硫酸交联壳聚糖干膜的13C CP MAS NMR研究

以不同浓度硫酸交联的壳聚糖干膜为研究对象,在国内首次采用¹³C CP MAS NMR技术从分子水平上对壳聚糖膜的结构进行研究,结果表明干膜壳聚糖分子的构象能直观地反映出膜的交联状况,交联状况与膜的分离性能密切相关,但仅对干膜的考察还不够全面.     

β-环糊精与几种菁染料包合物的动态结构及包合平衡的NMR研究

用核磁共振方法研究了β-CD与三种菁染料3,3′-二（3-磺丙基）噻菁三乙胺盐(d-yeA)、3,3′-二（3-磺丙基）-5-氯-噻菁三乙胺盐(dyeB)和3,3′-二（3-磺丙基） -5,5′-二苯基-9-乙基恶碳菁(dyeC)在溶液中的包合现象和包合物的动态结构,实验发现β-CD环糊精疏水腔中的H-3和H-5以及三种菁染料的芳环上质子的化学位移由于形成包合物而发生明显变化, 而且峰的位置随包合程度的不同而不同. 实验中发现包合物的荧光强度随β-CD浓度增加而减弱,相应计算表明β-CD与三种菁染料形成了1∶1的包合物.本文研究了三种包合物中主体部分OH-3和OH-6的化学位移随温度变化的情况,获得了包合物中氢键强弱的信息, 通过NMR化学位移滴定法计算得到了三种包合物在水溶液中的稳定常数, 在上述工作的基础上,本文提出了三种包合物的结构模型,描述了客体进入主体腔中的动态过程.     

CO32-掺杂纳米羟基磷灰石晶体的合成与表征

CO32-掺杂是提高纳米羟基磷灰石(n-HA)生物活性的有效方法之一。以Ca(NO3)2·4H2O和Na3PO4·12H2O为主要原料,Na2CO3作为CO2-3来源,合成纳米碳羟基磷灰石(n-CHA)晶体。采用TEM,XRD,FTIR,RS对合成晶体形貌和结构进行表征。结果表明:合成的n-HA晶体长度约为60~80nm,宽度在20~30nm之间,形状为针状,具有良好的结晶度,与自然骨磷灰石形貌相似;n-CHA晶体随CO2-3掺入量的增加,结晶度降低;合成的n-CHA晶体的晶胞参数a值随着CO2-3加入量的增大不断收缩,但c值增大,参数比c/a值增大,符合B型取代(取代PO3-4)的晶胞参数变化规律。红外谱图中,872cm-1附近出现AB混合型取代(同时取代OH-,PO3-4)的CO2-3面外弯曲振动特征红外峰,同时CO2-3的不对称伸缩振动红外峰在1 454和1 420cm-1附近出现分裂峰,1 540cm-1附近出现弱CO2-3峰;1 122cm-1附近出现CO2-3对称伸缩振动拉曼峰,1 071cm-1附近出现CO2-3的B型替代特征拉曼峰,通过计算PO3-4,CO2-3,OH-拉曼峰的积分面积比PO3-4/CO2-3,OH-/CO23,PO3-4/OH-,表明CO2-3在替换时,先以B型为主,随着CO2-3掺入量的增加,发生A型替代(取代OH-)。实验结果表明,合成的磷灰石晶体为B型取代(取代PO3-4)为主的AB混合型取代的n-CHA。与人骨磷灰石晶体在形态、尺寸、晶体结构和生长方式上具有相似性,可称为类骨磷灰石。     

皂苷Tb2个糖基化产物的NMR研究

利用¹H NMR、¹³C NMR、COSY、HSQC和HMBC等多种核磁共振技术,结合MS技术,确认了皂苷Tb的2个糖基化产物的结构,即偏诺皂苷元-3-O-α-D-葡萄糖-(1→3)[α-L-鼠李糖(1→2)]-β-D-葡萄糖苷（1）和偏诺皂苷元-3-O-α-D-葡萄糖-(1→4)-α-D-葡萄糖-(1→3)[α-L-鼠李糖-(1→2)]-β-D-葡萄糖苷（2）. 化合物1和2为新化合物,对其¹H NMR和¹³C NMR信号分别进行了全归属和详细分析.     

