两亲性羧甲基壳聚糖衍生物的表面活性研究

将羧甲基壳聚糖与烷基缩水甘油醚在碱性条件下反应,合成了一系列新型的两亲性化合物(2-羟基-3-烷氧基)丙基-羧甲基壳聚糖,对其表面性质的研究结果表明,对同一衍生物,在所研究范围内,取代度越高,降低表面张力的能力及效率越高;对同一取代度的不同衍生物,疏水链越长,降低表面张力的能力越强;对链较短和取代度较大的衍生物,如(2-羟基-3-丁氧基)丙基羧甲基壳聚糖(HBP-CMCHS),在外加电解质存在时溶液的表面张力曲线出现2个转折点,表明可能有分子内胶束形成;而对链较长的衍生物,如(2-羟基-3-十二烷氧基)丙基羧甲基壳聚糖(HDP-CMCHS),则无明显的临界胶束浓度,有外加电解质时表面张力曲线也未出现2个转折点.     

(2-羟基-3-丁氧基)丙基-羧甲基壳聚糖的合成及表面性质

(2-羟基-3-丁氧基)丙基-羧甲基壳聚糖的合成及表面性质;壳聚糖衍生物; (羟基丁氧基)丙基-羧甲基壳聚糖;表面活性;表面压     

N,O-羧甲基化羟丙基壳聚糖的制备及结构表征

用NaOH作为催化剂, 在异丙醇悬浮体系中环氧丙烷(PO)与壳聚糖(CS)在60 ℃下反应8 h, 制备取代度超过0.8的羟丙基壳聚糖(HPCS). HPCS在水溶液中与氯乙酸反应, 制备了一种结构新颖的两性聚合物N,O-羧甲基化羟丙基壳聚糖(HPCMS), 羧甲基取代度可控制在0.42～1.38之间. 采用NMR和FTIR对产物结构进行表征. 结果表明, 在壳聚糖的羟丙基化改性过程中, C6位羟基首先与环氧丙烷反应, 生成HPCS; 在与氯乙酸反应过程中, HPCS上的羟基和氨基同时与氯乙酸发生取代反应.     

新型含胍基和季铵基团壳聚糖衍生物的合成

N,N-二甲基-1,3-丙二胺与单氰胺经亲核加成反应制得中间体N,N-二甲基-N′-胍基-1,3-丙二胺（2）; 以壳聚糖为起始原料,依次与氯乙酸、环氧氯丙烷经取代反应制得N-（1-羟基-3-氯丙基）-羧甲基壳聚糖（4）; 4与2经季铵化反应合成了一系列含有胍基和季胺基团的羧甲基壳聚糖衍生物（5）,其结构经¹H NMR, IR和元素分析表征。研究了反应配比［γ=m（2）∶m（4）］和反应时间对5取代度的影响,结果表明,当γ为3∶1,反应时间为10 h时,取代度最高(73%)。     

羧甲基壳聚糖-PEG双缩水甘油醚凝胶微球的制备与表征

羧甲基壳聚糖是壳聚糖-NH2或-OH被羧甲基取代后的一类衍生物,具有优良的生物相容性和生物可降解性,同时具有抗菌作用。作为生物医用材料应用的潜力巨大。制备羧甲基壳聚糖生物膜或凝胶时多以戊二醛为交联剂[1],但戊二醛有一定的细胞毒性[2-3],用作医用材料的制备时有一定的局限     

新型两亲性壳聚糖衍生物的合成、表征及对难溶性药物的增溶性

以天然可生物降解的壳聚糖为原料, 通过在壳聚糖6位羟基上引入羧甲基, 在2位氨基上引入疏水烷基链, 制得N-辛基-O,N-羧甲基壳聚糖(OCC)两亲性衍生物, 分别用FTIR、1H NMR和元素分析等技术对其结构进行表征, 用广角X射线衍射(WAXD)和差示扫描量热法(DSC)对其物理性质进行分析, 并考察其在各种溶剂中的溶解性能及其对难溶性药物的增溶能力. 所制备的OCC羧甲基取代度为115.9%, 取代主要发生在6位羟基上; 辛基取代度58.0%, 取代主要发生在2位氨基上; 与壳聚糖相比, OCC分子间/内氢键作用减弱; OCC在常用的有机溶剂中不溶, 但在水中溶解度增加, 能够形成具有淡蓝色乳光的纳米胶体溶液, 对难溶性抗肿瘤药物紫杉醇具有优越的增溶能力, 使紫杉醇在水中的溶解度提高近500倍, 载药量为34.6%(质量分数), 包封率为89.9%. OCC是潜在的优良的难溶性药物增溶载体材料.     

