全文获取类型
收费全文 | 1425篇 |
免费 | 39篇 |
国内免费 | 7篇 |
专业分类
化学 | 1045篇 |
晶体学 | 15篇 |
力学 | 26篇 |
数学 | 56篇 |
物理学 | 329篇 |
出版年
2022年 | 7篇 |
2021年 | 14篇 |
2020年 | 14篇 |
2019年 | 19篇 |
2018年 | 8篇 |
2016年 | 25篇 |
2015年 | 24篇 |
2014年 | 24篇 |
2013年 | 64篇 |
2012年 | 53篇 |
2011年 | 79篇 |
2010年 | 40篇 |
2009年 | 43篇 |
2008年 | 72篇 |
2007年 | 83篇 |
2006年 | 68篇 |
2005年 | 71篇 |
2004年 | 61篇 |
2003年 | 64篇 |
2002年 | 74篇 |
2001年 | 41篇 |
2000年 | 34篇 |
1999年 | 30篇 |
1998年 | 21篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 11篇 |
1994年 | 13篇 |
1993年 | 17篇 |
1992年 | 38篇 |
1991年 | 21篇 |
1990年 | 20篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 15篇 |
1986年 | 7篇 |
1985年 | 22篇 |
1984年 | 15篇 |
1983年 | 17篇 |
1982年 | 13篇 |
1981年 | 15篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 11篇 |
1975年 | 10篇 |
1974年 | 13篇 |
1973年 | 15篇 |
1968年 | 9篇 |
排序方式: 共有1471条查询结果,搜索用时 31 毫秒
51.
52.
Kiyokawa T Kanaori K Tajima K Kawaguchi M Mizuno T Oku J Tanaka T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3548-3554
The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties. 相似文献
53.
Determination of chemical form of antimony in contaminated soil around a smelter using X-ray absorption fine structure. 总被引:1,自引:0,他引:1
Masaki Takaoka Satoshi Fukutani Takashi Yamamoto Masato Horiuchi Naoya Satta Nobuo Takeda Kazuyuki Oshita Minoru Yoneda Shinsuke Morisawa Tsunehiro Tanaka 《Analytical sciences》2005,21(7):769-773
Only limited information is available about the behavior of antimony (Sb) in contaminated soils. However, understanding the behavior of Sb in contaminated soils is important, because the toxicity or solubility of this element depends on its chemical state. In this study, we investigated the levels of Sb and the chemical forms of Sb in the soil around a smelter using X-ray absorption fine structure (XAFS) spectra. The highest Sb concentration in the contaminated soil was 2900 mg/kg dry soil. According to Sb-K edge X-ray absorption near edge (XANE) spectra, the Sb in the soil was in the form of Sb(V) compounds. The similarity of extended XAFS (EXAFS) spectra suggests that Sb speciation was independent of the sampling site, which indicates that Sb or Sb2O3 emitted from the smelter was converted into Sb(V) compounds in the soil. 相似文献
54.
127I M?ssbauer spectra of good quality were obtained at 20 K using a Zn127mTe source produced by high flux neutron irradiation of 66Zn-126Te at reactor core. The M?ssbauer spectra for KI and some iodine(III) compounds with absorption intensity of about 5% suggest that the 127I M?ssbauer spectroscopy is useful in elucidating the bonding nature of the iodine compounds. Preparative method of the M?ssbauer source and experimental technique are reported in detail. 相似文献
55.
We implemented ab initio self‐consistent field (SCF) fractional occupation numbers (FON) calculation with Dunlap's interpolation scheme for the twisted ethylene, which is a prototype molecule of a σ–π biradical system. The calculational results are compared with those of complete‐active‐space (CAS) SCF and spin‐unrestricted Kohn–Sham (UKS) calculations on potential surfaces, occupation numbers of natural orbitals, and correlation entropies. It was found that the UKS methods gave similar results to CASSCF, while the FON solutions appeared in only the nearly complete degenerate region. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 317–323, 2003 相似文献
56.