3-氧化木糖与硝基甲烷加合产物的结构确定

以3-氧化木糖为原料,通过Henry反应与硝基甲烷加成,得到两种硝基糖化合物1,2-O-异丙叉基-3-C-硝甲基-5-对甲苯磺酰基-α-D-呋喃核糖(1)和1,2-O-异丙叉基-3-C-硝甲基-4-甲烯基-α-D-呋喃核糖(2),其中化合物2为新型的硝基糖化合物.通过应用1D NMR和2D NMR测试了化合物2的1H NMR、13C NMR、1H-1H COSY、gHSQC和gHMBC,对化合物2的1H和13C进行了全归属.     

胭脂树低聚糖的结构分析

从胭脂树（Bixo orellana）种子中分离得到了一种胭脂树低聚糖：α-D-半乳糖-(1→3)-α-D-半乳糖-(1→6) -α-D-葡萄糖-(1→2)-β-D-果糖（BO-1）. 通过1D NMR和2D NMR实验技术对其¹H NMR和¹³C NMR谱信号进行了全归属.      

猪去氧胆酸衍生物的NMR研究

对6α-羟基-3α-苯甲酰氧基-5β-胆烷酸甲酯（化合物1）及3α-羟基-6α-苯甲酰氧基-5β-胆烷酸甲酯（化合物[STHZ]2[STBZ]）进行了¹H,¹³C NMR检测,通过DEPT及DQF-COSY,¹³C-¹H COSY, COLOC等NMR技术对其¹H和¹³C NMR数据进行了全归属和详细的解析,并指出了其NMR数据特征.     

β-环糊精与几种菁染料包合物的动态结构及包合平衡的NMR研究

用核磁共振方法研究了β-CD与三种菁染料3,3′-二（3-磺丙基）噻菁三乙胺盐(dyeA)、3,3′-二（3-磺丙基）-5-氯-噻菁三乙胺盐(dyeB)和3,3′-二（3-磺丙基）-5,5′-二苯基-9-乙基恶碳菁(dyeC)在溶液中的包合现象和包合物的动态结构,实验发现β-CD环糊精疏水腔中的H-3和H-5以及三种菁染料的芳环上质子的化学位移由于形成包合物而发生明显变化,而且峰的位置随包合程度的不同而不同. 实验中发现包合物的荧光强度随β-CD浓度增加而减弱,相应计算表明β-CD与三种菁染料形成了1∶1的包合物.本文研究了三种包合物中主体部分OH-3和OH-6的化学位移随温度变化的情况,获得了包合物中氢键强弱的信息,通过NMR化学位移滴定法计算得到了三种包合物在水溶液中的稳定常数,在上述工作的基础上,本文提出了三种包合物的结构模型,描述了客体进入主体腔中的动态过程.     

EDTA衍生物冠醚与4′-丹磺酰氨基苯并冠醚的~1H、~(13)C NMR谱线归属

本文测定了N(,N′)-(二)对甲苯磺酰基大环醚双内酯(附图11～6),N,N′-二羧甲基大环醚双内酯和大环胺双内酰胺(图18～2),4′-丹磺酰氨基苯并冠醚(图113～16)等十八个新冠醚的~1H,~(13)C NMR谱并进行了归属。作者发现,随着冠醚环的增大,冠1～6的次甲基b和冠8～11的次甲基a、b、c的~1H化学位移向低场移动,当冠环增大至21～24员时,这种偏移趋于极限。溶剂对8～11化合物的~1H NMR影响表明,次甲基a、b、c的~1H位移随溶剂的极性增大而增大,次序为:CD_3COOD>PY-d_5≥D_2O>>CD_3OD>CD_3CD_2OD>DMF-d_6>DMSO-d_6。     

