全文获取类型
收费全文 | 8708篇 |
免费 | 1305篇 |
国内免费 | 919篇 |
专业分类
化学 | 6909篇 |
晶体学 | 101篇 |
力学 | 371篇 |
综合类 | 94篇 |
数学 | 773篇 |
物理学 | 2684篇 |
出版年
2024年 | 25篇 |
2023年 | 128篇 |
2022年 | 246篇 |
2021年 | 245篇 |
2020年 | 337篇 |
2019年 | 346篇 |
2018年 | 251篇 |
2017年 | 235篇 |
2016年 | 428篇 |
2015年 | 448篇 |
2014年 | 493篇 |
2013年 | 666篇 |
2012年 | 696篇 |
2011年 | 693篇 |
2010年 | 566篇 |
2009年 | 484篇 |
2008年 | 643篇 |
2007年 | 522篇 |
2006年 | 493篇 |
2005年 | 464篇 |
2004年 | 394篇 |
2003年 | 345篇 |
2002年 | 293篇 |
2001年 | 234篇 |
2000年 | 191篇 |
1999年 | 156篇 |
1998年 | 109篇 |
1997年 | 92篇 |
1996年 | 90篇 |
1995年 | 76篇 |
1994年 | 66篇 |
1993年 | 59篇 |
1992年 | 62篇 |
1991年 | 57篇 |
1990年 | 34篇 |
1989年 | 25篇 |
1988年 | 28篇 |
1987年 | 26篇 |
1986年 | 23篇 |
1985年 | 25篇 |
1984年 | 20篇 |
1983年 | 12篇 |
1982年 | 12篇 |
1981年 | 15篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 10篇 |
1974年 | 11篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
901.
Chiang C. Mei 《Transport in Porous Media》1992,9(3):261-274
The theory of homogenization which is a rigorous method of averaging by multiple scale expansions, is applied here to the transport of a solute in a porous medium. The main assumption is that the matrix has a periodic pore structure on the local scale. Starting from the pores with the Navier-Stokes equations for the fluid motion and the usual convective-diffusion equation for the solute, we give an alternative derivation of the three-dimensional macroscale dispersion tensor for solute concentration. The original result was first found by Brenner by extending Brownian motion theory. The method of homogenization is an expedient approach based on conventional continuum equations and the technique of multiple-scale expansions, and can be extended to more complex media involving three or more contrasting scales with periodicity in every but the largest scale. 相似文献
902.
Xin Ping Ouyang Pan Zhang Chun Mei Tan Yong Hong Deng Dong Jie Yang Xue Qing Qiu 《中国化学快报》2010,21(12):1479-1481
<正>Lignosulfonate with low polydispersity index of 1.178-1.210 was isolated by gel column chromatography of Sephacryl S-100 eluted with 0.2 mol/L of NaNO_3 aqueous solution,whereas nearly monodisperse ligosulfonate fraction with polydispersity of 1.0(57 can be obtained after chromatographic separation twice.This method provides an available approach to investigate the structure and characteristics of lignosulfonate. 相似文献
903.
<正>The synthesis and mesomorphic properties of a new class of liquid crystalline cyclotriphosphazenes with rigid cyanostilbene groups and flexible alkoxy groups are reported.The thermal behaviors of cyclotriphosphazene derivatives 5a-5d are studied by the means of differential scanning calorimetry,polarizing optical microscopy.Nematic phases were observed in compounds 5a-5d both on heating and cooling.The clear temperatures of compounds 5a-5d slightly increased with increasing length of terminal alkyl chain.Compounds 5a-5d showed different mesogenic region from minimum 5℃to maximum 142℃. 相似文献
904.
<正>One chloride-terminated ionic liquid(CTIL) and two hydroxyl-terminated ionic liquids(HTILs) were synthesized and used as stationary phases for capillary gas chromatography(CGC).Molecular interactions of these stationary phases were evaluated by Abraham solvation parameter model,indicating that the CTIL exhibits remarkably strong H-bond basicity and the HTILs possess both H-bond basicity and acidity.The molecular interactions were further confirmed by separation of a complex mixture consisting of ketones,aldehydes,esters,alcohols and aromatic compounds.It was found that the obtained solvation parameters correlate well with the chromatographic performances of the analytes in terms of elution order and resolution.The well correlated relationship between the solvation parameters and the selectivity of the CTIL and HTILs stationary phases is quite helpful in predicting and understanding the retention behaviors of different types of analytes on these stationary phases. 相似文献
905.
