全文获取类型
收费全文 | 1933篇 |
免费 | 285篇 |
国内免费 | 259篇 |
专业分类
化学 | 1495篇 |
晶体学 | 129篇 |
力学 | 222篇 |
综合类 | 24篇 |
数学 | 48篇 |
物理学 | 559篇 |
出版年
2023年 | 12篇 |
2022年 | 26篇 |
2021年 | 61篇 |
2020年 | 67篇 |
2019年 | 58篇 |
2018年 | 46篇 |
2017年 | 64篇 |
2016年 | 85篇 |
2015年 | 63篇 |
2014年 | 85篇 |
2013年 | 169篇 |
2012年 | 95篇 |
2011年 | 127篇 |
2010年 | 95篇 |
2009年 | 100篇 |
2008年 | 105篇 |
2007年 | 137篇 |
2006年 | 94篇 |
2005年 | 97篇 |
2004年 | 107篇 |
2003年 | 100篇 |
2002年 | 72篇 |
2001年 | 80篇 |
2000年 | 78篇 |
1999年 | 57篇 |
1998年 | 38篇 |
1997年 | 56篇 |
1996年 | 51篇 |
1995年 | 45篇 |
1994年 | 52篇 |
1993年 | 35篇 |
1992年 | 18篇 |
1991年 | 21篇 |
1990年 | 12篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1987年 | 1篇 |
1986年 | 4篇 |
1985年 | 14篇 |
1984年 | 11篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 9篇 |
排序方式: 共有2477条查询结果,搜索用时 125 毫秒
91.
Howell EE Shukla U Hicks SN Smiley RD Kuhn LA Zavodszky MI 《Journal of computer-aided molecular design》2001,15(11):1035-1052
R67 dihydrofolate reductase (DHFR) is a novel enzyme that confers resistance to the antibiotic trimethoprim. The crystal structure of R67 DHFR displays a toroidal structure with a central active-site pore. This homotetrameric protein exhibits 222 symmetry, with only a few residues from each chain contributing to the active site, so related sites must be used to bind both substrate (dihydrofolate) and cofactor (NADPH) in the productive R67 DHFR?NADPH?dihydrofolate complex. Whereas the site of folate binding has been partially resolved crystallographically, an interesting question remains: how can the highly symmetrical active site also bind and orient NADPH for catalysis? To model this ternary complex, we employed DOCK and SLIDE, two methods for docking flexible ligands into proteins using quite different algorithms. The bound pteridine ring of folate (Fol I) from the crystal structure of R67 DHFR was used as the basis for docking the nicotinamide-ribose-Pi (NMN) moiety of NADPH. NMN was positioned by both DOCK and SLIDE on the opposite side of the pore from Fol I, where it interacts with Fol I at the pore's center. Numerous residues serve dual roles in binding. For example, Gln 67 from both the B and D subunits has several contacts with the pteridine ring, while the same residue from the A and C subunits has several contacts with the nicotinamide ring. The residues involved in dual roles are generally amphipathic, allowing them to make both hydrophobic and hydrophilic contacts with the ligands. The result is a `hot spot' binding surface allowing the same residues to co-optimize the binding of two ligands, and orient them for catalysis. 相似文献
92.
The degradation of unsaturated polyesters crosslinked with styrene was performed in sub-critical water (SCW) in the absence and presence of organic additives. The unsaturated polyesters were de-crosslinked by hydrolysis of ester chains to form polystyrene derivatives on SCW treatment at 300 °C. With an increase in treating time, carboxylic acid groups in the polystyrene derivatives were turned into carboxylic anhydride groups in SCW. The de-crosslinking rate was much enhanced on SCW treatment in the presence of hydroxy compounds with a long alkyl chain and alkylamines, while carboxylic acids, benzenesulfonate salts, and quaternary ammonium salts were ineffective even though they had a long alkyl chain. The degree of de-crosslinking was reduced in the presence of diamines and amino acids because re-crosslinking at both ends of the additive molecules proceeded. 相似文献
93.
Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time. 相似文献
94.
G. H. Hu S. Lorek Y. Holl M. Lambla 《Journal of polymer science. Part A, Polymer chemistry》1992,30(4):635-641
The aminolysis of poly(styrene-co-methyl acrylate) (SMA) by octadecylamine in solution and in the melt has been reported in Part I. We now have studied the aminolysis of poly(ethylene-co-methyl acrylate) (EMA) with the same amine in the melt and compared the two sets of data in this paper. With EMA, the data confirmed and precised the catalytic mechanism proposed in Part I. The best tautomeric catalysts are the ones which form an eight-atom ring structure with the ester and amine groups. With EMA aminolysis is faster than with SMA because of the steric hindrance of phenyl groups in SMA. But EMA aminolysis remains a rather slow reaction. In a corotating twin-screw extruder the conversion was only around 4% at 220°C with a mean residence time of 150 s. It was also shown that the EMA/octadecylamine/catalyst system, like the SMA system, is homogeneous in the molten state at temperatures around 200°C. 相似文献
95.
