全文获取类型
收费全文 | 9568篇 |
免费 | 194篇 |
国内免费 | 60篇 |
专业分类
化学 | 6596篇 |
晶体学 | 147篇 |
力学 | 254篇 |
数学 | 1706篇 |
物理学 | 1119篇 |
出版年
2021年 | 57篇 |
2020年 | 69篇 |
2019年 | 82篇 |
2018年 | 75篇 |
2017年 | 66篇 |
2016年 | 154篇 |
2015年 | 149篇 |
2014年 | 155篇 |
2013年 | 478篇 |
2012年 | 390篇 |
2011年 | 461篇 |
2010年 | 229篇 |
2009年 | 219篇 |
2008年 | 432篇 |
2007年 | 460篇 |
2006年 | 440篇 |
2005年 | 465篇 |
2004年 | 384篇 |
2003年 | 423篇 |
2002年 | 341篇 |
2001年 | 155篇 |
2000年 | 141篇 |
1999年 | 124篇 |
1998年 | 92篇 |
1997年 | 142篇 |
1996年 | 153篇 |
1995年 | 153篇 |
1994年 | 145篇 |
1993年 | 132篇 |
1992年 | 98篇 |
1991年 | 124篇 |
1990年 | 98篇 |
1989年 | 109篇 |
1988年 | 117篇 |
1987年 | 93篇 |
1986年 | 92篇 |
1985年 | 148篇 |
1984年 | 175篇 |
1983年 | 116篇 |
1982年 | 169篇 |
1981年 | 167篇 |
1980年 | 153篇 |
1979年 | 152篇 |
1978年 | 146篇 |
1977年 | 144篇 |
1976年 | 129篇 |
1975年 | 115篇 |
1974年 | 116篇 |
1973年 | 114篇 |
1972年 | 60篇 |
排序方式: 共有9822条查询结果,搜索用时 31 毫秒
101.
102.
103.
104.
Interactions of dendrimers with selected amino acids and proteins studied by continuous wave EPR and Fourier transform EPR 总被引:1,自引:0,他引:1
Ottaviani MF Jockusch S Turro NJ Tomalia DA Barbon A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):10238-10245
Interactions of polyamidoamine dendrimers, termed Gn, where n indicates the generation (=number of amidoamine layers), at different protonation levels with selected amino acids and proteins have been investigated by means of continuous wave electron paramagnetic resonance (cw-EPR) and pulsed-EPR (electron spin-echo = ESE) analyses. A low-generation dendrimer (G2) and a high-generation one (G6) were labeled with nitroxides for the EPR measurements. Gly, Glu, Arg, and Leu were selected as representative of neutral(zwitterionic)-polar, acidic, basic, and low-polar amino acids, respectively. The water-soluble proteins alpha-chymotrypsin and albumin were selected on the basis of a basic and an acidic isoelectric point, respectively. The cw-EPR spectra were analyzed by computing the line shapes to extract information about the dendrimer-biomolecule interactions. In general, dendrimers at a high protonation level interact stronger with amino acids than those at a low level of protonation. However, even for highly protonated dendrimers, a synergistic effect between hydrophilic and hydrophobic interactions promoted the formation of stable Gn-amino acid adducts, as demonstrated by the enhanced interactions with Leu. As expected from acid-base interactions, stable adducts were formed between Arg and highly protonated dendrimers and between Glu and low level protonated dendrimers. The relatively strong dendrimer interactions with the protein chymotrypsin and the poor interactions of dendrimers with albumin demonstrated that the protonated amino groups of the dendrimers are predominantly involved in the interactions with these proteins and indicated a significant role in the interactions with the dendrimers of the hydrophobic external residues of chymotrypsin. Computer-aided analysis of the ESE experiments was consistent with the cw-EPR results and supported the conclusion of a partial complexation of the nitroxides of the dendrimer with Leu and alpha-chymotrypsin. 相似文献
105.
Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment
Chen SY Cressman S Mao F Shao H Low DW Beilan HS Cagle EN Carnevali M Gueriguian V Keogh PJ Porter H Stratton SM Wiedeke MC Savatski L Adamson JW Bozzini CE Kung A Kent SB Bradburne JA Kochendoerfer GG 《Chemistry & biology》2005,12(3):371-383
Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future. 相似文献
106.
N-Alkoxycarbonyl- and N-carboxamido-oxaziridines are shown to react with aromatic alkenes to give epoxide, aziridine or hydro-oxidation products, in ratios depending on the oxaziridine structure. Chiral oxaziridines can effect epoxidation and hydro-oxidation with promising levels of asymmetric induction. 相似文献
107.
The first molal hydrolysis quotient, Q1.1, of Mg2+ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the
magnesium in solution could be followed before precipitation of brucite, Mg(OH)2(cr), occurred. The log Q1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants
are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported:
logK
1.1 = -11.68±0.05, †Hso = 70.1±1.2 kJ-mol-1, †So = 11±4 J-K-1-mol-1, and †C
p
o
= 0 J-K-1-mor-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis
reaction was zero,i.e., logQ
1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The
hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent
density using published results obtained at these extreme conditions. 相似文献
108.
The incorporation of explicit ions to mimic the effect of ionic strength or to neutralize the overall charge on a system in free energy calculations using molecular dynamics simulations is investigated. The difference in the free energy of hydration between two triosephosphate isomerase inhibitors calculated at five different ion concentrations is used as an example. We show that the free energy difference can be highly sensitive to the presence of explicit ions even in cases where the mutation itself does not involve a change in the overall charge. The effect is most significant if the molecule carries a net charge close to the site mutated. Furthermore, it is shown that the introduction of a small number of ions can lead to very severe sampling problems suggesting that in practical calculations convergence can best be achieved by incorporating either no counterions or by simulating at high ionic strength to ensure sufficient sampling of the ion distribution. 相似文献
109.
[reaction: see text] Gamma,delta-unsaturated beta-diketones have been prepared by the acylation of ketones with N-acylbenzotriazoles of various aliphatic and aromatic alpha,beta-unsaturated carboxylic acids. 相似文献
110.
Shoeib T Cunje A Hopkinson AC Siu KW 《Journal of the American Society for Mass Spectrometry》2002,13(4):408-416
Collision-induced dissociation experiments on the Ag+-phenylalanine complex using several collision energies were shown to yield ten different fragment ions. Unambiguous assignment of these fragment ions were made by careful analysis of deuterium labeling experiments. The losses of H2O, CO, CO2, and AgH were commonly observed; also encountered were the losses of H2, Ag, and H. Deuterium labeling experiments and density functional calculations have been employed to probe fragmentation mechanisms that account for all experimental results. 相似文献