硝酸酯类分子力学参数的确定和应用

运用MM2(85年版)分子力学程序, 以硝酸甲酯、硝酸乙酯的实验结构为参比, 调试确定了硝酸酯类化合物的伸缩力常数(K~s)、弯曲力常数(K~b)和旋转力常数(V~1、V~2、和V~3)。用这套力场参数计算了硝酸甲酯、硝酸乙酯和硝化甘油的平衡几何构型、生成热和偶极矩, 计算结果与实验值和从头计算结果相一致。还用这套参数计算了结构未见报道的异基硝酸酯、丙烯基硝酸酯和苯基硝酸酯, 所得结果与MNDO全优化几何构型相符。     

硝酸与石蕊试液反应本质的质疑

硝酸与石蕊试液的反应曾经是高中化学教材中硝酸的性质实验之一,此内容也多次在高中生近年来的化学试题中出现,而硝酸与石蕊试液的作用情况比较复杂,其一是石蕊试液与稀硝酸和浓硝酸的反应现象不相同;其二是在不同温度下石蕊试液与浓硝酸反应的现象也不完全相同。室温下将紫色石蕊试液滴人稀硝酸中,溶液立即变为红色,微热之,无明显变化发生;而室温下将紫色石蕊试液滴人浓硝酸中,溶液的颜色会由红色变为橙色,最后变为黄绿色,并伴随有大量红棕色气体产生。对此实验现象,有的教师解释为浓硝酸具有强氧化性,石蕊试液与浓硝酸作用时发生了氧化还原反应,逸出的红棕色气体是浓硝酸的还原产物二氧化氮。而稀硝酸的氧化性弱于浓硝酸,在此仅表现出酸性,因而只能使紫色石蕊试液变红。浓硝酸与石蕊试液作用是否主要发生的是氧化还原反应？黄绿色产物是什么物质？针对上述疑问,我们进行了反复研究,大量实验事实说明,浓硝酸与石蕊试液在发生酸色反应后,主要发生的是硝化反应,同时伴随有硝酸的分解反应,二者发生氧化还原反应的可能性很小。     

硝酸钇对离体蟾蜍,兔心脏和豚鼠乳头肌舒缩活动的影响

介绍了硝酸钇对离体蟾蜍、兔心脏和豚鼠乳头肌舒缩活动的影响。结果表明:低浓度时,硝酸钇对上述离体心脏及乳头肌有兴奋作用;高浓度时则呈抑制效应。硝酸钇对心脏的作用可能与心肌细胞上的钙通道及β-受体有关。     

苯二磺酚吸光光度法测定磷化液中硝酸根

磷化液中硝酸根的测定,以往采用离子交换-中和法。操作繁琐,分析周期长,满足不了生产的需要。苯二磺酚吸光光度法测定磷化液中硝酸根尚未见有报道。本人经过多年的实践,发现在碱性溶液中苯二磺酚与硝酸根可生成黄色络合物。最大吸收波长为410nm,摩尔吸光系数ε为8.5×10~3;硝酸根量在0.10～0.70mg/100ml范围内遵守比耳定律。许多常见离子都不干扰测定。我们认为用此法分析磷化液中硝酸根数据准确、速度快、成本低,用此法分析磷化液中硝酸根含量与中和法所测结果对照都得到满意结果。可分析硝酸根<70g·L~(-1)的磷化液中硝酸根的含量。     

硝酸钕和钐的水合物在水中溶解热的测定

本文用补偿式数字量热计测定了六水、四水硝酸钕和六水、五水硝酸钐298.15K时在水中的溶解热,求得了它们的标准生成热、相应的标准脱水焓和晶格能。     

硝酸与铝直接制取氢气实验的设计与研究

对硝酸与铝直接制取氢气的实验进行了设计与研究。实验发现,室温下一定浓度的稀硝酸与经去膜并用氯化汞溶液处理过的铝箔作用可产生氢气。进一步研究显示硝酸的最高浓度为1.6 mol/L,产生氢气最快时的硝酸浓度为0.07 mol/L;未经氯化汞溶液处理过的铝箔与稀硝酸作用几乎检测不到氢气的产生。     

