应用红外光谱研究脱灰对伊敏褐煤结构的影响

对伊敏褐煤的原煤和脱灰煤进行了红外光谱分析,并通过分段分峰拟合分析了脱灰前后伊敏煤结构的变化。结果表明,脱灰处理对煤中有机结构会产生一定影响。对脂氢和羟基氢键有机结构影响较小,脱灰后,脂氢结构中CH2不对称伸缩振动没有变化,CH伸缩振动明显减少,而CH2对称伸缩振动和CH3不对称伸缩振动略有增加;羟基氢键结构中羟基N羟基、自缔合羟基氢键以及羟基π氢键的强度有所降低,而环氢键和羟基醚氢键的吸收强度有所增加;对芳香结构和含氧官能团的影响较大,芳香结构由原煤中的苯环三取代占主导地位转变为脱灰煤中的苯环三和四取代;含氧官能团中烷基醚和脂肪羧酸脱灰后吸收峰的强度明显减弱,这是由于水解反应导致的,而酚羟基和羧酸脱灰后吸收强度明显增强。     

低煤化度煤低温热解脱氧后结构的变化

采用低温热解脱氧方法对低煤化度煤中含氧官能团化学活性进行了系列研究,测定了ＦＴＩＲ、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ及比表面积和孔径分布。得出了煤中含氧官能团的化学活性顺序,并发现低温热解脱氧的同时,煤分子中的Ｏ重新分布,Ｈ分布、Ｃ分布及孔径分布的变化,是低温热解导致煤分子改性的原因所在     

煤的性质对具有粘结剂冷压成型型煤质量的影响

研究了14种不同煤化程度煤的性质与其型煤质量的关系。实验表明,以淀粉为粘结剂,在相同成型条件下,14种型煤的抗压强度随着煤化程度降低而降低,褐煤的成型性能最低。影响其抗压强度的主要煤质因素,有煤的最高内在水分、含氧官能团、孔体积、煤表面石墨形态碳含量等,其值越高,型煤强度越低。然而,煤表面烷基侧链疏水形态碳含量低时,则有利于粉煤成型。     

应用红外光谱研究脱灰对伊敏褐煤结构的影响

对伊敏褐煤的原煤和脱灰煤进行了红外光谱分析,并通过分段分峰拟合分析了脱灰前后伊敏煤结构的变化。结果表明,脱灰处理对煤中有机结构会产生一定影响。对脂氢和羟基氢键有机结构影响较小,脱灰后,脂氢结构中CH₂不对称伸缩振动没有变化,CH伸缩振动明显减少,而CH₂对称伸缩振动和CH₃不对称伸缩振动略有增加;羟基氢键结构中羟基N羟基、自缔合羟基氢键以及羟基π氢键的强度有所降低,而环氢键和羟基醚氢键的吸收强度有所增加;对芳香结构和含氧官能团的影响较大,芳香结构由原煤中的苯环三取代占主导地位转变为脱灰煤中的苯环三和四取代;含氧官能团中烷基醚和脂肪羧酸脱灰后吸收峰的强度明显减弱,这是由于水解反应导致的,而酚羟基和羧酸脱灰后吸收强度明显增强。     

红外发射光谱法原位研究褐煤的低温氧化过程

用傅氏红外发射光谱法原位考察了低温氧化过程，用峰拟合程序处理光谱数据，在定量的基础他煤中各主要官能团的变化规律。数据表明，氧化时，煤的芳核部分是稳定的，氧原子主要进攻脂肪族基团，通过生成过氧化物进入煤结构中，整个过程表现为含氧基团的增多和脂肪族基的减少。作为煤低通氧化的一个特征是芳烃Ｃ－Ｈ含量的逐渐递增，这主要是由于它含有较多羧基，其中芳酸的羧基发生脱羧的结果。     

氧化石墨的谱学表征及分析

采用改进的Hummers法,通过改变氧化剂用量获得不同氧化程度的氧化石墨,用X射线衍射(XRD)、红外光谱(FTIR)和拉曼光谱(Raman)对产物进行结构和谱学特性的表征,并结合数学分析软件对部分红外和拉曼数据进行分峰拟合。结果表明,石墨经氧化后形成了含有C-OH、-COOH和C-O-C等官能团的石墨层间化合物;氧化剂用量较少时,石墨片层插层氧化不完全,产物的结构中仍存在未被氧化的原石墨周期性结构;随着氧化剂用量的增加,氧化石墨产物的XRD图中原石墨(002)衍射峰逐渐消失,结构中含氧官能团的量逐渐增加,产物的亲水性也逐渐增强;通过对红外光谱的拟合发现,氧化石墨样品在3 198 cm^-1附近有一个红外吸收峰,应归属于C-OH中OH的伸缩振动;随着氧化剂用量的增加,所得氧化石墨产物的拉曼光谱中D峰与G峰的强度积分比R(I_D/I_G)逐渐增大,产物结构中sp²平面域的平均尺寸逐渐减小。     

几种烟煤及其热处理后的溶胀性能研究

研究了四种不同变质程度烟煤及其二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂(1∶1,vol)的抽提物在不同溶剂中的溶胀性能,同时考察了四种煤样不同温度热处理后其溶胀性能的变化。结果表明,煤的溶胀率随煤化度增加而有所降低;变质程度较低的烟煤在极性溶剂中的溶胀率大于非极性溶剂,随着煤化度的增加,两者溶胀度差距减小;四种烟煤经混合溶剂抽提后,其抽余煤的交联密度降低,溶胀率增加。四种煤样150℃热处理后在CS2中的溶胀率均有所增加,表明热处理可以降低煤的交联密度。随着热处理温度提高至240℃,除气煤外,其余三种煤样在NMP和CS2中溶胀率均进一步增大,说明其交联密度进一步降低。这一结果与热处理煤样在混合溶剂中抽提率的变化趋势一致,如240℃热处理后瘦煤的抽提率由原煤的6.9%提高到17.3%。红外光谱研究表明,经过适当温度的热处理,可以脱除煤分子中的羰基和羟基等含氧官能团,破坏煤结构中的氢键,从而降低煤的交联密度,提高煤的溶胀率及其在混合溶剂中的抽提率。     

如何解释红外谱图

红外光谱(IR)主要提供分子的官能团和化学键的丰富的结构信息。通常一个化学键会出现多个不同位置的吸收峰,而图中每个峰又可能是不同化学键的加合峰。因此在红外光谱分析中,并不要求也不可能准确地归属出图中所有的峰,通常只要求能较确切地识别出其中几个特征峰已足矣。     

柴里煤人工氧化过程中性质和化学结构的变化

对鲁南柴里矿山西组三号煤层煤样进行了氧化模拟实验，对氧化系列煤样进行了元素分析、腐植酸含量和傅里叶变换红外光谱分析，讨论了氧化过程中元素成分和腐植酸含量的变化规律。以高岭石谱带为内标，利用差谱技术测定了氧化过程中柴里煤结构中含氧官能团、脂肪烃和芳烃的变化。结果表明，在煤氧化过程中，含氧官能团明显增加，主要是碳基；脂肪烃含量明显降低，但甲基、亚甲基之间没有发现优先攻击现象；而芳烃在氧化过程中基本上没有发生变化。     

Gaussian软件在红外光谱教学中的应用——同位素效应

借助Gaussian软件探讨了同位素效应对分子特征官能团红外光谱的影响,帮助学生在课堂上认识同位素取代可能造成的红外特征吸收峰的光谱频移,并进一步促进学生在课后独立思考,发挥主观能动性,自行设计有效的同位素取代方案,利用软件工具将课堂知识应用于化合物组分的鉴别中。     

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.