全文获取类型
收费全文 | 406篇 |
免费 | 80篇 |
国内免费 | 31篇 |
专业分类
化学 | 276篇 |
晶体学 | 2篇 |
力学 | 12篇 |
综合类 | 2篇 |
数学 | 20篇 |
物理学 | 99篇 |
综合类 | 106篇 |
出版年
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 9篇 |
2020年 | 19篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 12篇 |
2016年 | 23篇 |
2015年 | 19篇 |
2014年 | 32篇 |
2013年 | 36篇 |
2012年 | 20篇 |
2011年 | 26篇 |
2010年 | 24篇 |
2009年 | 22篇 |
2008年 | 23篇 |
2007年 | 36篇 |
2006年 | 28篇 |
2005年 | 21篇 |
2004年 | 19篇 |
2003年 | 23篇 |
2002年 | 17篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 14篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有517条查询结果,搜索用时 15 毫秒
1.
Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007. 相似文献
2.
Fumio Sanda Ritsuya Kawasaki Masashi Shiotsuki Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2007,45(19):4450-4458
Novel chiral acetylene monomers containing carbazole, 2‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 1 ), 3‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 2 ), 2‐ethynyl‐9‐[(S)‐2‐methylbutyl]carbazole ( 3 ), and 2‐ethynyl‐9‐[(S)‐4‐methylhexyl]carbazole ( 4 ) were synthesized and polymerized with [(nbd)RhCl]2? Et3N. The corresponding polyacetylenes with number‐average molecular weights ranging from 68,700 to 310,000 were obtained in good yields. Poly( 1 ) exhibited a large specific rotation and an intense Cotton effect in toluene, indicating that it formed a helix with predominantly one‐handed screw sense, while the other three polymers showed no evidence for taking a helical structure. Poly( 1 ) largely decreased the CD intensity upon heating from ?10 to 60 °C. Poly( 1 ) showed a Cotton effect in film state in a manner similar to solution state. No chiral amplification was observed in the copolymerization of 1 with achiral 2‐ethynyl‐9‐tert‐butoxycarbonylcarbazole ( 5 ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4450–4458, 2007 相似文献
3.
The viscosities of aqueous solutions of gelatin at different temperatures were carefully measured in a common glass‐capillary Ubbelohde viscometer at dilute to extremely dilute concentrations. The adsorption effect that occurred in the viscosity measurements was theoretically analyzed and discussed. A theory based on Langmuir isotherms could adequately describe the existing data. Some structural information was obtained by the use of an iterative fitting procedure to treat the reduced viscosity data, which disclosed that individual gelatin chains underwent a coil‐to‐helix transition as the solution cooled from 40 to 15 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1804–1812, 2006 相似文献
4.
Arijit BanerjeeSamir Kumar Maji Michael G.B. DrewDebasish Haldar Arindam Banerjee 《Tetrahedron letters》2003,44(4):699-702
A single-crystal X-ray diffraction study of the terminally protected tetrapeptide Boc-β-Ala-Aib-Leu-Aib-OMe 1 (Aib: α-aminoisobutyric acid; β-Ala: β-Alanine) reveals that it adopts a new type of double turn structure which self-associates to form a unique supramolecular helix through intermolecular hydrogen bonds. Scanning electron microscopic studies show that peptide 1 exhibits amyloid-like fibrillar morphology in the solid state. 相似文献
5.
The conformational transformation of a 30-residue peptide H(Ala-Gly-Ser-Gly-AIa-Gly)5OH, i.e., (AGSGAG)5, extracted from highly crystalline region of Bombyx mori (B. mori) silk fibroin was described by using the high resolution solid state 13^C NMR, and CD spectroscopies. Based on the conformation-dependent 13^C NMR chemical shifts of the Ala, Gly and Ser residues and the line-shape analysis of the conformation sensitive Ala Cβ resonance, the peptide revealed a strong preference for silk Ⅱ structural form, i,e,, an antiparallel fl-sheet structure (φ= - 140±20°and ψ= 135±20°) in solid state. On the contrary, the CD spectra of this peptide in the two non-native hexafluorinated fibre spinning solvents, hexafluoroisopropanol (HFIP) and hexafluoroacetone (HFA), exhibited the existence of an unusual tightly-folded conformation resembling 310-helix (φ=- 60±20° and ψ=-30±20°), as judged from the R ratio of [θ]222/[θ]203 in HFIP solution, whereas a dynamically averaged unordered structure in HFA, Taken together, the information inclined to hypothesis that the primary structure of the highly crystalline regions of B. mori silk fibroin may be easily accessible to the large conformational changes, which in turn may be critical for facilitating the structural transformation from unprocessed silk fibroin (silk I form) to processed silk fiber (silk Ⅱform). 相似文献
6.
Halogen bonding has been used to hold two hydrogen bonded aromatic amide foldamers to form supramolecular macrocycles. 相似文献
7.
大气压旋转螺旋状电极辉光放电等离子体催化甲烷偶联 总被引:2,自引:0,他引:2
采用新研制的具有旋转螺旋状电极的大气压辉光放电等离子体反应器催化甲烷偶联制碳二烃. 实验采用铜电极和不锈钢电极分别考察了输入电场峰值电压和甲烷、氢气进料流量等参数对甲烷转化率和碳二烃收率、选择性的影响. 在长时间连续反应无明显积碳的情况下, 最佳试验结果是电极材料为金属铜, 进料流量为60 mL•min-1, V(CH4 )/V(H2)=1的条件下, 输入电场峰值电压为2.3 kV时, 甲烷转化率为70.64%, 碳二烃单程收率及其选择性分别为69.85%和 99.14%. 相似文献
8.
A novel doublet chirality transfer (DCT) model was demonstrated in cis poly(3,5‐disubstituted phenylacetylene)s, i.e., S‐I , R‐I , and S‐I‐NMe . The chiral message from the stereocenter of alkylamide substituent at 3‐position induced the polyene backbone to take cis‐transoid helical conformation with a predominant screw sense. And in turn the helical backbone acted as a scaffold to orient the pyrene probes, which was linked to phenyl rings through 5‐position, to array in an asymmetric manner. A combinatory analyses of 1H NMR, Raman, FTIR, UV‐vis absorption, CD, and computer simulation suggested that the main‐chain stereostructure, solvent nature, and intramolecular hydrogen bonds played important and complex roles on DCT. High cis‐structure content and intramolecular hydrogen bonds were beneficial for the realization of DCT. Reversible helix‐helix transition was observed in S‐I by changing the nature of solvents. In DMF, S‐I adopted a relatively contracted helix, where the main chain exhibited strong optical activity, but that of pyrene was weak. In contrast, a relatively stretched helix formed in CHCl3, in which the optical activity of pyrene was much larger, whereas that of the polyene backbone was the weakest. This helix‐helix transition was attributed to the intramolecular hydrogen bonds, which was confirmed by solution‐state FTIR spectra and computer calculations. 相似文献
9.
Lancelot N Elbayed K Raya J Piotto M Briand JP Formaggio F Toniolo C Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1317-1323
A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis. 相似文献
10.
测头的调整对齿向精度测量结果的影响 总被引:2,自引:1,他引:2
黄富贵 《华侨大学学报(自然科学版)》1997,18(3):275-278
分析在万能工具显微镜上测头接触高度位置的调整误差,对斜齿轮分度圆螺旋角误差和齿向误差测量结果的影响,理论和实验结果表明,测头接触高度位置的变化地分度圆旋角误差测量结果没有影响,而对齿向误差测量结果的影响。 相似文献