Characterization of tri-o-methylcellulose by one- and two-dimensional NMR methods

Tri-O-methylcellulose was prepared from partially O-methylated cellulose and its chemical shifts (¹H and ¹³C), and proton coupling constants were assigned using the following NMR methods: (1) One-dimensional ¹H and ¹³C spectra of the title compound were used to assign functional groups and to compare with literature data; (2) double quantum filtered proton–proton correlation spectroscopy (¹H, ¹H DQF-COSY) was used to assign the chemical shifts of the network of 7 protons in the anhydroglucose portion of the repeat unit; (3) the heteronuclear single-quantum coherence (HSQC) spectrum was used to establish connectivities between the bonded protons and carbons; (4) the heteronuclear multiple-bond correlation (HMBC) spectrum was used to connect the hydrogens of the methyl ethers to their respective sugar carbons; (5) the combination of HSQC and HMBC spectra was used to assign the ¹³C shifts of the methyl ethers; (6) all spectra were used in combination to verify the assigned chemical shifts; (7) first-order proton coupling constants data (J_H,H in Hz) were obtained from the resolution-enhanced proton spectra. The NMR spectra of tri-O-methylcellulose and other cellulose ethers do not resemble the spectra of similarly substituted cellobioses. Although the ¹H and ¹³C shifts and coupling constants of 2,3,6-tri-O-methylcellulose closely resemble those of methyl tetra-O-methyl-β-D -glucoside, there are differences with regard to the chemical shifts and the order of appearances of the resonating nuclei of the methyl ether appendages and the proton at position 4 in the pyranose ring. H4 in tri-O-methylcellulose is deshielded by the acetal system comprising the β-1→4 linkage, and it resonates downfield. H4 in the permethylated glucoside is not as deshielded by the equitorial O-methyl group at C4, and it resonates upfield. The order of appearance of the ¹H and ¹³C resonances in the spectra of the tri-O-methylcellulose repeat unit (from upfield to downfield) are H2 < H3 < H5 < H6a < H3a < H2a < pro R H6B < H4 < pro S H6A ≪ H1 and C6a < C3a < C2a < C6 < C5 < C4 < C2 < C3 ≪ C1, respectively. Close examination of the pyranose ring coupling constants of the repeat unit in tri-O-methylcellulose supports the ⁴C₁ arrangement of the glucopyranose ring. Examination of the proton coupling constants about the C5-C6 bond (J_5,6A and J_5,6B) in the nuclear Overhauser effect difference spectra revealed that the C6 O-methyl group is predominantly in the gauche gauche conformation about the C5-C6 bond for the polymer in solution. © 1999 John Wiley & Sons, Inc.* J Polym Sci A: Polym Chem 37: 4019–4032, 1999     

5-芳基-2-呋喃甲醛腙的NMR谱研究

利用变温实验和DPFGSE-NOE实验,确定了5-(3-氯苯基)-2-呋喃甲醛-N-4-甲基苯氧乙酰腙和5-(3-氯苯基)-2-呋喃甲醛-N-4-硝基苯氧乙酰腙两个新化合物25 ℃时在二甲基亚砜中的空间构型,并对这两个新化合物在25 ℃和90 ℃时的质子的化学位移进行了全归属。     

非平均加权采样的重建

主要讨论了在加权的多生成平移不变空间Vv^p(Ф）中由非均匀采样{∫R^df(x)gxj(x)dx:j∈J}来重建信号的问题．同时也讨论了投影逼近迭代算法．     

Multivariate irregular sampling theorem

In this paper,we prove a Marcinkiewicz-Zygmund type inequality for multivariate entire functions of exponential type with non-equidistant spaced sampling points. And from this result,we establish a multivariate irregular Whittaker-Kotelnikov-Shannon type sampling theorem.     