[reaction: see text] Reaction of gamma-p-toluenesulfonyl-alpha,beta-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords alpha,beta-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions. 相似文献
57.
The garnet-type fluorides, Na3M2Li3F12 (M = Al, Cr, and Fe) were synthesized as the coprecipitates of ~1 to 10 μm powders from HF solutions. The garnet structures were always obtained under acidic conditions. The incorporation of water molecules into the structure of the Cr and Fe garnets was observed. After heat treatment at 300°C, very small unknown peaks were observed in the X-ray powder pattern in addition to the garnet phase which had a slightly smaller value of the lattice constant than that of hydrous garnets. From the measurement of magnetic properties and Mössbauer effects, the Fe and Cr garnets were found to be paramagnetic with both ions in the trivalent state. Presentation of infrared spectra of the garnets is also included. 相似文献
58.
The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs. 相似文献
59.
The protective effect of an anionic double-tailed surfactant, sodium bis(2-ethylhexyl)sulfosuccinate (AOT), on the structures of human serum albumin (HSA) and bovine serum albumin (BSA) in their thermal denaturations was examined by means of circular dichroism measurements. The structural changes of these albumins were reversible in the thermal denaturation below 50 degrees C, but became partially irreversible above this temperature. The effect was observed in the thermal denaturation above 50 degrees C. Although the helicity of HSA decreased from 66% to 44% at 65 degrees C in the absence of the surfactant, the decrement of it was restrained in the coexistence of AOT of extremely low concentrations. When the HSA concentration was 10 muM, the maximal protective effect appeared at 0.15 mM AOT. In the coexistence of the surfactant of this concentration, the helicity was maintained at 58% at 65 degrees C, increasing to the original value upon cooling to 25 degrees C. Beyond 0.15 mM AOT, the helicity sharply decreased until 3 mM AOT. A particular AOT concentration required to induce the maximal protective effect ([AOT]REQ) was examined at different HSA concentrations. [AOT]REQ shifted to higher values with an increase of the protein concentration. From the protein concentration dependences of [AOT]REQ, the maximal protection was estimated to require 8.0 and 5.0 AOT ions per a molecule of HSA and BSA, respectively. The AOT concentration, where the protective effect was observed, was too low to form its micelle-like aggregate. Then the protein structures might be stabilized by a cross-linking of surfactant monomers bound to specific sites. These specific sites might exist between a group of nonpolar residues and a positively charged residue located on several sets of amphiphilic helical rods in the proteins. Such a unique function of the double-tailed ionic surfactant is first presented by its characteristic nature as an amphiphilic material. 相似文献
60.
A rapid, sensitive and selective high-performance liquid chromatographic method is described for simultaneous determination of eight sulfa drugs in meat and meat products using pre-column derivatization with fluorescamine. The drugs are sulfisomidine, sulfadiazine, sulfamerazine, sulfadimidine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline. The method includes blender extraction of 3-g samples with chloroform, partition with 3 M hydrochloric acid, derivatization with fluorescamine at pH 3.0 and subsequent high-performance liquid chromatographic analysis on a C18 column with fluorescence detection at an excitation wavelength of 405 nm and an emission wavelength of 495 nm. The drugs were separated with a mobile phase of acetonitrile-2% acetic acid (3:5) at 55 degrees C. The average recovery from samples fortified at 0.1 ng/g was 92.6% with a coefficient of variation of 6.2%. The detection limit was 0.01 ng/g for sulfaquinoxaline and 0.005 ng/g for the other seven drugs. The method was field-tested in a survey of 37 samples including beef (five), pork (seven), chicken (seven), ham (five), sausage (eight), bacon (two) and roast beef (three). Sulfadimidine was detected in one pork sample at the level of 0.295 ng/g and in ham at 0.178 ng/g. 相似文献