Use of Magic Angle Spinning ~1H NMR Spectroscopy to Monitor Reactions in Solid-Phase Synthesis

Proton NMR-spectra of Wang resin bound compounds were obtained using the magic angle spinning 1HNMR technique with standard equipment. It was possible to analyse the spectra to evaluate their utility in solid-phase chernistry. A typical example was presented, which could directly monitor solid-phase reactions

Preliminary study in vitro brain tumor with high resolution magic angle spinning proton magnetic resonance spectroscopy

Objective： To explore water soluble metabolite features of brain tumor specimens with HRMAS-^1HMRS and its potential clinical value. Methods： There were thirty cases of pathologically proven brain tumor, including 6 Ⅰ-Ⅱ grade astrocytomas, 7 Ⅲ grade anaplastic astrocytomas, 10 IV grade glioblastomas and 7 meningiomas. Used Varian Company 600 MHz spectrometer with the Nano-probe for acquisition HRMASJHMRS, which was postprocessed with jMRUI 3.2 version software. These metabolic probability and their ratios to Cr were summed. Results： （1） HRMAS-^1HMRS could resolve NAA, PCr/Cr, GPC ± PCho ± Cho, Glu/GIn, Gly, Tau, Ala, Lac, ml and so on. All samples showed Lac, 6 samples showed unknown single peak at 3.72 ppm or 3.90 ppm. （2） The mean Cho/Cr of 6 Ⅰ-ⅡI grade astrocytomas was 2.42 ± 1.01 （P = 0.003, compared with glioblastoma）. The mean Cho/Cr of 7 anaplastic astrocytomas was 3.48 ± 0.59 （P = 0.01, compared with glioblastoma）. The Cho/Cr of 10 glioblastomas broadly ranged from 0.9 to 11.3 （mean 5.40 ± 1.23）. From Ⅰ-Ⅱ grade astrocytoma to glioblastoma, Ala/Cr, Tau/Cr and Gly/Cr trends were increased; the mean Ala/Cr of glioma was 0.31 ± 0.13. （3） Meningiomas showed higher Ala and Cho. Their Cr was lower than that of gliomas. 4/7 cases had no NAA, 3/7 patients had lower NAA. Mean Cho/Cr was 3.56 ± 1.01, Ala/Cr was 0.53 ±0.28 （P = 0.006, compared with glioma）. Conclusion： HRMAS-^1HMRS can show further details in vivo MRS, resolve in vivo spectroscopic metabolite of Cho compound and differentiate the extent of benign and malignant glioma. With the increase in the malignant degree of gliomas, Cho, ml, Ala, Tau and Gly will increase. HRMAS-^1HMRS is the only method of isotropic spectroscopy for pathological specimens.

Heteronuclear-filtered ^(1)H homonuclear multi-quantum correlation experiment at 100 kHz magic-angle spinning Dedicated to Professor Chaohui Ye on the occasion of his 80th birthday

Remarkable advances in fast magic-angle spinning(MAS)techniques significantly improve the resolution of^(1)H solid-state nuclear magnetic resonance(NMR)spectra.Here,we introduce a heteronuclear-filtered^(1)H homonuclear multi-quantum(MQ)correlation strategy available at a MAS rate of 100 kHz by combining^(1)H{X}heteronuclear-filtered methods and^(1)H homonuclear MQ correlation experiments.The proposed strategy was applied to selectively extract^(1)H signals of aluminum lactate(Al-Lac)in a mixture of Al-Lac and zinc lactate(Zn-Lac)using 27Al-filtered methods(i.e.,^(1)H{27Al}heteronuclear multiple quantum correlation(HMQC)or^(1)H{27Al}symmetry-based resonance-echo saturationpulse double-resonance(S-RESPDOR)).We demonstrate that incorporating these 27Al-filtered methods into two-dimensional(2D)^(1)He^(1)H double-quantum(DQ)/single-quantum(SQ),triple-quantum(TQ)/SQ,and even three-dimensional(3D)27Al/^(1)H(DQ)/^(1)H(SQ)experiments can facilitate the acquisition of spectra without signal overlap and targeted characterization of the^(1)H species surrounding 27Al sites.The proposed strategy is considered to efficiently extract key structural information from complex spin systems.

Solid-state NMR studies of proteins in condensed phases

Some proteins perform their biological functions by changing their material states through liquid-liquid phase separation.Upon phase separation,the protein condenses into a concentrated liquid phase and sometimes into a gel phase,changing its dynamic properties and intermolecular interactions,thereby regulating cellular functions.Although the biological significance of this phenomenon has been widely recognized by researchers,there is still a lack of a comprehensive understanding of the structural and dynamic properties of the protein in the condensed phase.In this phase,molecules usually contain domains with varied dynamic properties and undergo intermediate exchanges.Magic angle spinning(MAS)solid-state NMR(SSNMR)experiments are very powerful in studying rigid protein polymers such as amyloid.The incorporation of solution-like experiments into SSNMR and the development of J-coupling based MAS SSNMR techniques extend its ability to study partially mobile segments of proteins in a condensed liquid or gel phase which are not visible by solution NMR or dipolar-coupling based SSNMR.Therefore,it has been applied in studying protein condensation and has provided very important information that is hard to obtain by other techniques.

