聚氰丙基甲基硅氧烷—聚脲嵌段共聚物的NMR表征及研究

用高分辨NMR对聚甲基硅氧烷-聚脲嵌段共聚物以及聚氰丙基甲基硅氧烷-聚脲嵌段共聚物结构进行表征,对NH形成的各种氢键进行详细的研究,同时观察了氢键在力学性能中的作用,结果发现氢键强烈地影响着力学性能。用固体~1H宽线研究这类材料的相分离状况,并总结影响相分离的因素。保持硬段含量不变,增加软段分子量使相分离程度增加;保持软段分子量不变,增加硬段含量使相分离程度降低。软、硬段之间的相互作用(如氢键)使相分离程度降低。     

聚氰丙基甲基硅氧烷-聚脲嵌段共聚物的NMR表征及研究

用高分辨NMR对聚甲基硅氧烷-聚脲嵌段共聚物以及聚氰丙基甲基硅氧烷-聚脲嵌段共聚物结构进行表征,对NH形成的各种氢键进行详细的研究,同时观察了氢键在力学性能中的作用,结果发现氢键强烈地影响着力学性能。用固体¹H宽线研究这类材料的相分离状况,并总结影响相分离的因素。保持硬段含量不变,增加软段分子量使相分离程度增加;保持软段分子量不变,增加硬段含量使相分离程度降低。软、硬段之间的相互作用(如氢键)使相分离程度降低。     

伯胺萃取Cr(Ⅵ)的光谱学研究

利用等离子体发射光谱(ICP-AES),激光拉曼光谱,傅里叶变换红外光谱(FTIR),核磁共振(1H NMR)分析技术对伯胺在近中性条件下从水溶液中萃取Cr(Ⅵ)的过程进行了研究。ICP-AES对萃取前后水相Cr(Ⅵ)浓度测试结果显示,在近中性条件下,伯胺仍然能够萃取Cr(Ⅵ)。激光拉曼光谱显示,未经酸化的伯胺从近中性水溶液中萃取Cr(Ⅵ)后在890 cm-1处出现新峰。红外光谱显示在近中性条件下直接使用伯胺萃取Cr(Ⅵ)与经酸化处理后按离子交换历程萃取的萃取机理不同,Cr(Ⅵ)进入有机相后在885 cm-1处产生与拉曼光谱对应的新峰。1H核磁共振波谱显示,—NH₂上的质子峰向低场移动,伯胺在萃取过程中通过氢键与Cr(Ⅵ)结合。综合以上不同分析手段得到的结果可以推断,伯胺在近中性的水溶液中是以溶剂化萃取历程通过氢键结合方式萃取Cr(Ⅵ)。     

Study on spectrum of solvent extraction of chromium( VI) by primary amine

The Cr(VI) solvent extraction in near neutral aqueous solution by primary amine was experimentally studied by the inductively couple plasma-atomic emission spectrometry (ICP-AES), laser Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). The ICP-AES analysis of the aqueous phase before and after solvent extraction showed that primary amine could extract Cr(VI) from nearly neutral solution. Laser Raman spectroscopy of loaded organic phase showed that a new peak appeared at 890 cm(-1) after Cr(VI) was extracted by primary amine. FTIR showed the process that primary amine extracted Cr(VI) from nearly neutral aqueous solutions was different from anion exchange mechanism, and the Cr(VI) extracted into the organic phase resulted in the appearance of the peak at 885 cm(-1) of FTIR which justified that the peak at 890 cm(-1) of Raman was caused by Cr(VI). The 1H NMR spectroscopy showed that the value of chemical shift of protons of -NH2 decreased after extraction, and it is believed that primary amine was associated with Cr(VI) through hydrogen bonding. On the basis of the spectroscopic analysis results above, the mechanism of Cr(VI) extraction by primary amine from nearly neutral aqueous solutions was believed to be solvation with molecular association between primary amine and Cr(VI) through hydrogen bonding.     

