中药注射剂荧光光谱法的快速鉴别和热稳定性研究

红外光谱指纹图谱技术应用中药注射剂的快速鉴别中，某些试样因难于成膜造成制样困难，为此，直接或仅经水稀释后测定了12种21批次的常用中药注射剂的荧光光谱。结果表明：由于中药注射剂常含荧光性物质，但因不同注射剂所含具体荧光性物质不同，同种注射剂又因厂家的具体配方的差异或制备工艺条件的波动，均会使其特征的荧光激发、发射光谱不同或其强度呈现差异；从而可充分利用荧光分析的高灵敏度，使其作为中药整体红外指纹识别的一种辅助手段，根据注射剂的荧光图谱的差异达到快速鉴别、认定和控制配方、工艺的目的。比较而言，荧光法表现出来的差异更为一目了然，易于判断。此外，荧光光谱法还可用于中药注射液的热稳定性的研究。     

钛硅分子筛挤条成型催化剂热稳定性能的研究

采用在空气中程序升温焙烧的方式考察了钛硅分子筛挤条成型催化剂的热稳定性能．对不同温度焙烧得到的样品进行了XRD、IR、UV Raman和SEM表征．结果表明，在高温焙烧时，由于载体结构的改变引起载体与分子筛之问相互作用发生变化，导致成型催化剂中分子筛骨架破坏．随着焙烧温度的提高，IR谱图中960cm^-1处代表钛进入骨架的特征峰的强度迅速减弱，当焙烧温度达到1000℃时，960cm-1处的骨架钛特征峰移至948cm^-1．在紫外拉曼谱图中，骨架位钛物种的特征拉曼谱峰-1125cm^-1谱峰在加入SiO2载体后，高温下峰强度明显降低，这说明载体的加入降低了钛硅分子筛挤条成型催化剂的热稳定性能．     

同步辐射X光散射方法研究聚苯硫醚（PPS）的结晶动力学

本文报道了用同步辐射X光散射方法研究聚苯硫醚(PPS)等温过程结晶动力学,测定了在不同结晶温度Tc下,小角和广角散射强度曲线、散射峰极大值随结晶温度的升高而向小角度移动。由小角和广角测得的一系列不同Tc温度的时间解析谱图,计算出PPS结晶速度(?)1/2最小值为0.47min,相对应的Tc为189℃,低于100℃和高于250℃结晶速度极为缓慢。长周期随结晶温度升高而增大,接近250℃时减小;密度随结晶温度升高而增加,接近熔融时,则有较大的增加;由PPS 30～225℃之间Q随温度变化曲线上的折点,求出T_g=89±5℃(加热速度10℃/min);并计算出在T_g温度时PPS两相热膨胀系数差为:     

程序升温热脱附研究不同热处理的HZSM-5分子筛的表面酸性和催化活性

用静态程序升温热脱附方法研究了不同热处理条件对HZSM-5分子筛的酸性和催化活性时影响。测得了不同焙烧温度和不同抽空温度下氨在HZSM-5上的热脱附谱,计算了测定条件下所相应的HZSM-5的表面酸中心数。结果表明,在HZSM-5表面上存在的两种强弱不同的酸中心随热处理温度而变化的趋势是一致的。在小于650℃时,焙烧温度对异构化的活性中心的酸强度分布影响不大。不同焙烧温度的HZSM-5上邻二甲苯异构化活性与酸中心数有对应的关系,它们随焙烧温度的变化趋势颇为相似。     

温度对铽（III）-转铁蛋白溶液构象的影响

在pH 7.4，0.01 mol/L N-2-羟乙基哌嗪-N’-2-乙磺酸（Hepes）条件下，铽 （III）与N，N’-二（2-羟苄基）乙二胺-N，N’-二乙酸（HBED）结合并发生交换 相互作用使铽（III）荧光增强10~4倍，通过监测铽（III）545 nm荧光强度的变化 测定了Tb-HBED配合物的条件稳定常数是lgK = 14.30 ± 0.49；Tb-HBED配合物中 配体、铽（III）荧光强度均随着温度的升高而降低。在pH 7.4，0.01 mol/L Hepes条件下，Tb_N-apoTf-Tb_C配合物中蛋白质的荧光强度随着温度的升高而降 低，而能量受体铽（III）的荧光强度随着温度的升高而增强，主要源于铽（III） 与螺旋5色氨酸残基间的无辐射能量转移；当温度由0 ℃上升到55 ℃时，平均能量 转移效率AE值增加了29%，给体、受体间距离R有约4.2%的减小，温度变化引起 Tb_N-apoTf-Tb_C配合物大的构象变化；铽（III）与人血清脱铁转铁蛋白的结合使 蛋白质的变性温度降低。同样条件下，Tb_N-apoOTf-Tb_C配合物与Tb_N-apoTf- Tb_C配合物有所不同，虽然能量给体的荧光强度随着温度的增加而减小，但铽（ III）荧光强度没有明显的增强；铽（III）对蛋白质的变性温度几乎没有影响。     