Physicochemical Features of Phosphorus-Modified ZSM-5 Zeolite and Its Performance on Catalytic Pyrolysis to Produce Ethylene

The physicochemical features of phosphorus-modified ZSM-5 zeolites (SiO2/Al2O3 molar ratio is 25) were characterized by XRD(X-ray diffraction), BET(Brunauer, Emmett and Teller spcific surface area measurement), NH3-TPD(ammonia temperature-programmed desorption) and MASNMR(magic angle spinning nuclear magnetic resonance), and the performance on catalytic pyrolysis to produce ethylene was investigated with a light hydrocarbon fixed bed micro-reactor with n-octane as feed. The results show that the acid site density, acid intensity and hydrothermal stability of ZSM-5 zeolite were improved by phosphorus modification. When P2O5 content in ZSM-5 zeolite is higher than 2.5%, phosphorus modification can prevent ZSM-5 zeolite crystal structure transformation from orthorhombic to monoclinic. In addition, the dealumination of ZSM-5 zeolite framework was moderated by phosphorus modification under high temperature hydrothermal treatment. The results of n-octane pyrolysis on phosphorus-modified ZSM-5 zeolites show that ethylene yields of zeolites with different phosphorus content are almost the same under the same n-octane conversion. However, the modified zeolites with higher pyrolysis activity give lower yield of propene, butene and total olefin than lower pyrolysis activity under the same n-octane conversion.

Investigation on Acute Biochemical Effects of Ce（NO3 ）3 on Liver and Kidney Tissues by MAS 1H NMR Spectroscopic-Based Metabonomic Approach

High resolution magic angle spinning （MAS）-^1H nuclear magnetic resonance （NMR） spectroscopic-based metabonomic approach was applied to the investigation on the acute biochemical effects of Ce（NO3）3. Male Wistar rats were administrated with various doses of Ce（NO3）3（2, 10, and 50 mg·kg^- 1 body weight）, and MAS ^1H NMR spectra of intact liver and kidney tissues were analyzed using principal component analysis to extract toxicity information. The biochemical effects of Ce（NO3）3 were characterized by the increase of triglycerides and lactate and the decrease of glycogen in rat liver tissue, together with an elevation of the triglyceride level and a depletion of glycerophosphocholine and betaine in kidney tissues. The target lesions of Ce（NO3）3 on liver and kidney were found by MAS NMR-based metabonomic method. This study demonstrates that the combination of MAS ^1H NMR and pattern recognition analysis can be an effective method for studies of biochemical effects of rare earths.

MEASUREMENTS OF CHAIN INTERPENETRATION OF POLYMER GLASSES

The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale （several to tens of nanometer）. In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level.

NMR Study on Structural Characteristics of Rare Earth Doped Boro-Alumino-Silicate Glasses

The structural characteristics of Re2O3 doped B2O3-Al2O3-SiO2 glasses and factors such as the component and heat-treating conditions affecting the glass structure were investigated by magic angle spin nuclear magnetic resonance （MAS NMR） spectroscopy and differential thermal analysis （DTA）. It is found that, in B2O3-Al2O3-SiO2 glass, the boron （4）, and Al（5）, Al（6） changes to Al（4）. On the other hand, compared with Ba^2＋ , RE^3＋ can accumulate the boron network because of its higher field strength, which results in a large network structure. With the increase of samarium oxide, the silicate coordination Qa（3T） will have predominance gradually. Heat-treatment has little effect on the boron and aluminum coordination sites in the glass structure.

Nuclear Magnetic Resonance technique in tumor metabolism

Cancer is one of the most serious diseases that cause an enormous number of deaths all over the world.Tumor metabolism has great discrimination from that of normal tissues.Exploring the tumor metabolism may be one of the best ways to find biomarkers for cancer detection,diagnosis and to provide novel insights into internal physiological state where subtle changes may happen in metabolite concentrations.Nuclear Magnetic Resonance(NMR)technique nowadays is a popular tool to analyze cell extracts,tissues and biological fluids,etc,since it is a relatively fast and an accurate technique to supply abundant biochemical information at molecular levels for tumor research.In this review,approaches in tumor metabolism are discussed,including sample collection,data profiling and multivariate data analysis methods etc.Some typical applications of NMR are also summarized in tumor metabolism.

One-Pot Room-Temperature Synthesis of Mg Containing MCM-41 Mesoporous Silica for Aldol Reactions

One-pot synthesis of Mg containing MCM-41(Mg-MCM-41) materials was respectively carried out by a room temperature(RT) method and a hydrothermal(HT) method for aldol condensation of 4-nitrobenzaldehyde and acetone and self-condensation of acetone. The RT method can prepare MCM-41 materials containing large amounts of Mg while maintaining the structural characteristics of MCM-41 even at very low Si/Mg ratios(large Mg loadings), but the HT method cannot. The RT method can also give more active catalysts than the HT method, because the catalysts prepared by the RT method are more basic than those prepared by the HT one. The characterization indicates that Mg atoms in the Mg-MCM-41 prepared by the RT method exist as MgO disperses well on the wall surface of pores, while those in Mg-MCM-41 prepared by the HT method are included in the bulk with a smectite-like structure.