Phosphorus-31 MAS NMR investigations of pyridine stabilized dithiomonometaphosphoryl halides

Phosphorus-31 magic-angle spinning NMR spectroscopy was chosen in order to study a series of N-donor stabilized dithiomonometaphosphoryl halides (F, Cl, and Br) and to extract structural and bonding information from their spectra. Additionally, an unusual line splitting was observed in the 31P MAS NMR spectra of pyridine dithiomonometaphosphoryl chloride (Py-->PS2Cl) and the analogous bromide (Py-->PS2Br). It is shown that this effect is due to a residual dipolar coupling between phosphorus and chlorine or bromine, respectively. This work is to our knowledge the first observation of this effect between P and Br in 31P MAS NMR spectra.     

New proton conducting materials for technical applications: what can we learn from solid state NMR studies?

Many novel proton conducting materials are based on complex hydrogen bonding networks of amphoteric hydrogen bonded moieties. Solid state NMR provides unique methods to study the properties of such network and specific proton conduction mechanisms in detail. In particular 1H solid state NMR techniques under fast magic angle spinning are powerful tools in this area. Site specific studies of the dynamic behavior via variable temperature 1H MAS measurements provide insight in the thermodynamics of the hydrogen bonding as well as activation energies for the proton transfer between the amphoteric sites. On macroscopic length scales, pulsed field gradient NMR experiments are able to determine the proton mobility and the contribution of different conduction mechanisms. In this article, aspects of recent solid state NMR studies in the field are reviewed and typical experimental methods as well as their possible outcome are discussed.     

An advanced NMR protocol for the structural characterization of aluminophosphate glasses

In this work a combination of complementary advanced solid-state nuclear magnetic resonance (NMR) strategies is employed to analyse the network organization in aluminophosphate glasses to an unprecedented level of detailed insight. The combined results from MAS, MQMAS and (31)P-{(27)Al}-CP-heteronuclear correlation spectroscopy (HETCOR) NMR experiments allow for a detailed speciation of the different phosphate and aluminate species present in the glass. The interconnection of these local building units to an extended three-dimensional network is explored employing heteronuclear dipolar and scalar NMR approaches to quantify P-O-Al connectivity by (31)P{(27)Al}-heteronuclear multiple quantum coherence (HMQC), -rotational echo adiabatic passage double resonance (REAPDOR) and -HETCOR NMR as well as (27)Al{(31)P}-rotational echo double resonance (REDOR) NMR experiments, complemented by (31)P-2D-J-RESolved MAS NMR experiments to probe P-O-P connectivity utilizing the through bond scalar J-coupling. The combination of the results from the various NMR approaches enables us to not only quantify the phosphate units present in the glass but also to identify their respective structural environments within the three-dimensional network on a medium length scale employing a modified Q notation, Q(n)(m),(AlO)(x), where n denotes the number of connected tetrahedral phosphate, m gives the number of aluminate species connected to a central phosphate unit and x specifies the nature of the bonded aluminate species (i.e. 4, 5 or 6 coordinate aluminium).     

Hardware modification of a 7 mm MAS NMR probe to a single-crystal goniometer

Tensorial terms of the Hamiltonian can be measured by solid-state single-crystal nuclear magnetic resonance (NMR) spectroscopy which requires a goniometer NMR probehead. Goniometer probes; however, are not standard parts of solid NMR spectrometers and are available only at a much higher price than magic-angle spinning (MAS) probeheads widely used in research. Due to requirements of MAS experiments, modern probeheads are designed for small ceramic rotors, which are 1-4 mm in diameter, to reach very high angular frequencies, so there are several older 7 mm MAS probeheads used rarely todays in NMR laboratories. In this paper, a simple method is presented how to rebuild step-by-step a 7 mm Bruker MAS probehead to be suitable for single-crystal spectroscopy. In the second part (31)P chemical shift tensors of Na(4)P(2)O(7) x 10H(2)O are determined to demonstrate the functionality of the rebuilt probehead.     