Ga(OTf)3催化合成苯并二氮杂卓及其结构解析

以邻苯二胺和丙炔酸酯为原料,Ga(OTf)3催化一锅法合成了一类新型的1,5-苯并二氮杂卓衍生物,超声波辅助加快了反应的进行,该反应条件温和,反应时间短. 利用¹H NMR、¹³C NMR 确定了该产物的结构,并通过DEPT、¹H-¹H COSY、HMQC、HMBC等2D NMR谱,对化合物的¹H NMR和¹³C NMR数据进行了详细的归属,讨论了化合物的质谱裂解规律,进一步确证了该化合物的结构.     

Study on factors governing the conductivity performance of acylated chitosan-NaI electrolyte system

Hexanoyl chitosan and lauroyl chitosan were prepared by acyl modification of chitosan. Films of hexanoyl chitosan- and lauroyl chitosan-based polymer electrolytes incorporated with different weight concentrations of sodium iodide (NaI) were prepared using the solution casting technique. FTIR and differential scanning calorimetry (DSC) results suggested that NaI interacted with both hexanoyl chitosan and lauroyl chitosan. Maximum conductivities of 1.3 × 10^?6 and 1.1 × 10^?8 S cm^?1 are achieved for hexanoyl chitosan and lauroyl chitosan, respectively. Higher conductivity in hexanoyl chitosan is attributed to higher ion mobility as supported by DSC results. The dielectric constants of neat hexanoyl chitosan and lauroyl chitosan are 2.7 and 1.9, respectively, estimated from impedance spectroscopy. Higher dielectric constant of hexanoyl chitosan resulted in greater NaI dissociation and hence higher conductivity. Deconvolution of O═C-NHR and OCOR bands of polymer has been carried out to estimate the amount of dissociated Na⁺ ions from NaI. The findings were in good agreement with conductivity results. In order to assess quantitatively, the conductivity, parameter number, n, and mobility, μ, of ions were calculated using impedance spectroscopy. XRD results showed the influence of NaI on the crystalline content of the electrolyte system. Sample with lower crystalline content exhibited higher conductivity.     

Blends of hexanoyl chitosan/epoxidized natural rubber doped with EMImTFSI

Hexanoyl chitosan soluble in THF is prepared by acyl modification of chitosan. Epoxidation natural rubber (ENR25) (25 mol%) is chosen to blend with hexanoyl chitosan. Films of hexanoyl chitosan/ENR25 blends containing lithium bis(trifluoromethanesulfonyl)imide (LiN(CF₃SO₂)₂) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) are prepared by solution casting technique. FTIR results suggested that LiN(CF₃SO₂)₂ salt interacted with hexanoyl chitosan, ENR25, and EMImTFSI. EMImTFSI interacted with hexanoyl chitosan and ENR25 to form EMIm⁺-hexanoyl chitosan and EMIm⁺-ENR25 complexes, respectively. The effect of EMImTFSI on the morphology and thermal properties of the blends is investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC), respectively. The ionic conductivity of the electrolytes is measured by electrochemical impedance spectroscopy (EIS). Upon addition of 12 wt% EMImTFSI, a maximum conductivity of 1.3 × 10^?6 S cm^?1 is achieved. Methods based on impedance spectroscopy and FTIR are employed to study the transport properties of the prepared polymer electrolytes. The ac conductivity was found to obey universal law, σ(ω)?=?σ _dc ?+?Aω ^S . The temperature dependence of exponent s is interpreted by the small polaron hopping (SPH) model.     

