全文获取类型
收费全文 | 2040篇 |
免费 | 164篇 |
国内免费 | 373篇 |
学科分类
数理化 | 2577篇 |
出版年
2024年 | 7篇 |
2023年 | 59篇 |
2022年 | 149篇 |
2021年 | 139篇 |
2020年 | 76篇 |
2019年 | 66篇 |
2018年 | 56篇 |
2017年 | 92篇 |
2016年 | 76篇 |
2015年 | 88篇 |
2014年 | 92篇 |
2013年 | 168篇 |
2012年 | 136篇 |
2011年 | 133篇 |
2010年 | 113篇 |
2009年 | 177篇 |
2008年 | 130篇 |
2007年 | 136篇 |
2006年 | 109篇 |
2005年 | 80篇 |
2004年 | 90篇 |
2003年 | 55篇 |
2002年 | 55篇 |
2001年 | 50篇 |
2000年 | 53篇 |
1999年 | 27篇 |
1998年 | 30篇 |
1997年 | 33篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 21篇 |
1993年 | 11篇 |
1992年 | 15篇 |
1990年 | 4篇 |
1989年 | 11篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1976年 | 1篇 |
排序方式: 共有2577条查询结果,搜索用时 15 毫秒
1.
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):87
Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H–1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10−4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10−4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids. 相似文献
2.
A simple method of determining ultra-trace Au in natural water was presented by using graphite furnace atomic absorption spectrophotometry (GFAAS) after in situ enrichment with thiol cotton fiber (TCF). The sample solution was adjusted to pH 1.5-2.0 with HCl, then the water sample was passed through a column packed with 0.10-0.20 g TCF and the flow rate was controlled at 20-40 ml min−1. The effects of interferences, such as complexing and oxidizing agents and other elements adsorbed on TCF were overcome by chemical treatments prior to the desorption of Au. The adsorbed Au was adsorbed with 2.0 ml hot acid, then it was extracted with 1.00 ml methyl isobutylketone (MIBK). For a 5 l water sample, the detection limit of Au is 0.02 ng l−1. The relative standard deviation (R.S.D.) for the determination of 1.44 ng l−1 Au was 9.4%.The method was applied to determine ultra-trace Au both in suspended phase and soluble phase in natural water, the concentrations of total Au in natural water samples range from 0.51 to 67.82 ng l−1. The recovery of added 0.50-6.00 ng l−1 Au was 80-95%. The method is useful in prospecting for Au deposits by means of hydrogeochemical methods. The enrichment is carried out in the field, and then the determination of Au is completed later in the laboratory. 相似文献
3.
CuX(X=Al, Ga, In)分子的势能函数与稳定性的密度泛函研究 总被引:5,自引:3,他引:2
刘风丽 《原子与分子物理学报》2006,23(5):838-842
根据原子分子反应静力学原理导出了CuX(X=Al,Ga,In) 分子基态电子状态及其离解极限,并在B3LYP/LANL2DZ水平上计算了平衡几何、振动频率和解离能.利用Murrell-Sorbie 函数拟合出了解析势能函数,并计算出光谱参数和力常数.计算结果表明该分子体系是稳定存在的,其稳定性排序为 CuAl>CuGa>CuIn. 相似文献
4.
S. Park T. U. Kampen T. Kachel P. Bressler W. Braun D. R. T. Zahn 《Applied Surface Science》2002,190(1-4):376-381
The interaction of Ag and In with a thin film of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) was studied by near-edge X-ray absorption fine structure (NEXAFS). Upon Ag deposition on a PTCDA film of 20 nm thickness the relative intensities and lineshapes, as well as the angular dependence of the spectra remains unchanged, illustrating the formation of a chemically unreactive Ag/PTCDA interface. On the other hand, the adsorption of 0.3 nm In strongly decreases the intensity of the π* resonances in C and O K-edge NEXAFS spectra. This is attributed to a strong charge transfer between In and PTCDA, leading to a redistribution of the charge in the molecule. However, the absence of a strong shift or new features and negligible dependence of peak intensities corresponding to π* resonances on the In thickness indicate that the interaction between In and PTCDA is not accompanied by a covalent bond formation. 相似文献
5.
从4~10周龄药物流产胚胎的生殖嵴和肠系膜组织中分离原始生殖细胞(primordial germ cells,PGCs),培养在添加人重组白血病抑制因子(rh LIF)、人重组碱性成纤维细胞生长因子(rh bFGF)和Forskolin的小鼠饲养层细胞上.经过4~7 d培养,PGCs形成典型的鸟巢状集落.集落在传代过程中保持碱性磷酸酶活性,且胚胎阶段性特异抗原1(SSEA-1)、胚胎阶段性特异抗原3(SSEA-3)免疫荧光染色呈阳性.具有分化潜能的PGCs能在体外连续传代培养12代.结果表明从药物流产胚胎中分离的人类PGCs可以在体外培养成为具有分化潜能的多能性干细胞. 相似文献
6.