蟾毒灵对脂质体双分子层结构的影响:31P NMR研究

应用³¹P NMR方法研究了蟾毒灵(BF)对脂质体双分子层结构的影响.研究结果表明对于未经超声波处理的卵磷脂(PC),BF对磷脂双分子层膜具有稳定作用.另一方面,当PC经过超声波处理后,首次观测到纯PC的双分子层膜转变为胶束或微胞,后者的比例随着超声波处理的时间的增加而增加;而BF的存在可加速PC由双分子层结构向胶束相的转变.     

Correlation between 31P chemical shift tensor and local structure in lithium cyclohexaphosphates Li6P6O18 x 3H2O and Li6P6O18

To understand the surprising behavior between the variations of the P'-P-P" angles and the correlated variations of the O'-P-O" ones, two lithium cyclohexaphosphate compounds Li6P6O18 x 3H2O and Li6P6O18 are studied by solid state nuclear magnetic resonance (NMR) spectroscopy. The two compounds exhibit the same [P6O18]6- ring anions but with 3m or 1 internal symmetry, respectively. Such symmetries induce local distortions that are exhibited by NMR spectroscopy. One-dimensional (1D) NMR gives information on structural sites of 7Li and 31P ions and the crystallographic non-equivalencies are observed. Nevertheless, in the anhydrous compound, X-ray diffraction and NMR results do not completely agree and some discrepancy exists between the number of sites observed with the first technique and the number of lines exhibited in the NMR spectra either for 7Li or 31P nuclei. This problem is elucidated by using 2D double quantum NMR spectroscopy coupled with theoretical considerations. We find that the 31P chemical shift tensor is dependent on the deviations of the O-P-O angles from those in the regular tetrahedron. Within the same empirical model, we suggest that the surprising behavior between the variations of the P'-P-P" and the ones of the O'-P-O" is related to the overall charge on the PO4 group. We also find the positions of the isotropic lines for 7Li essentially depend on the site co-ordination of this nuclei.     

Dynamics of NaHSeO3 and NaHSeO4 single crystals by observation of 1H and 23Na spin-lattice relaxation

The 1H and 23Na spin-lattice relaxation times of NaHSeO3 and NaHSeO4 single crystals grown by the slow evaporation method were measured. The phase transitions of the two crystals were studied using differential scanning calorimetry (DSC), and the environments of the 1H and 23Na nuclei in these crystals were investigated by means of 1H and 23Na NMR spectroscopy. The DSC results show that NaHSeO3 crystals do not undergo phase transitions, whereas for NaHSeO4 crystals there is a small endothermic peak at 419 K. The dimers in NaHSeO3 stabilize its structure to the extent that there are no phase transitions even in the presence of disordered hydrogen bonds. In addition, the NMR results indicate that the temperature dependencies of T1 for the 1H and 23Na nuclei in the two hydrogen-bonded crystals-the NaHSeO3 crystal with 3-coordinated SeO3 and the NaHSeO4 crystal with 4-coordinated SeO4--are significantly different. The different trends in T1 for Na in the two crystals are accompanied by different shifts of the oxygen atoms from the 3-coordinated SeO3 and the 4-coordinated SeO4 species around the Na+ ions. Thus, although the two crystals have hydrogen-bonded structures, the differences between the hydrogen bonding of the 3-coordinated SeO3 in NaHSeO3 and the hydrogen bonding of the 4-coordinated SeO4 in NaHSeO4 result in different T1 temperature dependences and different phase transitions.     

2D 1H-31P solid-state NMR studies of the dependence of inter-bilayer water dynamics on lipid headgroup structure and membrane peptides

The dynamics of hydration-water in several phospholipid membranes of different compositions is studied by 2D (1)H-(31)P heteronuclear correlation NMR under magic-angle spinning. By using a (1)H T(2) filter before and a (1)H mixing-time after the evolution period and (31)P detection, inter-bilayer water is selectively detected without resonance overlap from bulk water outside the multilamellar vesicles. Moreover the (1)H T(2) relaxation time of the inter-bilayer water is measured. Lipid membranes with labile protons either in the lipid headgroup or in sterols exhibit water-(31)P correlation peaks while membranes free of exchangeable protons do not, indicating that the mechanism for water-lipid correlation is chemical exchange followed by relayed magnetization transfer to (31)P. In the absence of membrane proteins, the inter-bilayer water (1)H T(2)'s are several tens of milliseconds. Incorporation of charged membrane peptides shortened this inter-bilayer water T(2) significantly. This T(2) reduction is attributed to the peptides' exchangeable protons, molecular motion and intermolecular hydrogen bonding, which affect the water dynamics and the chemically relayed magnetization transfer process.     

