Characterization of mixed micelles of sodium cumene sulfonate with sodium dodecyl sulfate and cetyl trimethylammonium bromide by SANS,FTIR spectroscopy and NMR spectroscopy

The aqueous solutions of sodium cumene sulfonate (NaCS) and its mixtures with cetyl trimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) are studied by Small Angle Neutron Scattering (SANS), Fourier Transform Infrared (FTIR) spectroscopy and Nuclear Magnetic Resonance (NMR) spectroscopy. The compositions of mixed micelles are determined using Rubingh's Regular Solution Theory. NaCS when added to CTAB solution leads to the formation of long rod shaped micelles with dramatic increase in the CTAB aggregation number. Its addition to SDS on the other hand results in the formation of smaller mixed micelles where parts of SDS molecules in the micelle are replaced by NaCS molecules. NaCS–SDS mixed micelles prefer elongated ellipsoidal geometry in order to accommodate short NaCS molecules. The FTIR spectroscopy results indicate enhanced ordering of CTAB tails inside the NaCS–CTAB mixed micelles with reduction in the gauche/trans conformer ratio. Addition of NaCS to SDS on the other hand results in decreased ordering of SDS tails, as compared to SDS micelles alone. The chemical shifts observed in ¹H NMR spectra of NaCS–SDS and NaCS–CTAB mixture indicate that NaCS resides near the surface of the SDS micelle.     

水溶性聚合物与十二烷基硫酸钠相互作用的1H NMR研究

用¹H NMR方法研究了分别在2 g/L聚乙烯吡咯烷酮(PVP)和2 g/L聚乙烯醇（PVA）存在下，一系列不同浓度的十二烷基硫酸钠(SDS)溶液. 二维NOESY实验表明，SDS在浓度为2.5 mmol/L时形成胶束，且PVP被增溶到胶束内部；当SDS浓度低于2.5 mmol/L时，PVP与SDS之间没有明显的相互作用. 自旋-自旋弛豫时间的测量结果支持这一结论. 实验中没有检测到PVA与SDS之间的相互作用.     

<Superscript>1</Superscript>H and<Superscript>13</Superscript>C chemical shift assignments and stereochemistry of matrine and oxymatrine

Matrine and oxymatrine were extracted fromSophora flavescens, and their¹H and¹³C nuclear magnetic resonances (NMR) were unambiguously assigned by a combination of different two-dimensional 2-D¹H-¹³C and¹H-¹H correlation experiments of HMQC, HMQC-TOCSY and MAXY. The technique of using those experiments to make the assignment of the heavily overlapped spectrum is demonstrated. The coupling constants of matrine were measured by 2-DJ-resolved spectrum and 1-D spectra extracted from the slices of 2-D MAXY spectrum. The stereochemistry of the titled compounds was established from the NMR spectroscopy.     

Crystal growth, FTIR and thermal characterization of bis(ethyltriphenylphosphonium) tetrabromomanganate(II) dihydrate crystals

Single crystals of a novel compound, bis(ethyltriphenylphosphonium) tetrabromomanganate(II) dihydrate (BTP-Mn) were grown by solution growth-slow evaporation technique from aqueous solution of the compound at ambient temperature. The grown crystals were characterized by elemental analysis, powder X-ray diffraction, thermal analysis, nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infra-red spectroscopy (FTIR) techniques. The chemical composition of the compound was revealed by elemental analysis and its crystallinity was confirmed by powder X-ray diffraction. Thermal analysis confirmed that the compound was stable up to 125°C. The various kinds of protons and carbons present in the compound were confirmed by ¹H NMR and ¹³C NMR technique respectively and the presence of phosphorous was confirmed by ³¹P NMR spectrum in the compound. The modes of vibration of different molecular groups present in the compound were identified by FTIR spectral analysis. The second harmonic generation behaviour was tested by Nd:YAG laser source.     

水溶性磷酸盐柱[5]芳烃与吖啶橙的络合行为

本文首先构建了水溶性磷酸盐柱[5]芳烃（PP5A）与阳离子荧光染料吖啶橙（AO）主-客体络合物.然后通过紫外光谱（UV）、红外吸收光谱（IR）、分子荧光光谱（MFS）、一维和二维核磁共振（NMR）波谱技术（包括¹H NMR和NOESY）研究了PP5A与AO的络合行为.此外,还研究了pH及两种表面活性剂——十二烷基硫酸钠（SDS）和十六烷基三甲基溴化铵（CTAB）对AO/PP5A络合体系的荧光强度的影响.最后,采用分子对接计算了PP5A与AO和CTAB的络合模式及络合能.研究表明,AO与PP5A形成1：1的主-客体络合物;在pH=3~11范围内,PP5A均能使AO的荧光强度发生减弱或淬灭;SDS和CTAB的加入并不会对AO/PP5A络合体系的荧光强度产生显著影响.AO与PP5A络合时产生的荧光强度变化可为荧光传感器的设计提供理论基础.     