Hydroxyapatite Nano Sol Prepared via A Mechanochemical Route

Well-dispersed sol with crystalline hydroxyapatite (HAp) was obtained directly by milling a mixture comprising Ca(OH)₂, an aqueous solution of H₃PO₄ and a dispersant, an ammonium salt of polyacrylic acid. The average crystallite size of HAp was below 20 nm. Ca/P molar ratio of the product was 1.51 ± 0.04, i.e. Ca deficient from stoichiometric HAp. Minimum apparent viscosity was attained at a dispersant concentration 0.92wt% of sol. An as-milled sol was diluted by a factor 10–2.61 solid wt% to give a Newtonian fluid of 2 mPa s. From the diluted sol, we obtained a few m thick dense film of HAp by dip coating on the slide glass precoated by chitosan.     

On the possibility of regulating the rate of enzymatic destruction of chitosan in an acetic acid solution

The enzymatic destruction of chitosan in an acetic acid solution in the presence of sodium chloride and sulfate was considered. It was shown that the addition of these low-molecular electrolytes is accompanied by a tightening of the macromolecular coil, as indicated by a decrease in the α constant in the Mark–Kuhn–Houwink equation and the intrinsic viscosity of chitosan. As a consequence, the chitosan units become less accessible for interaction with the enzyme, and the kinetic parameters of the process (Michaelis constant K _M and the maximum rate of enzymatic destruction V _max) change accordingly. This suggests that the resistance of this polymer to the enzyme action can be enhanced by introducing low-molecular electrolyte salts in the solution or film coating to suppress the polyelectrolyte swelling of chitosan.     

Applications of polymeric micelles with tumor targeted in chemotherapy

The chitosan-coated magnetic nanoparticles (CS MNPs) were in situ synthesized by cross-linking method. In this method; during the adsorption of cationic chitosan molecules onto the surface of anionic magnetic nanoparticles (MNPs) with electrostatic interactions, tripolyphosphate (TPP) is added for ionic cross-linking of the chitosan molecules with each other. The characterization of synthesized nanoparticles was performed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS/ESCA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), thermal gravimetric analysis (TGA), and vibrating sample magnetometry (VSM) analyses. The XRD and XPS analyses proved that the synthesized iron oxide was magnetite (Fe₃O₄). The layer of chitosan on the magnetite surface was confirmed by FTIR. TEM results demonstrated a spherical morphology. In the synthesis, at higher NH₄OH concentrations, smaller sized nanoparticles were obtained. The average diameters were generally between 2 and 8?nm for CS MNPs in TEM and between 58 and 103?nm in DLS. The average diameters of bare MNPs were found as around 18?nm both in TEM and DLS. TGA results indicated that the chitosan content of CS MNPs were between 15 and 23?% by weight. Bare and CS MNPs were superparamagnetic. These nanoparticles were found non-cytotoxic on cancer cell lines (SiHa, HeLa). The synthesized MNPs have many potential applications in biomedicine including targeted drug delivery, magnetic resonance imaging?(MRI), and magnetic hyperthermia.     

低聚壳聚糖稀土铈(Ⅲ)配合物的合成与光谱表征

以低聚壳聚糖(L-CTS)为配位体,稀土铈(Ⅲ)为配位离子,在pH值1～2的酸性条件下制备了低聚壳聚糖稀土铈(Ⅲ)配合物(L-CTS-Ce),用紫外光谱、荧光光谱、红外光谱、核磁共振谱等手段对其结构进行了表征,并对配位机理进行了初步探讨。 结果表明,L-CTS与Ce(Ⅲ)发生配位作用的基团主要是羟基而不是氨基。     