亚慢性硝酸钐暴露对小鼠血常规指标的动态影响

探讨亚慢性硝酸钐暴露对小鼠血常规指标的动态影响。ICR小鼠80只,雌雄各半,随机分成5组,分别自由饮用含硝酸钐0,5,50,500,2000 mg.L-1的水溶液90 d,在染毒后30,60,90 d分别测定血常规。雄鼠各处理组在硝酸钐暴露30,60 d后,雌鼠硝酸钐暴露60 d后WBC比对照组显著或极显著升高(P<0.05,P<0.01),但硝酸钐暴露90 d后却显著或极显著下降(P<0.05,P<0.01)。在硝酸钐暴露30,60 d后,Gr#,Ly#,MO#比对照组显著或极显著增加(P<0.05(P<0.01),但暴露90 d后无差异显著性。雌性各染毒组的RBC在硝酸钐暴露30 d显著或极显著升高(P<0.05,P<0.01),雄性2000 mg.L-1组却在硝酸钐暴露60 d后RBC显著下降(P<0.05),而硝酸钐暴露90 d对雌雄各组RBC均无影响。雌雄鼠在硝酸钐暴露30,60 d后的HGB,HCT与对照组相比分别显著或极显著升高(P<0.05,P<0.01),但暴露90 d后各组之间的HGB无显著差异,而雌鼠50,500 mg.L-1组的HCT与对照相比显著升高(P<0.05)。亚慢性硝酸钐暴露可导致小鼠血常规部分指标的改变,且与钐暴露的时间、浓度及性别相关。     

六水合硝酸钆(Ⅲ)的晶体结构

文献已报道六水合硝酸镧的晶体结构,配位数为11,并认为六水合硝酸铈与其共结构;六水合硝酸镨、钕、钆的晶体结构为[RE(H_2O)_4(NO_3)_3]·2H_2O(RE=Pr,Nd,Y),配位数是10.而重镧系硝酸盐水合物的结构未见文献报道.本文报道六水合硝酸钆的晶体结构.实验部分     

促进知识素养化的教学——以“硝酸的性质”为例

以“铜制品抛光液”为情境素材,设计一系列的情境问题,旨在探究浓度、温度、酸度等因素对硝酸强氧化性的影响、硝酸的不稳定性及硝酸的贮输等核心内容。开展以化学实验为主的多种探究活动,学生在问题解决和探究过程中结构化“硝酸的性质”知识,利用结构化的知识评价铜制品抛光液的优缺点,并对此种抛光液提出合理的改进方案,促使知识素养化,落实学生的化学学科核心素养。     

有机硝酸酯合成及其在环境治理应用中的研究进展

有机硝酸酯是一类在医药、含能材料和合成化学等领域具有重要应用价值的化合物。大气中的有机硝酸酯是由人为源或自然源排放的挥发性有机物与大气中羟基或氮氧自由基等氧化生成的重要污染物,是环境大气中一类重要的活性氮氧化物,也是二次有机气溶胶的重要组成部分。大气中有机硝酸酯的变化特征及源汇机制已成为大气污染研究热点。本文综述了近年来有机硝酸酯合成研究进展,主要从烯烃官能团化硝酸酯化反应、碳氢键硝酸酯化和其它反应方面总结。同时总结了近年有机硝酸酯化合物标准物质合成及其在环境治理应用进展,展望了有机硝酸酯合成方法开发及其在环境科学领域的潜在应用价值。     

Determination of Organic Compounds,Fulvic Acid,Humic Acid,and Humin in Peat and Sapropel Alkaline Extracts

Black, brown, and light peat and sapropel were analyzed as natural sources of organic and humic substances. These specific substances are applicable in industry, agriculture, the environment, and biomedicine with well-known and novel approaches. Analysis of the organic compounds fulvic acid, humic acid, and humin in different peat and sapropel extracts from Lithuania was performed in this study. The dominant organic compound was bis(tert-butyldimethylsilyl) carbonate, which varied from 6.90% to 25.68% in peat extracts. The highest mass fraction of malonic acid amide was in the sapropel extract; it varied from 12.44% to 26.84%. Significant amounts of acetohydroxamic, lactic, and glycolic acid derivatives were identified in peat and sapropel extracts. Comparing the two extraction methods, it was concluded that active maceration was more efficient than ultrasound extraction in yielding higher amounts of organic compounds. The highest amounts of fulvic acid (1%) and humic acid and humin (15.3%) were determined in pure brown peat samples. This research on humic substances is useful to characterize the peat of different origins, to develop possible aspects of standardization, and to describe potential of the chemical constituents.     

