Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

盐酸非索非那定的NMR归属和立体化学研究

盐酸非索非那定(1),是第2代抗组胺药,其完整的NMR信号归属及其立体化学研究未见到报道. 由于大部分信号出现重叠,该化合物 ¹H NMR谱图解析比较困难,采用常规方法研究不易得到比较完整的NMR结构信息. 本文采用1D TOCSY、1D ROESY和2D NMR相结合的方法进行研究,得到了盐酸非索非那定完整的NMR信号归属. 此外,根据1D ROESY实验结果以及得到的有关偶合常数,推得该化合物的的立体结构,如（1）所示.     

Vibration and instability of a single-walled carbon nanotube in a three-dimensional magnetic field

The vibration and instability of a single-walled carbon nanotube (SWCNT) under a general magnetic field are of particular interest to researchers. Using nonlocal Rayleigh beam theory and Maxwell’s equations, the dimensionless governing equations pertinent to the free vibration of a SWCNT due to a general magnetic field were derived. The effects of the longitudinal and transverse magnetic fields on the longitudinal and flexural frequencies as well as their corresponding phase velocities were addressed and are discussed below. The critical transverse magnetic field (CTMF) associated with the lateral buckling of the SWCNT was obtained. The obtained results reveal that the CTMF increases with the longitudinally induced magnetic field. Further, its value decreases as the effect of the small-scale parameter increases.     

(E)-3-(4一羟苯基)-1-(哌啶-1-基)丙-2-烯-1-酮衍生物核磁共振特征与构象分析

设计并合成了一系列(E)-3-(4-羟苯基)-1-(哌啶-1-基)丙-2-烯-1-酮衍生物. 通过一维和二维核磁共振实验完成了¹H和¹³C信号的指认. 通过ROESY、变温实验和分子模拟技术对这类化合物的构象进行了分析.     

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.     

用核磁共振研究和确定乌拉尔甘草中一种新成分的化学结构

本文报告了用多种核磁共振实验方法并结合其它结构信息,研究并首次确定了内蒙产的乌拉尔甘草(Glycyrrhiza uralensis Fisch)中一种新甘草三萜内酯的化学结构并命名为甘乌内酯(Glyuranolide)。     

Preparation of NaYF4:,Er3+/TiO2 composite and up-conversion luminescence properties under visible light excitation

The up-conversion luminescence composite NaYF 4:Er 3+ /TiO 2 is prepared using the sol-gel method.The specimen has good crystallinity and two shapes,i.e.,viereck and round,while the sizes of viereck and round particles are both micron-sized.The TiO 2 has an anatase structure,while the NaYF 4 has a hexagonal phase,which can be hardly obtained through the common sol-gel method.Due to the big particle size and the high crystallinity of pure NaYF 4:Er 3+,the composite has a small specific surface area that is less than Degussa P25 TiO 2.The NaYF 4:Er 3+ /TiO 2 composite shows several emission peaks at 211,237,and 251 nm under the excitation of 388 nm,at 395 nm and 411 nm under the excitation of 500 nm,and at 467,481,492,and 508 nm under the excitation of 570 nm.     

Vitamin D and bone: — How does vitamin D regulate bone formation and resorption? —

Vitamin D was discovered as an anti-rachitic agent, but even at present, there is no direct evidence to support the concept that vitamin D directly stimulates osteoblastic bone formation and mineralization. It appears to be paradoxical, but vitamin D functions in the process of osteoclastic bone resorption. Osteoclasts, the only cells responsible for bone resorption, develop from hematopoietic cells of the monocyte-macrophage lineage. In 1992, we hypothesized that a membrane-bound factor, designated as “osteoclast differentiation factor (ODF)”, is expressed on the plasma membrane of osteoblasts/stromal cells in response to osteotropic factors including the active form of vitamin D₃, 1α,25-dihydroxyvitamin D₃ [1α,25(OH)₂D₃]. Recently, four research groups including ours independently identified three key molecules (RANKL, RANK, and OPG) responsible for osteoclastogenesis. A long-sought-after ligand, ODF, was identical to RANKL. RANKL was a member of the membrane-associated TNF ligand family, which induced differentiation of spleen cells (osteoclast progenitors) into osteoclasts in the presence of M-CSF. RANK, a member of the TNF receptor family, was a signaling receptor essential for the RANKL-mediated osteoclastogenesis. OPG, a secreted member of the TNF receptor family, was a decoy receptor for RANKL. The discovery of RANKL, RANK and OPG opens a new era in the study of bone biology and the therapy of several metabolic bone diseases such as osteoporosis, rheumatoid arthritis, and periodontal diseases.     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.     

Lorentz detuning and tuning system study of 3+1/2cell DC-SC photo-injector for PKU-FEL

A 3+1/2cell DC-SC photo-injector for PKU-FEL facility is under development, which is an upgrade design of the successful 1+1/2cell DC-SC photo-injector. The Lorentz detuning and tuning structure for the 3+1/2cell superconducting cavity is presented in this paper. The Lorentz force detuning coefficient is 7.2 Hz/(MV/m)2 with double stiffening rings for the half cell and single stiffening rings between the adjacent TESLA cells. With the special stiffening structure, the 3+1/2cell whole cavity needs only one tuner. The influences of the tuning on frequency shift, field flatness and average gradient are discussed in this paper. The simulation results show that the stiffening rings' design is successful.     

Neuroprotective effect of agmatine in rats with transient cerebral ischemia using MR imaging and histopathologic evaluation

Purpose

This study aimed to further investigate the effects of agmatine on brain edema in the rats with middle cerebral artery occlusion (MCAO) injury using magnetic resonance imaging (MRI) monitoring and biochemical and histopathologic evaluation.