钯II催化CO/乙烯共聚加压原位红外光谱研究 总被引:1,自引:1,他引:1
聚酿以其优良的物理、化学性能及原料(CO乙烯)简单易得的优点,在世界范围内已引起人们的普遍关注.为寻找价廉的催化剂或改良高效或(11)一双磷催化剂以推动聚酮的工业化进程,必须对共聚机理进行深入的研究.S;,n[’,’1、DrentP]等人根据对产品主链和端基的分析首先 相似文献
7.
在位分散聚合聚甲基丙烯酸甲酯/二氧化硅纳米复合材料研究 总被引:70,自引:0,他引:70
应用在位分散聚合方法制备了分散相粒径介于130nm左右的聚甲基丙烯酸甲酯/二氧化硅PMMA/SiO2纳米复合材料,并利用SEM,DMA,TGA等手段研究了该体系的性能.结果表明,经表面处理的SiO2无机填料在复合材料基体中分散均匀,界面粘结好.SiO2填充粒子的用量对基体的热稳定性,动态力学行为,光学行为以及拉伸强度,弹性模量,断裂伸长率等力学性能都有较大影响 相似文献
8.
Preparation of flame retardant polyamide 6 composite with melamine cyanurate nanoparticles in situ formed in extrusion process 总被引:1,自引:0,他引:1
This paper is focused on in situ preparation of melamine cyanurate (MCA) nanoparticles from reaction of melamine (MEL) and cyanuric acid (CA) and their flame retardant polyamide 6 (PA6) composite in the extrusion process through a novel reactive processing method. Fourier transform infrared (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were utilized to characterize the in situ formed MCA nanoparticles and their blends with PA6. Introduction of pentaerythritol (LTP) and water-bound plasticizer dioctyl phthalate (DPT) into the extrusion reaction system greatly inhibits the evaporation of water required for melamine and cyanuric acid reaction at high temperature (higher than 180 °C), laying a foundation for successful in situ preparation of MCA through reactive processing. XRD and FT-IR measurements indicate that under the effect of pentaerythritol, dioctyl phthalate and water, melamine really reacts with cyanuric acid to in situ form MCA in extrusion process. The reaction degree is close to 100%. A very important finding through SEM is that the in situ formed MCA particles, which were found to have aspect ratio of about 7.5, radial size in the range of 70-300 nm (mostly 70-90 nm) and crystallite size of less than 22 nm, are uniformly dispersed in the matrix PA6 at nanoscale. The in situ formed MCA nanoparticles greatly improve the flame retardancy and the mechanical properties of flame-retarded PA6 materials, and the introduced plasticizer dioctyl phthalate also ameliorates the related impact property. The obtained flame-retarded PA6 materials have good comprehensive performance with flame retardancy UL-94 V-0 rating at 1.6 and 3.2 mm thickness, tensile strength 48.0 MPa, elongation at break 106.3% and Izod notched impact strength 8.92 kJ/m2. Compared with flame-retarded PA6 material with in situ formed MCA, the one prepared through conventional blending of PA6 with commercial MCA product has improved tensile strength but deteriorated impact strength and flame retardancy. 相似文献
9.
In situ scanning tunneling microscopy (STM) was used to examine the structure of thiocyanate adlayers specifically adsorbed
on Rh(111) in solutions of potassium hydroxide and perchloric acid, both containing potassium thiocyanate (KSCN). An atomically
flat terrace-step structure was consistently observed on Rh(111) surfaces prepared by the flame-annealing-quenching method.
The Rh(111)-(1 × 1) atomic structure was discerned on the atomically flat terrace even in the alkaline solution. High-resolution
STM images disclosed two different structures of the SCN− adlayers, () and (2 × 2), in the alkaline and the acidic media, respectively. In each structure, an individual adsorbed SCN− ion appeared as a single spot with a constant corrugation height in STM images, suggesting that SCN− ions adsorbed predominantly with their
S-ends at particular bonding sites on Rh(111). The difference in the adlayer structure in the two solutions can be attributed
to the interaction between adsorbed SCN− and coadsorbed K+ in the alkaline solution, and is different from that between adsorbed SCN− and H+ in the acidic solution.
Received: 26 February 1997 / Accepted: 3 March 1997 相似文献
10.