羧甲基壳聚糖与钙离子络合作用的研究

羧甲基壳聚糖(carboxymethyl chitosan,CMCS)是壳聚糖Chitosan经化学改性得到的水溶性衍生物,由于羧基的引入,络合金属离子的能力及反应速度大大提高[1-6],在医药、化工、环保等领域有着广泛的应用前景。本文研究了羧甲基壳聚糖与Ca2 络合的条件,着重探讨了Pb2 在不同条件下对络合反应的影响,以期扩大羧甲基壳聚糖的应用范围。1材料与方法1.1仪器与试剂羧甲基壳聚糖(自制),其它试剂均为国产优级纯。TAS-986G原子吸收分光光度计;SX5-12箱式电阻炉;GL-20B高速冷冻离心机;Ori-on818型pH测试计。1.2实验方法1.2.1羧甲基壳聚糖与Ca2 络合…     

三苯基锡壳聚糖羧酸酯的合成及其灭螺活性

以羧甲基壳聚糖为接枝骨架,三苯基氯化锡为接枝单体,在80%甲醇中,于20℃反应2 d,合成了新化合物--三苯基锡壳聚糖羧酸酯(2),其结构经IR,TG,DTA和XRD表征.用火焰原子吸收光谱法测定了2中Na 和sn4 的含量,得到2的取代度为0.47.杀钉螺活性实验结果表明,在c(2)＞10 mg·L-1时,能抑制钉螺上爬;c(2)＞1 mg·L-1,室温浸泡3 d后,钉螺的死亡率达100%.2具有高效的杀钉螺活性.     

亲核取代法制备壳聚糖6-OH固载环糊精衍生物

通过苯甲醛对壳聚糖2-NH2希夫碱化保护后,将壳聚糖C6位—OH与对甲苯磺酰氯反应形成对甲苯磺酰酯;然后用β-环糊精(-βCD)的单—NH2取代衍生物与之发生亲核取代反应,将环糊精固载到壳聚糖分子链上;最后,将得到的固载产物中的希夫碱脱保护后得到壳聚糖6-OH定位固载环糊精衍生物.采用FTIR,13C-NMR,元素分析,UV等表征手段对各步产物的结构进行了表征.紫外光谱法测定表明,-βCD在壳聚糖分子链C6位上的固载率达到了170.81μmol.g-1,远高于文献报道的其它方法制得的固载产物.采用XRD对各步产物的结晶性能进行了研究.     

羧甲基壳聚糖对铅离子的吸附性能研究

本文研究羧甲基壳聚糖对Pb^2 的吸附作用,探讨反应时间,离子强度,溶液的PH值、羧甲基取代度,温度等因素对吸附性能的影响,结果表明羧基是吸附Pb^2 的主要活性基团,羧甲基壳聚糖对Pb^2 的饱和吸附量为3．1083mmol/g,吸附Pb^2 的能力比壳聚糖,水溶性低聚壳聚糖强。     

[Co(2,3-tri)(amp)Cl]^2^+几何经式异构体取代与重排规律、构效关系的研究

对[Co(2,3-tri)(amp)Cl]^2^+四个几何经式异构体在不同条件下的取代及重排反应进行了详细的考察。因二元胺中吡啶环造成的空间拥塞,使cis异构体碱水解速度比trans异构体约快100倍,控制碱水解实验结果表明,每一异构体的水解产物均含四个经式异构体,且具有相同分布。实验过程中未观察到面式异构体。在二甲亚砜中加热的重排反应中,异构体m1表现出最高的反应性,cis异构体均首先转化为trans异构体m3,而后可观察到trans异构体m3与m4的平衡。利用时间分辨核磁共振仪测定了氘代水里各异构体中各活性氢的氘代化速度。反应活性最低的异构体m4具有氘代速度最快的活性氢,当这些活性氢完全氘代化时仍未见其水解或重排产物;而相同实验条件下异构体m1或m2中相应活性氢的氘代化速度则要缓慢得多,但同时可观察到水解和重排产物。这说明在碱催化水解过程中氘代速度快的活性氢与异构体的反应性并非正比关系,然而活性氢的氘代化是观察到异构体水解重排的必要条件。利用量子化学从头计算法在赝势基组RHF/LANL2DZ的水平上对该体系各异构体进行了结构优化计算,与对应异构体的晶体结构参数比较,一般相对误差不超过3%,从能量角度来看,cis异构体比trans异构体高出约4kJ/mol,而面式异构体则至少比经式异构体高约17kJ/mol;考虑溶剂化影响,一般约低5kJ/mol。考察结构参数结果显示,结构变形性参数能较好地解释异构体反应活性。     