A Spectroscopic Study of the Interaction of the Fluorescent β-Carboline-3-carboxylic Acid N-methylamide with DNA Constituents: Nucleobases, Nucleosides and Nucleotides

Interaction between beta-carboline-3-carboxylic acid N-methylamide, betaCMAM, and nucleobases, nucleosides and nucleotides is studied in the ground state with UV-visible, (1)H NMR and (31)P NMR spectroscopies and in the first excited state, with steady-state and time-resolved fluorescence spectroscopy. Job plots show a predominant 1:1 interaction in both electronic states. Association constants are estimated from changes in the absorption spectra, and show that the strongest interaction is produced with the nucleosides: 2'-deoxyadenosine (dAdo) and thymidine (Thd), and with the mononucleotides: 2'-deoxycytidine 5'- monophosphate (5'-dCMP) and uridine 5'- monophosphate (5'-UMP). These results are corroborated by the upfield shifts of two (1)H NMR resonances of the betaCMAM indole group. The (31)P NMR resonance of nucleotides is shifted downfield, suggesting the presence of electrostatic or hydrogen bond interaction with betaCMAM. In the first electronic singlet excited state, static and dynamic quenching of betaCMAM emission is achieved upon addition of nucleobases, nucleosides and nucleotides. This has been analysed using Stern-Volmer kinetics.     

Synthesis/structural and mesomorphic properties of substituted hydrazide based calamitic molecules

A set of rod-shaped molecules with central hydrazide moiety has been synthesized and characterized using standard spectroscopic techniques. The thermal behaviors of the final compounds were established by the combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and high-temperature powder X-ray method (XRD). The structure and conformation of the molecules were achieved by FTIR, ¹H NMR, ¹³C NMR spectroscopy and DFT calculations. It is found that two compounds are non-liquid crystalline and two compounds are liquid crystalline (LC). The structure property correlations with alkyl chain, connecting position, hydrogen bonding and without hydrogen bonding were established. The studies envisaged that LC properties are induced due to hydrogen bonding and elongation of the molecular length.     

The effect of polysialic acid on molecular dynamics of model membranes studied by 31P NMR spectroscopy

The paper reports the results of our study on the dynamics of model phospholipid membranes studied by 31P NMR spectroscopy. The 31P NMR spectra of multilamellar vesicles in temperatures below the main phase transition of PC are reported. The 31P NMR spectra revealed changes caused by an increase of the membrane fluidity when polysialic acid (polySia) was applied as a modifying agent. The presence of polySia in the external environment of the phospholipid vesicles changes the motional freedom in the region of phosphate group of lipids. Increase of polysialic acid concentration changes structural properties of a membrane by increasing its fluidity.     

NMR studies of hydrogen diffusion in hydrogen uranyl phosphate tetrahydrate (HUP)

¹H NMR spin-lattice relaxation times, T₁ (Zeeman) and T_1ϱ (rotating frame) and spin-spin relaxation times, T₂, and ³¹P NMR solid-echoes are reported for phase I and II of hydrogen uranyl phosphate tetrahydrate (HUP) at temperatures in the range 200–323 K. The spectral density functions extracted from the measured relaxation times for phases I and II are consistent with a 2D diffusion mechanism for hydrogen motion. ³¹P second moments determined from the solid-echoes show that all the hydrogens diffuse rapidly in phase I, and that the hydrogen-bond site nearest to the phosphate oxygen is not occupied in phase II. The mechanism for diffusion in phase II is discussed.     