Properties of different natural organic matter influence the adsorption and aggregation behavior of TiO2 nanoparticles

Natural organic matter (NOM) has considerable influence on the aggregation and stability of titanium dioxide nanoparticles (TiO₂ NPs). However, the effect of chemical properties of NOM on the interface interaction and the aggregation process is still not clear. In this study, we investigated the effects of two typical types of NOM (fulvic acid (FA) and humic acid (HA)) on its adsorption onto TiO₂ nanoparticles and their aggregation behavior in aqueous phase. Nuclear Magnetic Resonance (NMR) was used to study their functional groups, indicating that HA has a stronger hydrophobicity than FA. The presence of HA or FA lowered the critical coagulation concentration (CCC) of TiO₂ NPs, while FA showed a more significant effect. HA promotes the aggregation of TiO₂ NPs when ionic strength (IS) > CCC, which was likely due to the bridging effect. Contact angle measurements indicate that HA has higher hydrophobic properties than FA, and it is easier to transfer from water to the surface of TiO₂ NPs. Transmission Electron Microscopy (TEM) was applied to investigate the aggregate formation and colloid interface morphology of NOM-coated-TiO₂ NPs and NOM entanglement. Different structures of HA and FA result in various behavior and their interface interaction mechanisms including IS-induced entanglement and NOM/IS bridging.     

玉米秸秆堆腐过程中形成富里酸的结构分析

采用傅里叶变换红外光谱及＾１Ｈ和＾１３Ｃ核磁共振波谱对玉米秸秆堆腐过程中形成的富里酸的结构进行了表征。结果表明,玉米秸秆腐解过程中形成的富里酸包括羧基或羰基基团,芳香结构,烷基片断和碳水化合物结构。     

顺、反丁烯二酸在铅电极上的电还原特性

采用循环伏安、计时电量及电化学阻抗等方法, 研究了顺、反丁烯二酸在铅电极上的电化学还原行为, 获取了传递系数、表观活化能和扩散系数等动力学参数, 并讨论了电化学还原机理. 结果表明, 顺、反丁烯二酸在铅电极上的电还原过程均为二电子不可逆反应, 扩散过程是速率控制步骤; 反丁烯二酸(FA)的还原电位要比顺丁烯二酸(MA)高约0.1 V, 较顺丁烯二酸难还原; 0.04 mol·L-1顺、反丁烯二酸在0.1 mol·L-1硫酸介质中的扩散系数分别为7.96×10^-6和6.72×10^-6 cm2·s-1. 电化学阻抗研究表明, 在铅电极上顺丁烯二酸较反丁烯二酸有更好的反应活性, 在较低偏置电压下FA和MA的电化学还原过程受电子转移控制, 随着偏置电压的增加, 逐渐转变为扩散控制. 顺丁烯二酸和反顺丁烯二酸的不同空间结构, 使顺、反丁烯二酸在铅电极表面电还原行为存在差异.     

煤中腐植酸与尿素相互作用机理的研究

采用化学法和波谱分析法对泥炭、褐煤、风化煤腐植酸（ＨＡ）与尿素的相互作用机理进行了研究。结果表明,ＨＡ与尿素之间发生了极其复杂的反应,包括离子化、络合配位、亲核加成、自由基反应及氢键缔合等,形成不同的化学键。羧基对反应深度的影响最大;含官能团（特别是羧基）最多的风化煤ＨＡ反应性最高。本项研究为有机长效尿素的研制提供了理论依据     

Fluorescence analysis of humic and fulvic acids from two Brazilian oxisols as affected by biosolid amendment

