差示扫描量热法测定对乙酰氨基酚原料药纯度

建立差示扫描量热(DSC)法测定对乙酰氨基酚原料药纯度的方法。考察升温速率、称样量、坩埚类型对测定结果的影响,确定最佳测定条件:升温速率为1.0℃/min,称样量为2.0~2.2 mg,选用Tzero密封铝坩埚作为样品盘。DSC法测定对乙酰氨基酚原料药纯度为99.91%,测定结果的相对标准偏差为0.03%(n=6),DSC法测定结果与紫外可见分光光度法测定结果(99.85%)基本一致,且DSC法测定结果的相对标准偏差较小。该方法简便、快速、准确,无需标准品,可用于对乙酰氨基酚原料药纯度的测定。     

L-聚乳酸固相缩聚的工艺研究

以L-乳酸单体为原料,采用复合催化剂通过直接熔融法合成低聚左旋聚乳酸(PLLA),然后分段控温进行固相缩聚(SSP).对固相缩聚的工艺条件进行了详细的研究.采用粘度法和凝胶渗透色谱法(GPC)对固相缩聚产物PLLA的特性粘数([η])和分子量进行了表征.用差示扫描量热(DSC)研究了固相缩聚产物的熔融行为和结晶度.结果...     

六羟基化合物为骨架的高分子固-固相变材料的合成与性能

分别使用三种含6个羟基的化合物(山梨醇、双季戊四醇和肌醇)作为分子骨架,聚乙二醇(PEG)作为相变功能链,4,4'-二苯基甲烷二异氰酸酯(MDI)为交联剂,合成了3种具有不同交联结构的新型固-固相变储能材料。通过傅里叶变换红外光谱(FT IR)、X-射线衍射(XRD)、偏光显微镜(POM)、示差扫描量热法(DSC)和热重量分析法(TG)分别对合成材料的分子结构、结晶性能、相变行为和热稳定性进行了研究。结果显示,所制备的材料在30~70℃温度范围内具有典型的固-固相变特性,其升温和冷却过程的相变焓最高可达107.5J/g和102.9J/g。此外,通过热重分析发现所合成材料具有较好的可重复使用性和热稳定性。因此,合成的新型固-固相变材料在热能储存和控温领域具有巨大的应用潜力。     

低熔点DNAN/RDX混合材料的热行为及分解机理

利用动态测压热分析法(DPTA)、差式扫描量热法(DSC)、热重分析法(TG)、热烤法研究了低熔点含能材料DNAN/RDX的热行为和分解机理。研究得到结论：1)DPTA法测试结果表明DNAN/RDX的热安定性较好；在固相分解阶段，运用Satava-Sestak法得出20～100℃时非等温固相分解阶段机理函数为G(α)=[(1-α)^-1/3-1]²,E_S=85.64 kJ/mol, lgA_s=11.57;等温阶段的等温分解动力学机理函数为G(α)=[(1-α)^1/3,反应速率常数k=1.515 32×10^-4。2)DSC法和TG法研究结果表明RDX主要为熔融液相形式分解，DNAN主要为气相形式分解；混合体系中RDX促进了DNAN的分解过程，DNAN/RDX的受热质量损失过程主要为DNAN的挥发过程和RDX的热分解过程。运用DSC法研究升温速率为5℃/min时DNAN/RDX的热分解过程，普适积分法得出在224～320℃范围内的分解过程机理函数为G(α)=[-...     

差示扫描量热法测定草酸艾司西酞普兰纯度

采用差示扫描量热法(DSC),根据DSC曲线利用纯度分析软件测定草酸艾司西酞普兰的纯度。对实验条件进行了优化,升温速率为4.0 K/min,称样量为2~3.2 mg。测得草酸艾司西酞普兰的纯度为99.17%,相对标准偏差为0.05%(n=6)。该法测定结果与非水滴定法测定结果(99.24%)基本一致。差示扫描量热法可用于测定草酸艾司西酞普兰纯度,方法操作简便、结果准确。     

高热值多面体硼氢化合物十氢十硼酸双四乙基铵的合成、热分解机理及动力学研究

以四氢硼酸四乙基铵为原料,通过热解反应合成了十氢十硼酸双四乙基铵,并采用红外光谱(IR),核磁共振波谱(1H NMR,11B NMR)及元素分析对其结构进行了表征.采用差热-热重(DSC-TG)分析研究了其在氩气及氧气气氛下的热稳定性,发现其在氩气中仅发生热分解反应,放热量较小,而在氧气中则先分解,再发生氧化反应并放出大量的热.采用Kissinger方法及Coat-redfern方程得到其热分解主反应的动力学方程,并进一步通过热裂解原位池-傅里叶变换红外光谱(FTIR)联用技术和同步热分析-红外-质谱(DSC-TGFTIR-MS)联用技术研究了其热分解机理,推测在加热升温过程中,化合物在303.2℃下快速分解,气相产物主要为乙烷与少量氨气及氢气,固相产物为单质硼.     