2H chemical shift anisotropies from high-field 2H MAS NMR spectroscopy

2H chemical shift anisotropies (CSAs) have been determined for the first time for polycrystalline samples employing 2H MAS NMR spectroscopy at high magnetic field strength (14.1 T). The 2H CSA is reflected as distinct asymmetries in the manifold of spinning sidebands (ssbs) observed for the two overlapping single-quantum transitions. Least-squares fitting to the manifold of ssbs allows determination of the 2H CSA parameters along with the quadrupole coupling parameters. This is demonstrated for KD2PO4, ND4D2PO4, KDSO4, KDCO3, alpha-(COOD)2, alpha-(COOD)2.2D2O, and boehmite (AlOOD) which exhibit 2H shift anisotropies in the range 13< or =deltasigma< or =27 ppm. For fixed values of the shift anisotropy and the 2H quadrupole coupling it is shown that the precision of the CSA parameters depends strongly on the asymmetry parameter (etaQ) for the quadrupole coupling tensor, giving the highest precision for etaQ approximately 0. The 2H CSA parameters (deltasigma and etasigma) are in good agreement with 1H CSA data reported in the literature for the corresponding protonated samples from 1H NMR spectra employing various homonuclear decoupling techniques. The determination of 2H quadrupole coupling parameters and 2H (1H) CSAs from the same 2H MAS NMR experiment may be particularly useful in studies of hydrogen bonding since the 2H quadrupole coupling constant and the CSA appear to characterize bond lengths in a hydrogen bond in a different manner.     

The influence of Fermi energy on structural and electrical properties of laser crystallized P-doped amorphous silicon

A series of phosphorous-doped hydrogenated amorphous silicon films (a-Si:H) were crystallized using step-by-step laser crystallization process. The structural changes during the sequential crystallization process were detected by Raman measurements. The dehydrogenation was monitored by measuring the Si-H local vibrational modes using Raman spectroscopy and hydrogen effusion measurements. Interestingly, hydrogen bonding is affected by doping of the amorphous material. The influence of doping concentrations, thus the Fermi energy on electronic properties has been investigated employing secondary ion mass spectroscopy (SIMS), dark-conductivity- and Hall-effect measurements. The results from hydrogen effusion are consistent with the results obtained from Raman spectroscopy, Hall-effect- and dark-conductivity measurements.     

D-樟脑与β-环糊精包合物的结构表征

采用饱和水溶液搅拌法制备β-环糊精(β-CD)/D-樟脑包合物.1H NMR确定了β-CD与D-樟脑形成包合物的化学计量比为1∶1.X-射线衍射图谱和红外光谱图证明D-樟脑和β-CD分子间的相互作用.1H ROESY NMR分析结果说明包合物的结构型式是D-樟脑的二环[2.2.1]-2-庚酮位于β-CD空腔内,其三甲基部分位于β-CD空腔外.通过量子化学计算得到形成β-CD/D-樟脑包合物最低结合能和结构优化状态,氢健的存在证实了上述分析结果的准确性.     

Investigation in hydrated thorium phosphates by NMR I-relation proton phosphorus

The relations between (1)H and (31)P nuclei are investigated by multinuclear and multidimensional nuclear magnetic resonance (NMR) spectroscopy in order to obtain structural information along the transformation of the thorium phosphate hydrogen phosphate hydrate (TPHPH) into the thorium phosphate diphosphate (TPD) when heating. The raw sample obtained at 120 degrees C was heated at 300, 400, 600, 800 or 1100 degrees C and then studied at room temperature. Single acquisition on (1)H and (31)P nuclei, cross-polarization (CP) at the magical angle spinning, Lee-Golburg homonuclear decoupling in two-dimensional experiments, rotational echo double resonance (REDOR and CP-REDOR) and heteronuclear correlation (HETCOR) were performed. These experiments contribute to evidence the differences between the raw sample and that heated. Indeed, above 300 degrees C, hydrogen phosphate groups (HPO(4)) are completely condensed as diphosphate entities (P(2)O(7)). These results confirm that the TPHPH is successively transformed into a low-temperature form of the TPD (called alpha-TPD), then into its well-known beta-form above 950 degrees C.