声光可调滤光片作为电热原子吸收光谱仪波长选择器的研究

研究了声光可调滤光片（AOTF）的性能，并以AOTF为波长选择系统，钽丝为原子化器，用原子吸收光谱法测定了Na。考察了空心阴极灯电流，保护气流量，钽丝原子化器和干燥电压和原子化电压对Na吸收信号的影响。在选定的最佳实验条件下，测定Na的特征浓度为0.045μg/mL，精密度为2．6％（n=8)。在0.050-1.0μg/mL范围内，Na的浓度与吸光度值有良好的线性关系。     

废旧F732测汞仪部件与原子吸收光度计联用测定水中痕量汞

水中痕量汞的测定目前多采用冷原子吸收法。而借助原子吸收分光光度计的标尺扩展功能较一般测汞仪具有更好的灵敏度。本文利用废旧F732测汞仪的薄膜泵和石英管吸收池作为汞的原子化装置,使汞在普通原子吸收分光光度计上的测定变得简便、易行。用于水中痕量汞的测定,得到满意的效果。     

基于液芯波导原理的微流控芯片长光程光度检测系统

提出了一种基于液芯波导(Liquidcorewaveguide,LCW)原理的微流控芯片吸收光度检测系统.通过芯片与外界接口技术实现液芯波导管与芯片的耦合,建立了芯片上长光程(毫米至厘米级)吸收光度检测池.采用邻菲啉-铁(Ⅱ)显色体系验证系统分析性能,以5.5cm外覆TeflonAF液芯波导管作为检测池(检测池体积240nL)时,芯片系统的检测线性范围为0.03～50μmol/L,对邻菲啉-铁(Ⅱ)配合物的检出限为8nmol/L,检测池有效光程达1.7cm,分析精度RSD(n=5)为0.8%.     

石墨炉原子吸收光谱法测定人尿和血以及发中铝

铝在临床医学领域内日益引起人们的兴趣和关注,在职业性危害中吸入铝的粉尘和烟能引起“铝尘肺”;测定铝的方法过去采用比色法,费工耗时,火焰原子吸收光谱法灵敏度不够,采用石墨炉原子吸收光谱法测定,大大提高了灵敏度,而且需样量少,可作为一种在临床上有较高应用价值的诊断手段。 将制备好的样品,注入石墨炉原子化器中,原子化后,待测元素的基态原子吸收来自同种元素,空心阴极灯发出的特征潜线(Al 309.3nm),Al在一定范围内,吸光度与其含量成正比,与标准系列比较进行定量。     

RP-HG-AFS联用研究长期汞暴露人群补硒前后血清中汞的形态

建立了反相色谱-氢化物发生原子荧光光谱联用测定血清中汞形态(无机汞和甲基汞)的方法,优化了载流液,还原剂以及2-巯基乙醇的浓度,以正辛醇作为消泡剂,成功地解决了测定血清样品时原子荧光仪器内气液分离器中产生大量泡沫的难题。采用反相色谱柱对无机汞和甲基汞形态进行了分离,回收率在95％～110％之间,无机汞和甲基汞的精密度R...     

石墨炉原子吸收光谱分析的理论基础 Ⅰ.有关石墨炉原子吸收信号形状的理论

1955年首先由Walsh建立起来的利用原子共振吸收现象的原子吸收光谱法是一种高灵敏度的光谱化学仪器分析方法,已成为无机分析领域中的一种有力的常规分析手段。1959年L′vov发表了石墨炉原子化器在原子吸收定量分析上应用的经典论文。其后,随着这种原子化器的不断改进与完善,石墨炉原子吸收法已成为与质谱分析、活化分析並列的超微量     

关于高含量组分光度测定中吸收池误差的消除

对高含量组分的测定,采用高吸收差示分析法可提高吸光度测定的准确度和精密度。但在测定中由于吸收池光程的不匹配而引起的误差往往重视不够。本文研究了吸收池不匹配所引起的误差的消除方法,并应用于陶瓷结合剂中高含量二氧化硅的测定,取得较好效果,测定结果的相对标准偏差小于0.3％。 1 方法原理 在进行一次光度测定中,所测得的吸光度值包括被测物质的吸收、溶液体系的背景吸收以及试剂空白的吸收。在吸收池完全匹配的情况下,按Lambert-Beer定律可得:     

气相色谱-原子吸收联用技术测定人体体液中烷基汞

建立了一种用于生物样品中分子形态分析的气相色谱与原子吸收联用系统。系统的转移线为聚四氟乙烯管,组分在色谱住内分离后,经转移线运送到原子吸收检测系统。实验证明:系统具有灵敏度高、选择性好的优点,例汞绝对检测限为10-2ng,并首次用于人体血液和尿液中烷基隶的两种形态即氯化甲基汞和二甲基汞的定性和定量分析。     

冷原子吸收光谱法直接测定尿汞

汞属于剧毒物质,进人人体的无机汞可转变为毒性更大的有机汞,引起全身中毒作用.目前测定尿汞的方法主要有冷原子吸收光谱法、冷原子荧光法.尿样的前处理多采用常压湿法消解,存在试剂消耗量大,处理时间长,回收率低等缺点.本工作采用不进行消化处理直接取样,采用冷原子吸收光谱法测定职业人群的尿汞,此法快速、简单、试剂用量少,回收率高.     

相同光程吸收池的红外光谱法同时测定绝缘油结构族组成和T501抗氧化剂的含量北大核心CSCD

根据标准GB/T 7602.3-2008和DL/T 929-2018,采用傅里叶变换红外光谱仪,分别用光程为0.1 mm和0.5 mm的KBr吸收池测定绝缘油结构族组成和T501抗氧化剂含量,对检测结果的差异性进行分析。结果表明:两种光程吸收池测定绝缘油的结构族组成结果符合DL/T 929-2018的再现性要求,并且不存在显著性差异,而0.5 mm光程吸收池测得的芳香烃和烷链烃的吸光度更大,适用于绝缘油结构族组成的准确测定;两种光程吸收池测定绝缘油中T501抗氧化剂含量结果偏差较大,不符合GB/T 7602.3-2008的再现性要求,而0.5 mm光程吸收池测得的T501抗氧化剂的峰形较好,无吸收干扰,适用于绝缘油中T501抗氧化剂含量的测定,并且采用峰面积定量所得结果的再现性相对较好。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.