Proton Relaxation and Spin Label Studies of Papaverine Localization in Ionic Micelles

The localization of papaverine (PAV) in micelles of zwitterionic N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS), cationic cetyltrimethylammonium chloride (CTAC), and anionic sodium dodecyl sulfate (SDS) in D₂O was studied by ¹H NMR and ESR in the presence and absence of 5-doxyl- or 12-doxyl-stearic acid. PAV, surfactants, and spin probes are characterized by restricted anisotropic motion in micelles. The rotational correlation time of doxyl fragment was in the range of 0.2 to 0.5 nanoseconds. Binding of PAV to micelles decreases the mobility of both probes, suggesting the localization of PAV inside the hydrophobic part of micelles near the micelle-water interface. According to the NOE data, the methoxy groups of PAV are located in the vicinity of the nitrogen atom in CTAC and HPS micelles, the methoxy groups of the PAV heterocycle being immersed slightly deeper inside the micelle. The T₁ relaxation enhancements by two different spin probes show that the H5 and methoxy substituents of the PAV heterocycle are in close proximity to the α-CH₂ of acyl chains in all types of micelles, whereas H3 and H12 are the most distant from the α-CH₂. No significant differences were found for the protonated and neutral PAV in SDS micelles at pD 4.9 and 11.2. These data show that the geometry of the PAV-micelle complex is practically independent of the PAV charge and surfactant headgroup.     

Assignments of Nonexchangeable Proton Resonances and the Solution Structures of d–TGGGT

In this paper, we report the studies of the solution structures of synthetic pentadeoxyribonucleotide d-TGGGT(NH₄ ⁺ salt) using 2D–NMR. The 1H–NMR experiments with different temperatures and concentrations reveal an equilibrium between single strand and aggregation. In the experimental condition(22°C, 13mmol/ L), the cross peaks in the COSY spectrum are mainly from single strand, and the spin systems of sugar resonances of this component can be assigned. In contrast, the cross peaks in the NOESY spectrum mainly come from aggregation and the sequential assignments of bases, sugar 1′, 2′ and 2″ protons can be carried out. From NOE connectivities, it is obvious that the aggregation adopts a right–handed helix conformation. It is suggested that the aggregation in our experiment corresponds to the tetramolecular complex.     

NOE Effect of Sodium Dodecyl Sulfate in Monomeric and Micellar Systems by NMR Spectroscopy

This paper describes the particular nuclear Overhauser effect (NOE) of sodium dodecyl sulfate (SDS) in monomeric and micellar systems. Two-dimensional NOE spectroscopy nuclear magnetic resonance (NMR) spectra of SDS in solution with concentration lower and higher than critical micellar concentration were recorded. In the first case diagonal and cross-peaks have different signs, and the opposite one was in the second case. This paper discusses theoretical background of this effect and we supposed that particular NOE can be used for inspection of SDS micelle formation during NMR researches. As a rough estimate of micelles formation an approach based on the difference between the chemical shifts in the monomer and micellar form of SDS was used.     

Poly(ethylene glycol) and phospholipid packing in the structure of reverse micelles

The influence of water substitution by a substance with a different polarity on the structure of phospholipid monolayer interface in water-in-oil microemulsion has been studied by the Fourier-transform pulsed-gradient spin-echo (FT PGSE)¹H nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spin-label methods. For this purpose the soybean phosphatidylcholine-based microemulsion and water soluble poly(ethylene glycol) with molecular weight 400 (PEG400) were used. Self-diffusion coefficients of all microemulsion components obtained by the FT PGSE NMR technique provided information about both the size of reverse micelles and distribution of components between different microemulsion compartments. The maximum hyperfine splitting, 2A _max, in the ESR spectra was used to characterize the degree of the phospholipid hydrocarbon chain mobility. It was shown that PEG400 alters significantly the size of the reverse micelles and the motion of the labeled segments of the lipid tails. A mechanism of PEG400 acting in solution of the phospholipid-based reverse micelles on the basis of the rough decrease of the micelle core polarity was suggested.     