Materials and methods

Following surgical induction of MCAO for 90 min, agmatine was injected 5 min after beginning of reperfusion and again once daily for the next 3 post-operative days. The events during ischemia and reperfusion were investigated by T2-weighted images (T2WI), serial diffusion-weighted images (DWI), calculated apparent diffusion coefficient (ADC) maps and contrast-enhanced T1-weighted images (CE-T1WI) during 3 h–72 h in a 1.5 T Siemens MAGNETON Avanto Scanner. Lesion volumes were analyzed in a blinded and randomized manner. Triphenyltetrazolium chloride (TTC), Nissl, and Evans Blue stainings were performed at the corresponding sections.

Results

Increased lesion volumes derived from T2WI, DWI, ADC, CE-T1WI, and TTC all were noted at 3 h and peaked at 24 h–48 h after MCAO injury. TTC-derived infarct volumes were not significantly different from the T2WI, DWI-, and CE-T1WI-derived lesion volumes at the last imaging time (72 h) point except for significantly smaller ADC lesions in the MCAO model (P < 0.05). Volumetric calculation based on TTC-derived infarct also correlated significantly stronger to volumetric calculation based on last imaging time point derived on T2WI, DWI or CE-T1WI than ADC (P < 0.05). At the last imaging time point, a significant increase in Evans Blue extravasation and a significant decrease in Nissl-positive cells numbers were noted in the vehicle-treated MCAO injured animals. The lesion volumes derived from T2WI, DWI, CE-T1WI, and Evans blue extravasation as well as the reduced numbers of Nissl-positive cells were all significantly attenuated in the agmatine-treated rats compared with the control ischemia rats (P < 0.05).

Conclusion

Our results suggest that agmatine has neuroprotective effects against brain edema on a reperfusion model after transient cerebral ischemia.     

NMR Studies of Agricultural Products. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Fungicide,Triadimefon.

Abstract

The 60 MHz ¹H NMR spectra of the systemic agricultural fungicide, triadimefon, 1, have been studied in CDCl₃ at 28±1° (as the racemic free base) with the added achiral lanthanide shift reagent (LSR), tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium(III), Eu(FOD)₃, 2, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene)-(+) -camphorato)europium(III), Eu(HFC)₃, 3, to induce enantiomeric shift differences (ΔΔδ) for several nuclei. Significant ΔΔδ values were seen for the two protons of the heterocyclic ring, the OCH methine, and aryl H-2′, 6′ of the chlorophenoxy ring. For each of these nuclei exhibiting ΔΔδ with added 3, the ΔΔδ magnitudes reached maximum values with 3: 1 molar ratios ca. 0. 18–0. 29, and decreased with higher levels of 3. To confirm analytical utility of 3 for % e. e. determinations of 1, a nonracemic (“spiked”) sample of racemic 1, with added R-(?) triadimefon, was examined with 3. At low 3: 1 ratios, both triazole H-3 and H-5, as well as the OCH and aryl H-2′, 6′ protons of (?)-1 showed a downfield sense of magnetic nonequivalence with (+) -3. With 3: 1 ratios ca. 0. 8, triazole proton H-3 reversed its sense of magnetic noneguivalence. The H-3 and H-5 signals were useful for % e. e determinations at this higher 3: 1 ratio.     

The He scattering and reactions on C and cluster states of C

The ⁶He+¹²C elastic and inelastic scattering and the ⁶He+¹²C→α+¹⁴C reaction have been measured using a 18.0 MeV ⁶He beam. Experimental results for the elastic scattering are in fair agreement with optical model predictions, using the potentials found in the analysis of ⁶Li scattering on ¹²C at similar energies. In triple coincidences, the ⁶He+¹²C→¹⁰Be+2α reactions were clearly seen, with the ¹⁰Be nucleus left in ground and several excited states. The dominant mechanism of this reaction is sequential decay through cluster states of ¹⁴C.     

High T c,structural instabilities and electronic properties of Nb3Ge

Abstract

A number of Nb₃Ge samples with rather high T _c,on (T _c,on ? 22.5 K) were prepared by CVD and characterized by the electrical resistance, X-ray diffraction and scanning electron microscope patterns. It was found that the crystal growth patterns are roughly divided into two categories, (i) a particles-pattern in a nearly single phase of Nb₃Ge and (ii) a network pattern with a fairly large amount of the Nb₅Ge₃ phase but with rather a large resistance ratio and a small resistivity at T ? T _c,on. The latter type of samples shows generally higher T _c,on. It is deduced that the origin of high T _c,on comes mainly from a deformation of the atomic potential at the Nb-site into an anharmonic and rather unstable shape due to the coexistence of the Nb₅Ge₃ phase. The mechanism of the formation of different patterns is discussed on the basis of the theory of non-equilibrium thermodynamics of Prigogine.     

Reflection and Absorption Spectra of Fluorite in the UV Spectral Region

We have calculated the R(E) and ₁(E) spectra from the theoretical ₂(E) spectra of five models in the region 8–27 eV and the ₂(E) and ₁(E) spectra from the experimental R(E) spectrum in the region 6–35 eV. The results are compared with the known theoretical ₂(E) spectra of five models. The basic features of all of the R(E), ₂(E), and ₁(E) spectra have been revealed. It is established that the experimental R(E) spectrum and the ₂(E) and ₁(E) spectra calculated with the use of experimental data are in good agreement with the results of theoretical calculations for the models of ₂(E). On the basis of the known theoretical calculations of the fluorite zones, a scheme of the nature of the principal maxima of R(E) and ₂(E) is suggested.