La0.8Sr0.2-xCaxCo0.9Fe0.1O3-δ的合成与电性能

利用X射线衍射 (XRD)、差热 热重 (DSC/TG)与直流四探针测试分析方法研究了少量Ca取代LaCoO3 中部分La的合成过程及对其电导率的作用。采用固相反应合成的La0 .8Sr0 .2 -xCaxCo0 .9Fe0 .1 O3 -δ(LSCCF ,0≤x≤ 0 1)氧化物为单一钙钛矿相 ,其烧结过程可以分为 3个阶段 :即反应原料的变化 ;LaCoO3 基氧化物的生成 ;LSCCF固溶体的形成。LSCCF复合掺杂材料电导率的最大值都超过了 10 0S·cm- 1 ,其导电机制可以用p型小极子的绝热空隙理论来解释     

没食子酸铋锆的制备、表征及其燃烧催化作用

以没食子酸、硝酸铋和硝酸氧锆为原料, 首次合成出了双金属有机盐——没食子酸铋锆, 采用有机元素分析、X射线荧光(XRF)光谱和傅里叶变换红外(FTIR)光谱对其进行了表征. 在程序升温条件下, 利用热重(TG)分析、差示扫描量热法(DSC)、固相原位反应池/FTIR 联用技术, 研究了没食子酸铋锆的热行为和热分解机理,描述了没食子酸铋锆的热分解过程, 分析得出其最终分解产物为Bi₂O₃、ZrO₂和C. 利用螺压工艺制备了含没食子酸铋锆的推进剂样品, 研究了没食子酸铋锆对双基(DB)推进剂燃烧性能的影响, 分析了其燃烧催化作用. 结果表明, 没食子酸铋锆对双基推进剂的燃烧具有良好的催化作用, 是一种高效的燃烧催化剂; 没食子酸铋锆热分解的最终产物是催化燃烧的主要物质, 锆和碳则起辅助催化的作用.     

相变微胶囊型吸热剂MPCM-2的制备及其控热效果

以十二水合磷酸氢二钠为芯材,乙基纤维素为壁材,采用原位聚合工艺制备了相变微胶囊型吸热剂MPCM-2,其结构和性能经IR、 DSC、TG和粒度分析表征。结果表明：MPCM-2的相变温度为43.34和58.77 ℃,总相变焓值为144.82 J·g^-1,包裹率为67.5%; MPCM颗粒中径为57.26 μm,同时,MPCM-2应用于深水固井水泥浆体系可实现对水化热及水化温升的有效控制。     

吹扫捕集/气相色谱-质谱联用测定水中挥发性有机物

随着生态环境的变化和工业的发展,有毒有害化学品正在威胁着人们的饮水安全。我国对饮用水中有机污染物的监测正在逐步重视和加强,一些研究表明饮用水中挥发性有机物种类较多,含量较高[1,2]。因此,笔者对吹扫捕集/气相色谱-质谱联用测定水中挥发性有机物的方法进行了验证,并对9种饮用水中挥发性有机物的净化效果进行了研究。1实验部分1.1主要仪器与样品气相色谱-质谱联用仪:6890-5973型,美国Agilent公司;吹扫捕集仪:Tekmar3100型,美国Tekmar公司;自来水(编号1),开水(编号2),两种市售瓶装纯净水(编号3、4),某净化器净化后热,冷水(编号5、6),矿物质水(编号7),市售桶装纯净水(编号8),地下饮用水(编号9)。1.2分析条件[1,3]毛细管色谱柱:HP-5型(30m×0.32mm,0.25μm);升温程序:柱温120℃,保持3min,以20℃/min升至160℃,保持2min,再以20℃/min升至200℃,保持1min;载气:氦气,纯度大于99.999%,恒流控制1.0mL/min;分流进样,分流比为10∶1。进样口温度:200℃;传输线温度:280℃;四级杆温度:150℃。扫描范围...     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

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.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.