Nanoparticle carriers based on copolymers of poly(<Emphasis Type="SmallCaps">l</Emphasis>-aspartic acid co-<Emphasis Type="SmallCaps">l</Emphasis>-lactide)-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine for drug delivery

A novel poly(l-aspartic) derivative (PAL-DPPE) containing polylactide and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) segments has been successfully synthesized. The chemical structures of the copolymers were confirmed by Fourier-transform infrared spectroscopy (FTIR), NMR (¹H NMR, ¹³C NMR, ³¹P NMR), and thermogravimetric analysis (TGA). Fluorescence spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM) confirmed the formation of micelles of the PAL-DPPE copolymers. In order to estimate the feasibility as novel drug carriers, an anti-tumor model drug doxorubicin (DOX) was incorporated into polymeric micelles by double emulsion and nanoprecipitation method. The DOX-loaded micelle size, size distribution, and encapsulation efficiency (EE) were influenced by the feed weight ratio of the copolymer to DOX. In addition, in vitro release experiments of the DOX-loaded PAL-DPPE micelles exhibited that faster release in pH 5.0 than their release in pH 7.4 buffer. The poly(l-aspartic) derivative copolymer was proved to be an available carrier for the preparation of micelles for anti-tumor drug delivery.     

Methodology of1H NMR spectroscopy of the human brain at very high magnetic fields

An ultrashort-echo-time stimulated echo-acquisition mode (STEAM) pulse sequence with interleaved outer volume suppression and VAPOR (variable power and optimized relaxation delays) water suppression was redesigned and optimized for human applications at 4 and 7 T, taking into account the specific requirements for spectroscopy at high magnetic fields and limitations of currently available hardware. In combination with automatic shimming, automated parameter adjustments and data processing, this method provided a user-friendly tool for routine¹H nuclear magnetic resonance (NMR) spectroscopy of the human brain at very high magnetic fields. Effects of first- and second-order shimming, single-scan averaging, frequency and phase corrections, and eddy currents were described. LCModel analysis of an in vivo¹H NMR spectrum measured from the human brain at 7 T allowed reliable quantification of more than fifteen metabolites noninvasively, illustrating the potential of high-field NMR spectroscopy. Examples of spectroscopic studies performed at 4 and 7 T demonstrated the high reproducibility of acquired spectra quality.     

<Superscript>57</Superscript>Fe NMR study of multiferroic BiFeO<Subscript>3</Subscript>

The effects of the ⁵⁷Fe isotope content and high-frequency magnetic field amplitude h ₁ on the shape of the NMR spectrum of multiferroic BiFeO₃ at T = 4.2 K are studied by pulsed nuclear magnetic resonance. The NMR spectrum shape and transverse relaxation time T ₂ are found to depend strongly on the ⁵⁷Fe isotope content and h ₁ in multiferroic BiFeO₃ in the presence of a spatial spin-modulated structure of a cycloid type. In a sample with a high ⁵⁷Fe isotope content, the Suhl-Nakamura interaction contributes substantially to T ₂. When these dynamic effects are taken into account for analysis of the NMR spectrum shape, an undisturbed (without an anharmonicity effect) spatial spin-modulated structure of a cycloid type is shown to exist in BiFeO₃.     

Nuclear Magnetic Resonance Spectra of Polyhydroxylated Fullerene C60(OH)n

Polyhydroxylated fullerene C₆₀(OH)_n (with an estimated number of hydroxyl groups n = 38–44) synthesized from pure fullerene by mixing a benzene solution of C₆₀ with a NaOH aqueous solution in the presence of a catalyst was studied with ¹H and ¹³C solid-state nuclear magnetic resonance. Possible features of the structure of a molecule shell were revealed from ¹H NMR data. The ¹³C spectrum showed a peak splitting with an increase in temperature, which is probably due to fullerenol isomers.

     

Solution Conformation of a Pentapeptide by NMR and Molecular Modeling Studies

High resolution NMR studies and molecular modeling calculations were performed on a linear pentapeptide BOC-Tyr-Gly-Gly-Pro-Leu-OMe. This molecule exhibits two conformations in the solution state. While the ¹³C spectrum in nonpolar solvents such as acetonitrile shows only one form, in DMSO-d₆ and MeOD there are two forms. The appearance of the major (M) and minor (m) resonances is attributed to cis-trans isomerization about the X-Pro bond.

The assignments of several proton resonances for the major conformer were made through the combined analysis of two dimensional (2D) homonuclear correlated spectroscopy (COSY) and available data on similar peptides. The solution conformation of the major moiety was probed using the distance constraints obtained from 2D-NOE spectroscopy (NOESY). In addition, other information such as presence of internal hydrogen bonds and dihedral angle values from coupling constants for the amide protons were also used.     

