基于核磁共振T2谱测量水包油型原油乳状液含水率的实验探索

采用超声波制备出不同含水率的水包油型原油乳状液样品,采用CPMG自旋回波法测量了核磁共振T_2谱。根据实验结果分析,提出了分别基于水包油型原油乳状液T_2谱中T_2N峰的弛豫时间T_(23),T_2谱各峰面积和加入过量MnCl_2·4H_2O后T_2谱总峰面积测量含水率的3种可能方法。验证实验表明:两种基于T_2谱峰面积的测量方法具有较强的可行性和有效性;基于横向弛豫时间的测量方法因受原油乳状液乳化程度的影响较大,可行性较差。该研究成果为测量水包油型原油乳状液的含水率提供了新的方法。     

低场核磁结合偏最小二乘回归预测含油污泥水和油含率

快速准确分析处理过程中含油污泥的含水率和含油率有助于现场评价其原油回收效率和优化处理工艺参数。以Dean-Stark装置测定的含油污泥样品的含水率和含油率作为参考值,利用低场核磁共振结合偏最小二乘回归法建立了样品含水率和含油率校正集模型,考察了回波衰减曲线和横向弛豫时间T2曲线对校正集模型性能的影响。结果表明,采用前者建立的校正集模型性能优于后者;在此基础上,建立了31个样品的含水率和含油率通用校正集模型,其含水率和含油率模型的决定系数(R2)分别为0.965 7和0.978 5,校正标准差(RMSECV)分别为2.73%和2.22%。利用3个不同批次采集的HZ-OS样品对该模型进行验证,对于含水率和含油率模型,其验证集R2分别为0.914 1和0.924 7,预测标准差(RMSEP)分别为1.85%和2.04%,与RMSECV值比较接近,说明该模型的稳定性较好,可用于准确分析样品的含水率和含油率。     

石墨炉原子吸收光谱法间接测定蒸汽含水率

利用石墨炉子吸收光谱法测定蒸汽发生器循环水和蒸汽冷凝水中的铯则间接测定蒸汽含水率。蒸汽含水率等于冷凝水中铯的浓度除以循环水中铯的浓度。石墨炉原子吸收光谱可以准确测定０．１ｇ／Ｌ至１ｍｇ／Ｌ浓度的铯,样品中可能存在的一些物质对测定没有干扰。本方法可以满足测定蒸汽含水率的要求,实现了数百份含水率样品的测试。     

聚乙烯醇/纳米羟基磷灰石/丝素蛋白复合水凝胶的制备及其性能研究

本文以聚乙烯醇(PVA)、纳米羟基磷灰石(n-HA)和丝素蛋白(SF)为原料,采用物理共混法、反复冷冻解冻法和NaCl粒子制孔法制得了具有三维结构的PVA/n-HA/SF多孔复合水凝胶,以作为人工角膜支架材料。测试了这种多孔复合材料的含水率、拉伸强度和断裂伸长率,并对其进行了红外谱图、X射线衍射光谱、热重及电子扫描显微镜分析。结果表明,丝素蛋白的添加量增加时,多孔复合水凝胶的含水率相应提高,含水率稳定在75～82%之间;其拉伸强度在0.43～1.00MPa之间,断裂伸长率在183.76～237.53%之间,可以达到人体正常状态下眼压要求,其中复合水凝胶的最佳配比为:PVA:SF:n-HA=10:5:1。;IR和XRD分析表明复合水凝胶在物理交联过程中,各种成分均匀复合,无化学键变化;扫描电镜显示该水凝胶材料具有均匀的三维多孔结构。     

肝素钠/聚乙烯醇复合水凝胶的制备与性能

通过循环冷冻-解冻法,制成了肝素钠/聚乙烯醇(HS/PVA)复合水凝胶材料。 探讨了不同质量分数肝素钠对复合水凝胶材料的可见光透过率、含水率、亲水性、力学性能以及肝素钠释放量的影响。 结果表明,复合水凝胶的可见光透过率为92%以上,溶胀平衡的含水率为72%~78%,亲水性较纯PVA水凝胶有所提升,拉伸强度和断裂伸长率都稍有下降。 细胞粘附实验结果表明,适量的肝素钠的释放可以达到减少细胞粘附的效果。 这种HS/PVA复合水凝胶材料有望用作人工角膜中心区材料。     