The thermal properties, i.e., heat capacity, enthalpy, entropy, and Gibbs function, and the transition behavior of the copolymer system of 4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid have been studied based on differential scanning calorimetry. The heat capacities of the glass, crystal, and anisotropic melt are shown to be largely additive on a molar basis. Additivity is lost in the two transition regions, glass transition and disordering transition. Isothermal crystallization experiments on the copolymers revealed the existence of two types of crystals which melt at high temperature (fast-grown crystals) and low temperature (slowly grown crystals). The ATHAS computation method is used to bring heat capacities of the solid state into agreement with approximate frequency spectra. The changes in heat capacity at the glass transitions occur at 434°K for the poly(oxy-1,4-benzoyl) [33.2 J/(K mol)] and at 420°K for poly(oxy-2,6-naphthoyl) [46.5 J/(K mol)]. The copolymers have a transition range of above 100°K. The anisotropic melt is linked to the well-known condis state of poly(oxy-1,4-benzoyl) by a continuous changes in disorder and mobility without an additional first-order transition. 相似文献
96.
Extrudate swell behaviors of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts in a dual channel die, having mixed circular/slit flow channels, in a constant shear rate rheometer were examined. The extrudate swell ratio for PS melt was observed to be higher than that for LLDPE melt for all cases, this being associated with the differences in molecular structures that could be described in terms of power law indexes and secondary flows near the die entrance. In single channel die, the extrudate swell of both PS and LLDPE melts in circular flow channel die was greater than that in slit flow channel, whereas, in dual channel die the slit channel exhibited a higher extrudate swell ratio, the results being explained by revealing the flow patterns of the melt in the barrel and die of the rheometer. It was found that the dimensionless size of the vortex flows near the entrance, and the extent of disentanglement of molecular chains on entering the die were the important factors for the differences in the extrudate swell ratios of the melts at the die exit influenced by the die designs used. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
97.
《Journal of Polymer Science.Polymer Physics》2018,56(10):803-813
Superheated water (shH2O) is investigated as a process aid in conventional aliphatic polyamide (PA) systems. The polymers investigated include PA 6 (PA6), PA 6,6 (PA66), PA 6,12 (PA612), and PA 12 (PA12). It is shown that the PA melting and crystallization temperatures are significantly reduced when exposed to shH2O. For example, the melting temperature of PA6 is depressed from 206 to 153 °C in the presence of shH2O. A relationship between amide group density and thermal transition temperature reduction is observed. Processing these materials in shH2O has led to a variety of materials ranging from low‐density foams to higher density locally anisotropic foamed morphologies. In situ observations of PAs melting in the presence of shH2O are performed using a specially designed reactor. Results from these experiments are used to estimate the diffusion coefficient of shH2O in PA6. Finally, low‐temperature extrusion is performed with PA6 and shH2O at temperatures as low as 180 °C and mixture viscosity is estimated. A 20‐fold depression in the melt viscosity of PA6 is observed at 240 °C with shH2O. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 803–813 相似文献
98.
A magnetic cotton/polyester fabric with photocatalytic, sonocatalytic, antibacterial and antifungal activities was successfully prepared through in-situ sonosynthesis method under ultrasound irradiation. The process involved the oxidation of Fe2+ to Fe3+ via hydroxyl radicals generated through bubbles collapse in ultrasonic bath. The treated samples were analyzed by X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy and vibrating sample magnetometry. Photocatalytic and sonocatalytic activities of magnetite treated fabrics were also evaluated toward Reactive Blue 2 decoloration under sunlight and ultrasound irradiation. Central composite design based on response surface methodology was applied to study the influence of iron precursor, pH and surfactant concentration to obtain appropriate amount for the best magnetism. Findings suggested the potential of one-pot sonochemical method to synthesize and fabricate Fe3O4 nanoparticles on cotton/polyester fabric possessing appropriate saturation magnetization, 95% antibacterial efficiency against Staphylococcus aureus and 99% antifungal effect against Candida albicans, 87% and 70% dye photocatalytic and sonocatalytic decoloration along with enhanced mechanical properties using only one iron rich precursor at low temperature. 相似文献
99.
Robert Z. Greenley 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):427-443
Recalculation of reactivity ratios has led to improved Q and e values for a variety of monomers. 相似文献
100.