质子化改性壳聚糖吸附硫酸根行为及其光谱分析

壳聚糖(CTS)具有活性基团氨基和羟基,可用作吸附剂。在酸性介质中其氨基容易质子化形成氨基正离子,具有吸附阴离子的能力,同时也导致吸附剂的溶解流失;进行交联处理可提高吸附剂的酸稳定性,但也导致吸附性能的下降。因此可进行氨基保护后进行交联以改善其酸溶液稳定性,再脱去氨基保护剂进行质子化处理以获得较好的对阴离子的吸附性能。以甲醛为氨基保护剂,戊二醛为交联剂,通过反相悬浮法制得交联壳聚糖(CCTS),对其进行质子化制得质子化改性壳聚糖吸附剂(P-CCTS),并首次将该吸附剂用于处理水溶液中的硫酸根离子。通过静态吸附实验,考察了质子化改性壳聚糖对硫酸根的吸附性能;利用X射线能谱元素分析(EDS)和红外光谱分析(FTIR)对该吸附剂的制备以及对硫酸根离子的吸附过程进行了表征,探索了交联反应和吸附反应的发生机理。实验结果表明：质子化改性壳聚糖吸附剂与交联壳聚糖相比,其对硫酸根离子的吸附性能提高了约10倍;甲醛、戊二醛的醛基与壳聚糖的交联反应主要发生在的氨基(—NH₂)和部分一级羟基(C₆—OH)上;质子化过程中交联壳聚糖的氨基与质子化剂形成了氯化壳聚糖氨盐;对硫酸根离子的吸附则主要是质子化氨基上氯离子与硫酸根离子的交换作用。     

Design of peptide affinity ligands for S-protein: a comparison of combinatorial and de novo design strategies

Design of peptide affinity ligands against biological targets is important for a broad range of applications. Here, we report on de novo and combinatorial strategies for the design of high-affinity and high-specificity peptides against S-protein as a target. The peptide libraries employed in this study contain (1) consensus motif (CM) sequences identified from high-throughput phage combinatorial screening, (2) point mutations of CM sequences, and (3) de novo sequences rationally designed based on stereo-chemical information of the complex between S-protein and its natural ligand, S-peptide. In general, point mutations to CM allowed for modulating peptide affinity and specificity over a broad range. This is particularly useful in designing peptides with varying affinities and specificities for the target. De novo sequences, especially those based on the S-protein binding pocket, on average bound with higher affinities within a narrow range (10–100 nM) as compared to point mutations to CM (1 nM–2 $\mu $ M). As such, the approaches described here serve as a general guide for optimizing the design of peptide affinity ligands for a wide range of target proteins or applications.     

Center-of-mass problem in truncated configuration interaction and coupled-cluster calculations

The problem of center-of-mass (CM) contaminations in ab initio nuclear structure calculations using configuration interaction (CI) and coupled-cluster (CC) approaches is analyzed. A rigorous and quantitative scheme for diagnosing the CM contamination of intrinsic observables is proposed and applied to ground-state calculations for ⁴He and ¹⁶O. The CI and CC calculations for ¹⁶O based on model spaces defined via a truncation of the single-particle basis lead to sizable CM contaminations, while the importance-truncated no-core shell model based on the N_maxΩ space is virtually free of CM contaminations.     

阶梯式循环冲击下煤中氢键红外光谱变化规律

煤结构中存在的大量氢键对其化学结构和性质具有重要影响。为了研究煤在冲击破坏过程中氢键的变化。设计落锤循环冲击系统,实现对煤样的循环定量冲击。利用红外光谱仪进行光谱分析。研究得出东庞1/3焦煤主要的氢键类型是free OH groups, OH…π, OH…OH, cyclic OH tetramers和OH…N以及它们随冲击破坏的变化规律。在冲击力的作用下,煤体分子间氢键吸收强度变化非常明显,自由羟基也在冲击作用下发生机械力化学反应。对红外光谱进行高斯函数拟合分峰,发现各类氢键吸收强度随着冲能量的增加而减小,但其趋势在放缓。统计两者关系,得到各类氢键的光谱吸收强度与冲击能量的拟合方程,两者符合幂函数关系。对比拟合方程的幂指数,得出氢键在受冲击破坏时发生变化的敏感性顺序：free OH groups>cyclic OH tetramers>OH…N>OH…π>OH…OH。