烷基化改性壳聚糖制备条件对酚类化合物吸附的影响

采用脂肪醛与壳聚糖反应生成Schiff's碱,再用NaBH4还原制备了N-烷基化壳聚糖衍生物. 用元素分析测定了其取代度. 考察了不同烷基化条件对庚醛改性壳聚糖取代度和吸附性能的影响. 结果表明,反应时间、醛/壳聚糖配比和反应温度等因素影响烷基化壳聚糖的取代度. 在n(醛)∶ n(壳聚糖)=4∶ 1、反应温度为100 ℃和反应时间为8 h条件下,庚醛改性壳聚糖的取代度趋于最大值,取代度的增加有利于改性壳聚糖对2,4-二氯酚的吸附. 不同链长脂肪醛改性壳聚糖对酚的吸附影响结果表明,随着烷基化链长的增加,改性壳聚糖产物对酚的吸附量增加,但链长超过7个C时,吸附量反而下降.庚醛改性壳聚糖的吸附效果最好.     

巯基化壳聚糖/明胶的制备研究

仿生杂化构建可注射水凝胶支架是制备组织工程材料的一条有效途径,而天然聚合物的改性即成为其前提条件。本文以巯基乙酸和4-丁巯内酯为反应试剂采用均相反应法制备了巯基化天然聚合物衍生物。结果表明,利用壳聚糖和明胶上的氨基等活性基团,可采用不同途径对它们进行巯基化改性;在水溶性碳二亚胺的活化作用下巯基乙酸的羧基与壳聚糖的氨基形成酰胺键,从而将活性巯基引入到壳聚糖中,但大部分被氧化;随着贮存时间的延长,各改性物中的巯基含量逐渐降低,因此需将改性物保存于低温惰性环境中,以保持其反应活性。     

壳聚糖及其衍生物在组织工程中的应用

壳聚糖由于具有良好的生物相容性、生物可降解性以及具有可反应的活性基团,因而在生物、医学等领域具有广泛的研究和应用。随着组织工程学研究的深入,壳聚糖及其衍生物材料作为天然高分子组织工程支架越来越受到重视,综述了近年来国内外壳聚糖及其衍生物在组织工程上的研究和应用情况,包括壳聚糖及其衍生物支架材料的制备方法、壳聚糖的改性以及壳聚糖复合材料等。     

交联羧甲基壳聚糖对铅离子的吸附研究

以壳聚糖为原料,先在氨基上引入羧甲基制备出N-羧甲基壳聚糖,再和环氧氯丙烷发生交联反应,合成出新型交联羧甲基壳聚糖,FTIR表征其结构。研究了交联羧甲基壳聚糖对Pb2+的吸附性能,探讨了交联剂用量、铅离子溶液的pH值、温度、吸附时间等因素对其吸附性能的影响,并考察了交联羧甲基壳聚糖对铅离子吸附动力学和热力学实验。实验结果表明,交联羧甲基壳聚糖对铅离子的吸附量优于壳聚糖,平衡吸附量可达297.6 mg/g。交联羧甲基壳聚糖对铅离子的吸附符合准二级动力学模型和Langmuier等温吸附,吸附主要依靠结构中的羧基和氨基基团。     

化学修饰壳聚糖的血液相容性

壳聚糖是无毒、可生物降解、具有生物相容性的天然碱性多糖。本文综述了近年来提高壳聚糖的血液相容性的方法及以壳聚糖为原料制备肝素替代品的研究。壳聚糖分子上接枝血液相容性高分子、引入亲水基团或负电基团、酰化改性等均能提高壳聚糖的血液相容性;以壳聚糖为原料制备肝素的替代品可通过在壳聚糖分子上引入磺酸基,或将壳聚糖氧化成6-羧基壳聚糖后再引入磺酸基来实现。对今后如何进一步提高壳聚糖衍生物的血液相容性研究前景进行了展望。     

邻苯二酚基团改性壳聚糖组织胶黏剂的制备和表征

分别通过1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐/N-羟基丁二酰亚胺(EDC/NHS)偶联反应和席夫碱-还原反应,并以高碘酸钠(NaIO4)为氧化交联剂,得到2种邻苯二酚接枝改性的壳聚糖基水凝胶组织胶黏剂(CHI-C和CCS)。利用红外光谱(FT-IR)、核磁共振氢谱(~1 H-NMR)、抗菌实验和黏结强度测试对壳聚糖衍生物的结构和性能进行了表征。探讨了胶黏剂配比对其成胶性能和黏结强度的影响。结果表明:此种胶黏剂的成胶时间短,邻苯二酚基团和NaIO4含量的增加均有利于凝胶形成,CHI-C的最大黏结强度为40.42kPa,CCS的最大黏结强度为15.68kPa。两种壳聚糖衍生物均具有优良的抑菌性能。     