褐煤中水分对油煤浆流变性质的影响

针对云南褐煤,用真空干燥脱水和恒温恒湿箱处理获得了不同含水率的褐煤,在常温常压(t=19.3℃,p=1.01×105Pa)条件下研究了褐煤含水率对油煤浆流变特性的影响。研究表明,原料煤含水率对油煤浆黏度和流变特性有一定的影响。随褐煤含水率增加,油煤浆黏度先减小后增加。油煤浆浓度不同,剪切速率不同,黏度出现最低值的含水率值wmin也不同。浓度为45.45%的油煤浆,剪切速率小于4.4 s-1时,wmin为9.20%;剪切速率大于4.4 s-1时,wmin为7.80%。浓度为55.56%的油煤浆,剪切速率小于1.32 s-1时,wmin为7.40%;剪切速率大于1.32 s-1时,wmin为10.00%。随剪切速率变化,油煤浆黏度上下行曲线之间形成滞后环,表明油煤浆体系有触变性,并且不同含水率煤浆体系触变性不同,含水率越大,触变性越明显。实验中不同含水率褐煤油煤浆都属于假塑性流体,且含水率对模型参数有一定的影响。     

化学-物理法制备聚乙烯醇/壳聚糖/纳米羟基磷灰石复合水凝胶及其性能

采用化学 物理交联法制备了聚乙烯醇/壳聚糖/纳米羟基磷灰石（PVA/CS/n-HA）复合水凝胶材料。 通过对比其含水率、拉伸强度、红外光谱和TG谱图,探讨了PVA含量及戊二醛加入量对材料性能的影响。 结果表明,m(PVA)∶m（CS+n-HA）=5∶1,戊二醛质量分数为2%时,复合水凝胶材料具有较好的综合性能：含水率为82.0%、拉伸强度为2.14 MPa、断裂伸长率为343.26%;同步热分析表明,25~140 ℃,仅存在水分的蒸发,直至360 ℃材料才发生分解,说明材料的热稳定性良好;红外分析表明,CS与戊二醛发生了交联反应。     

化学-物理法制备聚乙烯醇/壳聚糖/纳米羟基磷灰石复合水凝胶及其性能

采用化学-物理交联法制备了聚乙烯醇/壳聚糖/纳米羟基磷灰石(PVA/CS/n-HA)复合水凝胶材料。通过对比其含水率、拉伸强度、红外光谱和TG谱图,探讨了PVA含量及戊二醛加入量对材料性能的影响。结果表明,m(PVA)∶m(CS+n-HA)=5∶1,戊二醛质量分数为2%时,复合水凝胶材料具有较好的综合性能:含水率为82.0%、拉伸强度为2.14 MPa、断裂伸长率为343.26%;同步热分析表明,25~140℃,仅存在水分的蒸发,直至360℃材料才发生分解,说明材料的热稳定性良好;红外分析表明,CS与戊二醛发生了交联反应。     

多孔β-磷酸三钙/壳聚糖/聚乙烯醇复合水凝胶的制备与性能

以NaCl为致孔剂,采用溶盐致孔法制备了多孔β-磷酸三钙/壳聚糖/聚乙烯醇（β-TCP/CS/PVA）复合水凝胶材料。 通过对比其含水率、溶胀比、拉伸强度、X射线衍射谱图、SEM和热重分析曲线,探讨了在相同环境下壳聚糖与β-磷酸三钙（β-TCP）的不同用量对聚乙烯醇(PVA)的结晶度以及对材料性能的影响。 此复合材料含水率为70%~76%。 当壳聚糖与β-TCP的质量比为2∶8时,复合材料的拉伸强度为0.56 MPa,断裂伸长率达到370%,其较好的力学性能,足以承受正常人眼压,可用作人工角膜周边支架材料。     

X射线荧光光谱法同时测定矿石中铀和钍

建立了X射线荧光光谱法测定矿石样品中铀、钍含量的快速分析方法。采用高压粉末制样法,对不同含量的放射性样品的压片压力、粒径、含水率、用量等处理条件到进行单因素实验。在400 MPa压力下压制,克服了低压制样的弊端,制备的样片表面光滑、致密,大幅改善了制样重现性,有效地减少了部分基体效应,铀校准曲线的标准偏差从0.053%降到0.0071%,钍校准曲线的标准偏差从0.062%降到0.0057%。经国家一级标准物质验证,表明方法准确、可靠,能满足样品中铀、钍含量日常分析要求。     

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%.     

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.     

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.     

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%).     

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.     

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.     

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.     

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.