用在位X-射线衍射技术对PAN纤维的动态热解特征和环化动力学的研究

本文用在位X-射线衍射技术研究了PAN(聚丙烯腈)纤维的预氧化过程。由广角测得不同温度下试样随热解时间而变化的一系列的解析谱图中计算出样品的结晶度、微晶尺寸、晶面间距和芳构化指数,并对这些参数随实验条件变化的瞬间情况给予了解释。同时,还描述了PAN纤维在预氧化过程中的环化动力学行为。求解了各温度下的环化反应速率和活化参数。     

用在位X-射线衍射技术对PAN纤维的动态热解特征和环化动力学的研究

本文用在位Ｘ－射线衍射技术研究了ＰＡＮ（聚丙烯腈）纤维的预氧化过程。由广角测得不同温度下试样随热解时间而变化的一系列的解析谱图中计算出样品的结晶度、微晶尺寸、晶面间距和芳构化指数,并对这些参数随实验条件变化的瞬间情况给予了解释。同时,还描述了ＰＡＮ纤维在预氧化过程中的环化动力学行为。求解了各温度下的环化反应速率和活化参数。     

CO_2环境中P110钢阳极溶解过程EIS特征

研究了P110油管钢在CO2 饱和的模拟油田采出液中 ,阳极极化下的EIS谱随温度的变化规律 .结果表明 :在低于 90℃的范围内 ,存在一个谱图转变临界温度 ,临界温度之下为三个时间常数型谱图 ,临界温度之上为两个时间常数型谱图 .从阳极反应机理和CO2 腐蚀特征出发对试验结果进行了解释 .     

傅里哀变换红外发射光谱法研究金属氧化物催化剂 I. 实验建立及氧化钼的还原-氧化研究

本文报导了傅里哀变换红外发射光谱法研究多相氧化物催化剂的实验装置的建立及实验条件的考察。设计加工了一个温度范围宽, 可在各种气氛和真空条件下原位研究氧化物催化剂的红外发射池。以MoO_3为例, 考察了样品厚度, 测试温度对发射光谱的影响。当样品量小于1 mm·cm~(-2)时, 随样品量增加, 谱峰强度线性增加, 但峰形不发生变化。当样品量高于1 mg·cm~(-2)时, 随样品量增加, 谱图严重畸变。随样品温度升高,谱峰强度近似线性增加。并用该方法研究了MoO_3在还原和再氧化过程中表面氧物种的变化。结果表明桥式MO—O—Mo物种比端基Mo=O物种较易还原, 再氧化时, Mo=O物种比Mo—O—Mo物种优先形成。     

傅里哀变换红外发射光谱法研究金属氧化物催化剂——Ⅰ.实验建立及氧化钼的还原-氧化研究

本文报导了傅里哀变换红外发射光谱法研究多相氧化物催化剂的实验装置的建立及实验条件的考察。设计加工了一个温度范围宽,可在各种气氛和真空条件下原位研究氧化物催化剂的红外发射池。以MoO_3为例,考察了样品厚度,测试温度对发射光谱的影响。当样品量小于1mm·cm~(-2)时,随样品量增加,谱峰强度线性增加,但峰形不发生变化。当样品量高于1mg.cm~(-2)时,随样品量增加,谱图严重畸变。随样品温度升高,谱峰强度近似线性增加。并用该方法研究了MoO_3在还原和再氧化过程中表面氧物种的变化。结果表明桥式MO?O?Mo物种比端基Mo=O物种较易还原,再氧化时,Mo=O物种比Mo?O?Mo物种优先形成。     

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.