Combined Use of 2-D NMR Correlation Experiments, GIAO DFT 13C Chemical Shifts and 1-D NOESY Methods in Regioisomeric and Conformational Structure Determination of Cyclophanes in Solution

The combined application of two-dimensional nuclear magnetic resonance (2-D NMR) correlation experiments and gauge-including atomic orbital (GIAO) ¹³C NMR chemical shift calculations allowed reliable and simple determination of regioisomeric structure of heterocyclic substituents on the calix[4]arene lower rim. Moreover, the 1-D double pulsed field gradient nuclear Overhauser effect technique allows quick and efficient measurement of small nuclear Overhauser effects and, in doing so, establishes a 3-D structure of calix[4]arene simply and unequivocally. In general, these methods may find application in the regio- and stereoisomeric structure determination of complicated macrocyclic compounds.     

阿立哌唑的谱学研究

对抗精神分裂症新药阿立哌唑的紫外光谱(UV)、红外光谱(IR)、核磁共振谱(NMR)以及质谱(MS)进行了解析。根据该化合物的紫外光谱探讨了其在溶液中的存在形式,讨论了红外光谱的特征吸收峰所对应的官能团的振动形式以及质谱的特征同位素离子峰,利用1H—1H cosy,HSQC,HMBC等二维核磁共振技术推断并确证了该化合物的结构,对NMR谱信号进行了归属,并根据化学位移、偶合常数以及二维相关谱分析了该化合物结构中的10个不同的亚甲基。     

Application of two-dimensional pulsed EPR nutation spectroscopy to a disordered system with largeg-anisotropy

Two-dimensional (2-D) pulsed electron paramagnetic resonance (EPR) nutation spectroscopy is applied to a disordered system with strongly anisotropicg-factors. The analysis and interpretation of a 2-D nutation spectrum is performed by theoretical calculations appropriate for ferric myoglobin cyanide in frozen solution. The observed and calculated 2-D spectra show broad signals which correspond to the principalg-values. The advantage of nutation spectroscopy is demonstrated by measuring theg _x=0.93 signal, which cannot be observed in a conventional field-swept spectrum due to largeg strain broadening. It is shown that the 2-D nutation experiment can be considered as a sort of an angle-selected method but a nutation spectrum gives a powder pattern even for magnetic field settings at extreme field values of an EPR spectrum. This is in contrast to angle-selected electron nuclear double resonance, which gives a single-crystal type spectrum. The advantage of sine Fourier transform (FT) over complex FT is demonstrated for data processing in the nutation domain. Problems of experimental and data-processing procedures are also discussed.     

Effects of Surfactant and Polyelectrolyte on Distribution of Silicate Species in Alkaline Aqueous Tetraoctylammonium Silicate Solutions Using 29Si NMR Spectroscopy

In the present work, the structure-directing effect of the surfactant sodium dodecyl sulfate (SDS) on the distribution of the silicate species present in alkaline aqueous silicate solutions is studied using silicon-29 nuclear magnetic resonance (NMR) spectroscopy. Also, the distribution of silicate anions in the presence of polyelectrolytes is investigated using ²⁹Si NMR spectroscopy through the use of different bases including tetraoctylammonium hydroxide and sodium hydroxide as templates (their cations) in these solutions. Both the SDS and polyelectrolytic solutions are shown to stabilize low molecular weight silicate species and thus inhibit polymerization.     

硒钨簇合物中有机取代基的1H、13C NMR归属

用二维异核多量子化学位移相关谱¹H-¹³C HMQC,HMBC和二维同核NOESY谱研究了两个新合成的双钨核有机硒化合物的结构,归属了该化合物的¹H,¹³C NMR谱线.     

A New Antimicrobial Sesquiterpene Lactone from Artemisia giraldii

A new antimicrobial eudesmanolide, 1-oxo-8α-hydroxy-11αH-eudesm-4-en-12, 6α-olide (1), was isolated from a medicinal plant Artemisia giraldii and its structure was elucidated by spectroscopic methods (IR, MS, ¹H NMR, ¹³C NMR, ¹H-¹H COSY and NOESY). Antimicrobial bioassay indicated that this compound inhibited the growth of human pathogenic bacteria Staphylococcus auerus, Bacillus subtilis and Escherichia coli as well as human opportunistic pathogenic fungi Candida tropicalis, Gecotrichum candidun, Aspergillus flavus and A. nigers.