C59H3N异构体的结构与稳定性的理论研究

分别用MNDO,AM1和PM3三种半经验方法对C59HN所有1-2,1-4和1-6氢加成物C59H3N的异构体进行几何构型全优化,结合频率分析及HF/6-31G单点能计算,确定了各异构体的基态结构及其相对稳定性,计算结果表明,C59HN氢加成物的立体选择性规律与C60和C60H2的不同,最稳定异构体不是1-2加成物,而是1-4加成的6,18-或12,15-异构体,次稳定异构体为1-2加成物,三种半经验方法计算得到的两者能量差为13～15kJ/mol,N原子取代碳笼骨架C原子后,改变了碳笼氢加成物的立体选择性规律.     

Stereochemistry of the Heterocyclic Alcohols Containing Piperidine Unit

The stereochemistry of the heterocyclic alcohols (R₁-OH~R₄-OH,see Fig.1) containing piperidine unit has been studied on the basis of the calculations of molecular mechanics and quantum chemistry. The calculations of alcohols (R₁-OH~R₄-OH) and their carboxylate derivatives were carried out, and the results of these calculations were listed in Tab.1 and Tab.2. It was showed that there existed the non-classical orbital super-conjugated interactions between the nitrogen atom and oxygen atom which caused the conformations to be more stable when the hydroxylic group lay at axial than at equatorial with respect to the piperidine ring in compounds (R₁-OH) and (R₃-OH). If the axial hydrogen atoms at C₂ and C₆ positions in the piperidine ring were substituted, or the molecular existed in the polar solutions, this non-classical orbital super-conjugated interactions would be much weak even diminished. In this case,the conformations were more stable when the hydroxylic group at equatorial than at axial in these compounds. These consistented with the experimental results.     

4种C_(12)H_(12)多面体烷振动频率及生成焓的DFT研究

采用密度泛函方法,在B3LYP/D95*水平上对4种C12H12多面体分子的构型进行了全优化,计算了其振动频率及红外吸收强度,并模拟了它们的红外光谱图。采用统计热力学方法,在200～600K的温度范围内,分别计算了立方烷生成这4种C12H12多面体分子的热力学函数。由计算得到的自由能得知,这些分子都比立方烷稳定,因此从热力学角度来说,既然立方烷能够合成,这4种C12H12多面体分子也应该能够合成出来。根据计算得到的热力学函数及立方烷的生成焓,求出了这4种C12H12多面体分子的生成焓。     

A disilapentalene and a stable diradical from the reaction of a dilithiosilole with a dichlorocyclopropene

The reaction of 1,1-dilithio-2,3,4,5-tetraphenylsilole (1) with 1,1-dichloro-2,3-diphenylcyclopropene (2) leads to the novel 1,4-disila-1,4-dihydropentalene (4), as well as an exceptionally stable diradical for which the structure 3 is suggested. The diradical is unreactive toward water, methanol, and chloroform; upon heating it transforms into 4. Structure 3 for the paramagnetic species is proposed on the basis of EPR data and theoretical calculations. The trans-trans isomer of diradical 3 was calculated to be more stable than its cis-cis isomer. The strong and stable EPR signal in the reaction mixture is probably due to the trans-trans isomer of diradical 3 in the triplet state. A reaction scheme describing the formation of 3 and 4 is presented.     

Gas-phase Watson-Crick and Hoogsteen isomers of the nucleobase mimic 9-methyladenine x 2-pyridone.