Complete assignments of 1H and 13C NMR data for seven arylnaphthalide lignans from Justicia procumbens

Three new arylnaphthalide lignans named 6'-hydroxy justicidin A (1), 6'-hydroxy justicidin B (2) and 6'-hydroxy justicidin C (3) have been isolated from the whole plant of Justicia procumbens, together with four known ones, neojusticin A (4), chinensinaphthol methyl ester (5), isodiphyllin (6) and taiwanin C (7). The complete assignments of 1H and 13C NMR chemical shifts for the new lignans and the 13C NMR chemical shifts for the known lignans were obtained for the first time by means of 2D NMR techniques, including HSQC and HMBC.     

新型抗肿瘤卡铂类衍生物的氢谱特征

卡铂是第二代铂类金属抗癌药物最重要的药物之一,广泛应用于临床. 为发现抗肿瘤活性更强的卡铂类药物,我们合成了6个新的卡铂类衍生物. 本文详细报道4个合成的新型卡铂衍生物的氢谱特征和归属.      

新药炎琥宁的碳氢NMR信号全归属

炎琥宁为中药提取物穿心莲内酯经结构改造后获得的一个抗菌、抗病毒新药,本文应用1D NMR和脉冲梯度场2D NMR实验技术（gCOSY,gHSQC,gHSQC-TOCOSY,gHMBC）对其结构进行了研究,并首次对其¹H NMR、¹³C NMR谱信号进行了全归属.     

A Control Simulation Method of High-Speed Trains on Railway Network with Irregular Influence

Based on the discrete time method, an effective movement control model is designed for a group of high-speed trains on a rail network. The purpose of the model is to investigate the specific traffic characteristics of high-speed trains under the interruption of stochastic irregular events. In the model, the high-speed rail traffic system is supposed to be equipped with the moving-block signalling system to guarantee maximum traversing capacity of the railway. To keep the safety of trains' movements, some operational strategies are proposed to control the movements of trains in the model, including traction operation, braking operation, and entering-station operation. The numerical simulations show that the designed model can well describe the
movements of high-speed trains on the rail network. The research results can provide the useful information not only for investigating the propagation features of relevant delays under the irregular disturbance but also for rerouting and rescheduling trains on the rail network.     

涡虫代谢物组成的核磁共振分析

作为扁形动物门的代表动物,涡虫因其特殊的演化地位和极强的再生能力,迅速成为实验动物学、细胞遗传学、发育生物学和再生生物学等研究中的理想模式生物. 众多与涡虫相关的研究都取得了突破性进展,而其在核磁共振和代谢组领域的相关科研报道却极为匮乏. 该研究使用甲醇水提取方法获得了涡虫身体提取物样品,同时利用高分辨的1 GHz NMR谱仪对该样品采集了¹H NMR谱图和5种2D NMR谱图（¹H-¹H COSY,¹H-¹H TOCSY,¹H-¹H J-RES,¹H-¹³C HSQC和¹H-¹³C HMBC）. 通过归属得到涡虫身体提取物里所含有的53种代谢物质,包括氨基酸、糖类、脂类、有机羧酸、酮体、胺类、胆碱类以及核苷酸等. 这些物质覆盖了多种代谢途径,为涡虫代谢组研究提供了基本的NMR相关信息.     

The Sensitivity Analysis for the Flow Past Obstacles Problem with Respect to the Reynolds Number

In this paper, numerical sensitivity analysis with respect to the Reynolds number for the flow past obstacle problem is presented. To carry out such analysis, at each time step, we need to solve the incompressible Navier-Stokes equations on irregular domains twice, one for the primary variables; the other is for the sensitivity variables with homogeneous boundary conditions. The Navier-Stokes solver is the augmented immersed interface method for Navier-Stokes equations on irregular domains. One of the most important contributions of this paper is that our analysis can predict the critical Reynolds number at which the vortex shading begins to develop in the wake of the obstacle. Some interesting experiments are shown to illustrate how the critical Reynolds number varies with different geometric settings.