Conventional monodimensional fluorescence spectroscopy in the emission, excitation, and synchronous-scan modes and total luminescence spectroscopy have proven to be sensitive techniques for characterization and differentiation of humic acid (HA) and fulvic acid (FA) fractions isolated from an aerobically and anaerobically digested and limed biosolid, two layers of a sandy and a clayey Brazilian oxisol, and the corresponding biosolid-amended soils. The spectral patterns and the relative fluorescence intensities suggest greater molecular heterogeneity, less aromatic polycondensation, and less humification of biosolid HA and FA compared with soil HA and FA. However, the differences are smaller for the FA fractions than for the HA fractions. Fluorescence properties of soil HA and FA differ slightly as a function of soil type and soil layer. Biosolid application causes a shift to shorter wavelengths of the main fluorescence peaks and marked variation of the relative fluorescence intensities of HA and FA isolated from amended soils. These results suggest that molecular components of relatively small molecular size, with a low level of aromatic polycondensation, and low degree of humification present in biosolid HA and FA are partially and variously incorporated into amended soil HA and FA. In general, these modifications seem to be smaller in HA and FA from the clayey soil layers than in those from the sandy soil layers, possibly because of protective effects exerted by clay minerals of native soil HA and FA against disturbances caused by biosolid application.     

Binding of cadmium to Laurentide fulvic acid. Justification of the functionalities assigned to the predominant acidic moieties in the fulvic acid molecule

The binding of cadmium to a fulvic acid (FA) extracted from peat was studied as a function of pH (4–8), ionic strength (0.01 and 0.10 M NaNo₃) and ratio of fulvic acid to metal ion concentrations (FA/Cd = 8, 4, and 2). An overall complex formation function of approximately 10^3.14 was determined to enable comparison with previous studies. Additionally, literature values of complex formation constants were employed to describe the interaction between Cd(II) and the individual acidic sites. A good prediction of the experimental results is considered as a justification of the functionalities assigned to the predominant acidic sites in the fulvic acid molecule.     

离子液体萃取阿魏酸和咖啡酸的性能研究

以1-甲基-3-丁基咪唑六氟磷酸盐([C4mim][PF6])和1-甲基-3-己基咪唑六氟磷酸盐([C6mim][PF6])离子液体为萃取剂,采用紫外分光光度法研究了溶液pH值、温度、相比率及盐的种类和浓度对其萃取阿魏酸和咖啡酸效率的影响,考察了被萃取物的回收及离子液体的循环使用,探讨了两种离子液体替代传统有机溶剂阿魏酸和咖啡酸的可能性。实验结果表明:萃取温度和无机盐的种类及浓度对FA和CA萃取效率的影响较小;水相pH值对萃取效率有较大的影响,萃取FA适宜pH应小于3.67,萃取CA适宜pH应小于3.71;被萃取物浓度增大,萃取效率降低,而相体积比增大其萃取效率升高;两种离子液体对FA和CA的萃取效率[C4mim][PF6]大于[C6mim][PF6],同种离子液体对FA的萃取效率大于CA;在萃取相中的FA和CA可定量回收,且被萃取物中离子液体的残留[C6mim][PF6]小于[C4mim][PF6],离子液体可循环使用。     

Enhanced Transdermal Absorption of Hyaluronic Acid via Fusion with Pep-1 and a Hyaluronic Acid Binding Peptide

It is always big challenges for hyaluronic acid (HA) in transmembrane absorbing and efficient delivering to the skin. Pep-1, as one of the cell-penetrating peptides, has been documented to permeate various substances across cellular membranes without covalent binding. Here, a novel hyaluronic acid binding peptide (named HaBP) is designed, and then combined with Pep-1 to enhance the cell-penetrating efficiency of HA. The results of ELISA and immunofluorescence assay show that HaBP could bind with HA very well, and a combination of Pep-1 and HaBP could efficiently improve the transmembrane ability of HA. Furthermore, HA gradually enters the dermis from the surface of the skin in mice when it is administrated with both HaBP and Pep-1, while there are no obvious allergies or other adverse reactions during this process. This study finds a new method to promote the efficient transmembrane and transdermal absorption of HA, and throws some light on further research on the development of hyaluronic acid and its related cosmetics or drugs.