2-Pyridone (pyridin-2-one) is a mimic of the uracil and thymine nucleobases, with only one N--H and C==O group. It provides a single H-bonding site, compared to three for the canonical pyrimidine nucleobases. Employing the supersonically cooled 9-methyladenine2-pyridone (9MAd x 2PY) complex, which is the simplest base pair to mimic adenine-uracil or adenine-thymine, we show that its gas-phase UV spectrum consists of contributions from two isomers. Based on the H-bonding sites of 9-methyladenine, these are the Watson-Crick and Hoogsteen forms. Combining two-color two-photon ionisation (2C-R2PI), UV-UV depletion and laser-induced fluorescence spectroscopies allows separation of the two band systems, revealing characteristic intermolecular in-plane vibrations of the two isomers. The calculated S(0) and S(1) intermolecular frequencies are in good agreement with the experimental ones. Ab initio calculations predict the Watson-Crick isomer to be slightly more stable (D(0)=-16.0 kcal mol(-1)) than the Hoogsteen isomer (D(0)=-15.0 kcal mol(-1)). The calculated free energies Delta(f)G(0) of the Watson-Crick and Hoogsteen isomers agree qualitatively with the experimental isomer concentration ratio of 3:1.     

Infrared spectra of the protonated neurotransmitter histamine: competition between imidazolium and ammonium isomers in the gas phase

The infrared (IR) spectrum of protonated histamine (histamineH(+)) was recorded in the 575-1900 cm(-1) fingerprint range by means of IR multiple photon dissociation (IRMPD) spectroscopy. The IRMPD spectrum of mass-selected histamineH(+) ions was obtained in a Fourier transform ion cyclotron resonance mass spectrometer coupled to an electrospray ionization source and an IR free electron laser. A variety of isomers were identified and characterized by quantum chemical calculations at the B3LYP and MP2 levels of theory using the cc-pVDZ basis set. The low-energy isomers are derived from various favourable protonation sites--all of which are N atoms--and different orientations of the ethylamine side chain with respect to the heterocyclic imidazole ring. The measured IRMPD spectrum was monitored in the NH(3) loss channel and exhibits 14 bands in the investigated spectral range, which were assigned to vibrational transitions of the most stable isomer, denoted A. This imidazolium-type isomer A with protonation at the imidazole ring and gauche conformation of the ethylamine side chain is significantly stabilized by an intramolecular ionic Nπ-H(+)···Nα hydrogen bond to the ethylamino group. The slightly less stable ammonium-type isomer B with protonation at the ethylamino group is only a few kJ mol(-1) higher in energy and may also provide a minor contribution to the observed IRMPD spectrum. Isomer B is derived from A by simple proton transfer from imidazole to the ethylamino group along the intramolecular Nπ-H(+)···Nα hydrogen bond via a low barrier, which is calculated to be of the order of 5-15 kJ mol(-1). Significantly, the most stable structure of isolated histamineH(+) differs from that in the condensed phase by both the protonation site and the conformation of the side chain, emphasizing the important effects of solvation on the structure and function of this neurotransmitter. The effects of protonation on the geometric and electronic structure of histamine are evaluated by comparing the calculated properties of isomer A with those of the most stable structure of neutral histamine A(n).     

HBO2异构体的结构和相对稳定性

用ab initio方法在MP2/6 311＋＋G(d,p)水平下优化得到了HBO2体系的若干异构体和过渡态，并在QCISD(t)/6 311＋＋G(3df,2p)//MP2/6 311＋＋G(d,p)水平下进行了单点能量校正.对计算结果的分析表明，无论是在热力学还是在动力学上，具有链状结构的HOBO异构体(E1)是势能面上最稳定的结构，并对E1的电子结构进行了分析；另一具有C2v对称性的HBO(O)结构的异构体(E2)的能量比E1高381.72 kJ•mol－1，由于E2处于一个较深的势垒中，因此是比较稳定的，可以推断，在适合的实验中应该可以观察到异构体E2.     

Properties of stable organic bond-stretched non-Lewis molecules

The conditions required for the existence of a stable bond-stretched singlet isomer of hetero derivatives of bicyclo[2.1.0]pentane (which is a cyclopentane-1,3-diyl derivative) are discussed. Such species are non-Lewis systems with a ruptured C-C bond (formally diradicals), in which two electrons occupy the nonbonding orbital. A high-level calculation shows that in contrast with the carbon substituted compounds, in which the open form is a transition state between two classical-bonded closed bicyclic forms, in the heterosubstituted molecules, the open form is calculated to be a stable minimum. The ionization potentials of the open forms are considerably lower than those of their bicyclic isomers and also of regular organic radicals/diradicals. Nitrogen atoms are found to be more effective than oxygen or sulfur in stabilizing the open isomer. In this case, the open isomer is calculated to be a little more stable than the bicyclic compound, and a barrier of approximately 40 kcal/mol is computed for the ring closing reaction. Thus, the open isomer is both thermodynamically and kinetically stable. This result rationalizes some experimental observations that indicated the existence of non-Lewis singlet species.