壳聚糖含磷衍生物的合成、表征及其应用研究*

壳聚糖是一种可再生的天然碱性多糖,具有多种优良的特性。但是,由于壳聚糖本身的溶解性很差,只能溶解在一些稀酸中,这就在一定程度上限制了其进一步的研究与应用。因此,通过修饰改性提高其已有功能、赋予新的功能是壳聚糖重要的研究领域。其中,通过磷酸化或磷酰化改性是壳聚糖改性研究的方向之一。本文综述了在壳聚糖链上引入含磷/膦基团合成壳聚糖含磷衍生物的研究进展;介绍并讨论了壳聚糖含磷衍生物的合成及纯化方法;对壳聚糖含磷衍生物结构、性能及表面形貌的表征进行了详细的阐述;对壳聚糖含磷衍生物的应用进行了总结,并展望了壳聚糖含磷衍生物未来的应用前景。     

羟烷基壳聚糖制备及应用研究进展

壳聚糖是由甲壳素通过脱乙酰作用得到的一种天然高分子多糖,具有良好的生物相容性、抗菌性、无毒和可生物降解等优点,但壳聚糖水溶性差限制了其在很多方面的应用。为克服壳聚糖在水溶性上的不足,利用壳聚糖结构中氨基和羟基上的活泼氢进行化学改性以引进羟烷基等亲水性基团成为重要手段。本文主要对壳聚糖羟烷基化改性的方法及羟烷基壳聚糖在医药、水处理和组织工程材料等领域的研究和应用现状进行介绍,并对羟烷基壳聚糖未来的发展趋势进行了展望。     

庚醛改性壳聚糖的制备及其对酚类化合物的吸附性能

在相转移催化剂存在下由庚醛与壳聚糖反应生成Schiff's碱,再用NaBH4 还原制备了N-烷基化壳聚糖衍生物,改性壳聚糖(CTS)产物的结构用FTIR和XRD进行了表征,研究了它对2,4-二氯酚的吸附性能. 考察了吸附时间、溶液pH值、2,4-二氯酚浓度和改性剂用量等因素对吸附的影响. 结果表明,改性CTS具有较好的抗酸碱性能;溶液的pH值对吸附的影响较大,在pH=6.0,吸附2 h时对2,4-二氯酚的吸附量最大,酚浓度对吸附的影响符合Freundlich吸附等温方程;改性壳聚糖对2,4-二氯酚的吸附性能明显优于未改性的CTS,对质量浓度为0.6 g/L的2,4-二氯酚溶液的吸附量分别为70.0和7.7 mg/g.     

N-羧丙酰壳聚糖钠增强改性壳聚糖棒材

采用原位沉析法制备N-羧丙酰壳聚糖钠增强改性的三维壳聚糖复合棒材, 并用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)、热重(TG)分析、扫描电镜(SEM)以及力学性能测试等方法研究复合棒材结构与性能之间的关系. FTIR分析表明, 壳聚糖分子中的氨基官能团和乙酰氨基官能团均与N-羧丙酰壳聚糖钠分子中的羧酸盐官能团发生强烈的静电相互作用. 加入N-羧丙酰壳聚糖钠后: 两种分子间产生强烈的静电相互作用, 限制了大分子链的运动, 使得大分子链趋于刚性, 同时复合棒材的层状叠加结构变得更加紧密, 提高了复合棒材的热稳定性与力学性能; 大分子链的刚性增强, 限制了分子链排入晶格, 从而降低了壳聚糖的结晶度. 当复合棒材中含有15% (w)的N-羧丙酰壳聚糖钠时, 其弯曲强度和弯曲模量可达156.0 MPa、5.3 GPa, 与纯壳聚糖棒材相比, 分别提高了68.8%、29.3%.因此, N-羧丙酰壳聚糖钠可有效地增强改性三维壳聚糖棒材, 该三维复合物棒材有望用作骨折内固定材料.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.     

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%).