作用越大, 吸附越弱. 另外还从计算的吸附热数据以及实验上HCOO的分解温度估算了反应CO2+1/2H2→HCOO的活化能, 其大小顺序为Au(110)>Ag(110)>Cu(110).     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

Studies on the Formation of Catalytically Active PGM Nanoparticles from Model Solutions as a Basis for the Recycling of Spent Catalysts

The paper presents basic studies on the precipitation of platinum, palladium, rhodium, and ruthenium nanoparticles from model acidic solutions using sodium borohydride, ascorbic acid, and sodium formate as reducing agents and polyvinylpyrrolidone as a stabilizing agent. The size of the obtained PGM particles after precipitation with NaBH₄ solution does not exceed 55 nm. NaBH₄ is an efficient reducer; the precipitation yields for Pt, Pd, Ru, Rh are 75, 90, 65 and 85%, respectively. By precipitation with ascorbic acid, it is possible to efficiently separate Pt, Rh, and Ru from Pd from the two-component mixtures. The obtained Pt, Pd, and Rh precipitates have the catalytic ability of the catalytic reaction of p-nitrophenol to p-aminophenol. The morphological characteristic of the PGM precipitates was analyzed by AFM, SEM-EDS, and TEM.     

Direct Quantitation of Phytocannabinoids by One-Dimensional 1H qNMR and Two-Dimensional 1H-1H COSY qNMR in Complex Natural Mixtures

The widespread use of phytocannabinoids or cannabis extracts as ingredients in numerous types of products, in combination with the legal restrictions on THC content, has created a need for the development of new, rapid, and universal analytical methods for their quantitation that ideally could be applied without separation and standards. Based on previously described qNMR studies, we developed an expanded ¹H qNMR method and a novel 2D-COSY qNMR method for the rapid quantitation of ten major phytocannabinoids in cannabis plant extracts and cannabis-based products. The ¹H qNMR method was successfully developed for the quantitation of cannabidiol (CBD), cannabidiolic acid (CBDA), cannabinol (CBN), cannabichromene (CBC), cannabichromenic acid (CBCA), cannabigerol (CBG), cannabigerolic acid (CBGA), Δ9-tetrahydrocannabinol (Δ9-THC), Δ9-tetrahydrocannabinolic acid (Δ9-THCA), Δ8-tetrahydrocannabinol (Δ8-THC), cannabielsoin (CBE), and cannabidivarin (CBDV). Moreover, cannabidivarinic acid (CBDVA) and Δ9-tetrahydrocannabivarinic acid (Δ9-THCVA) can be distinguished from CBDA and Δ9-THCA respectively, while cannabigerovarin (CBGV) and Δ8-tetrahydrocannabivarin (Δ8-THCV) present the same ¹H-spectra as CBG and Δ8-THC, respectively. The COSY qNMR method was applied for the quantitation of CBD, CBDA, CBN, CBG/CBGA, and THC/THCA. The two methods were applied for the analysis of hemp plants; cannabis extracts; edible cannabis medium-chain triglycerides (MCT); and hemp seed oils and cosmetic products with cannabinoids. The ¹H-NMR method does not require the use of reference compounds, and it requires only a short time for analysis. However, complex extracts in ¹H-NMR may have a lot of signals, and quantitation with this method is often hampered by peak overlap, with 2D NMR providing a solution to this obstacle. The most important advantage of the COSY NMR quantitation method was the determination of the legality of cannabis plants, extracts, and edible oils based on their THC/THCA content, particularly in the cases of some samples for which the determination of THC/THCA content by ¹H qNMR was not feasible.     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

New Complexes of Ditopic Ligands with “d” and/or “s” Metal Ions

Abstract

The asymmetric compartmental macrocycles containing one N₂O₂ or N₃O₂ Schiff base and one O₂O₃ or O₂O₄ crown-ether like chamber, have been obtained by condensation reaction of the formyl precursors 3,3′-(3-oxapentane-1, 5-diyldioxy) bis (2-hydroxybenzaldehyde) or 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) with ethyl ethylenediamine (H₂L_A, H₂L_C), 1,5-diamino-3-azamethylpentane(H₂L_B, H₂L_D), also in the presence of metal ions as templating agents. These ditopic ligands, with dissimilar coordination sites, have been designed and used for the selective complexation of “d” and/or “s” metal ions, respectively into the Schiff base and the crown ether chamber. The selectivity of these processes strongly depends on the size and on the donor atom sets of the sites. The possibility to obtain mononuclear M(L)·nH₂O (M = Ni²⁺, Cu²⁺, Co²⁺), Mn(L)(CH₃COO)·nH₂O or Na(L) and hetero-dinuclear MNa(L)(CH₃COO) (M = Ni²⁺, Cu²⁺, Co²⁺) and MnNa(L)(CH₃COO)₂·nH₂O complexes has been successfully tested. The ligands and complexes have been characterized by ir, nmr, mass spectrometry and magnetic susceptibility measurements.

Two of the ligands used for the preparation of the solid samples, i.e., to H₂L_A and H₂L_B, have been employed to study complexation reactions of Co(II) and Na(I) in solution. In order to obtain information on the ligand preorganization effect toward the complex stabilities, a simpler open chain parent compound of H₂L_B (H₂L_E) has been also prepared and studied. FT-IR spectra show that H₂L_A is unable to complex Na⁺ in DMSO while the complexation reactions of Na⁺ by H₂L_B and of Co²⁺ by H₂L_A take place with slow kinetics. Therefore, thermodynamic data have been obtained only for the systems Co²⁺/H₂L_B and Co²⁺/H₂L_E. The thermodynamic parameters obtained for the complexation reactions show that the pre-organization of the donor atoms in H₂L_B does not add a significant contribution to the stabilities of the complexes. Both H₂L_B and H₂L_E form in DMSO 1:1, 1:2 and 1:3 = M:L complexes with very similar stabilities and almost equal enthalpies of formation. Physico-chemical studies suggest besides that the slow reaction of Na⁺ with H₂L_B is probably due to the formation of a 1:1 complex where the metal cation, initially occupying the O₃ cage of the ligand, slowly binds also the oxygens of the phenolic moieties. Spectral and calorimetric data on solutions containing H₂L_B and different Co²⁺: Na⁺ ratios evidence that in DMSO no stable heterodinuclear complexes form when the neutral ligand is considered.     

具有聚集诱导发光性质的近红外荧光染料

聚集诱导发光(AIE)现象的发现为解决传统有机荧光分子在高浓度和聚集形态下存在的荧光猝灭问题提供了最佳方案,并实现了在光电器件、化学传感、生物成像和靶向治疗等众多领域的广泛应用.随着对AIE 发光机理研究的不断深入,AIE 分子体系得到了极大的扩展.其中,一类具有给体-受体结构的AIE分子能够显著降低分子能隙,使发光分...