<正>A novel polyamide containing xanthene structure and trifluoromethylphenoxy pendent was prepared from 9,9-bis[4-(4- aminophenoxy)phenyl]xanthene,a novel diamine with 2-(4-trifluoromethylphenoxy)terephthaloyl chloride,by the low temperature polycondensation.This new polyamide with the inherent viscosity of 0.95 dL/g was amorphous and readily soluble in polar solvents such as DMAc,m-cresol,etc.This polyamide showed the glass transition temperature(T_g) of 236℃,decomposition temperature (Td) at 5%weight loss of 455℃and char yield of 56%at 800℃in N_2.Transparent,flexible,and tough film of the polymer cast from DMAc solution exhibited tensile strength of 93 MPa,elongation at break of 14%,initial moduli of 2.2 GPa.The electric properties such as the dielectric constant of 3.03(1 MHz) and surface resistance(2.78×10~(14)Ω),and the moisture uptake of 1.36% were also described. 相似文献
906.
Differential proteins expressing in ectopic and eutopic endometria were investigated by means of proteomic analysis. Five patients in secretary phase were diagnosed as endometriosis by laparoscopy. The five ectopic endometria(two at stage Ⅱ, two at stage Ⅲ and one at stage IV) and five eutopic endometria were surgically excised. One-dimensional electrophoresis coupled with liquid chromatography and mass spectrometry was used to screen and identify differential proteins. Three differential bands in one-dimensional electrophoresis were resolved by liquid chromatography and mass spectrometry and 14 up-regulated proteins were identified, including collagen α-1, α-2, α-3(VI), α-1(XIV) chain, actin, annexin A2, EMILIN-1, ferritin light polypeptide variant, fucosyltransferase 10, myosin-9, protein S100-A9, KIAA1783 protein, and two hypothetical proteins. Our data provides a list of potential biomarkers for endometriosis. The identifications may be used to develop new diagnoses for endometriosis. 相似文献
907.
Total internal reflection microscopy was used to directly measure the interaction potentials between a micron-sized silica sphere and a flat silica surface in the presence of a linear poly(N-isopropylacrylamide) (PNIPAM) aqueous solution. When the PNIPAM concentration was low, no discernible forces were detected. A further increase in PNIPAM concentration resulted in a long-range attraction which was likely due to a combined of the reduced electrostatic interaction between the silica particle and the flat surface after the polymer adsorption and polymer bridges formation. On the other hand, for a fixed PNIPAM concentration, the interaction potential profiles between the particle and flat surface were once again characterized by attraction as temperature was increased. This attractive force can be explained in terms of the conformational changes of PNIPAM chains at the surfaces, which subsequently affected the polymer adsorption and enhanced the segment–segment interaction among the adsorbed polymer chains. 相似文献
908.
Luo Mei Sun Jie Zhou Shi-Ming Yin Hao Hu Ke-Liang 《Research on Chemical Intermediates》2010,36(9):1049-1054
Two opposite configuration (R/S) of chiral complexes (C8H11N)2·CuCl2 were obtained from the reaction of chiral d(+)/l(−)-α-ethylphenyl amine with copper chloride (II) in dry ethanol. The crystal structures of 1a and 1b were characterized by
IR, elemental analysis and X-ray crystallography. 相似文献
909.
Ming‐Zhong Wang Cong‐Ying Zhou Man‐Kin Wong Dr. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5723-5735
Ruthenium porphyrins (particularly [Ru(2,6‐Cl2tpp)CO]; tpp=tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles to 3‐{[(N‐aryl‐N‐alkyl)amino]methyl}indoles (yield: up to 82 %, conversion: up to 95 %) and the alkylation of N‐alkyl or N‐H indoles to 3‐[p‐(dialkylamino)benzyl]indoles (yield: up to 73 %, conversion: up to 92 %). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 C? H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N‐arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three‐component coupling reaction of the in situ generated formaldehyde with an N‐alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium‐labeling experiments are consistent with the alkylation of N‐alkylindoles via pathway B. The relative reaction rates of [Ru(2,6‐Cl2tpp)CO]‐catalyzed oxidative coupling reactions of 4‐X‐substituted N,N‐dimethylanilines with N‐phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants σ (R2=0.989), giving a ρ value of ?1.09. This ρ value and the magnitudes of the intra‐ and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4‐X‐substituted N,N‐dimethylanilines. Ruthenium‐catalyzed three‐component reaction of N‐alkyl/N‐H indoles, paraformaldehyde, and anilines gave 3‐[p‐(dialkylamino)benzyl]indoles in up to 82 % yield (conversion: up to 95 %). 相似文献
910.
Eric Chi‐Ho Kwok Dr. Mei‐Yee Chan Dr. Keith Man‐Chung Wong Dr. Wai Han Lam Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(40):12244-12254
A series of platinum(II) alkynyl‐based sensitizers has been synthesized and found to show light‐to‐electricity conversion properties. These dyes were developed as sensitizers for the application in nanocrystalline TiO2 dye‐sensitized solar cells (DSSCs). Their photophysical and electrochemical properties were studied. The excited‐state property was probed using nanosecond transient absorption spectroscopy, which showed the formation of a charge‐separated state that arises from the intramolecular photoinduced charge transfer from the platinum(II) alkynylbithienylbenzothiadiazole moiety (donor) to the polypyridyl ligand (acceptor). A lifetime of 3.4 μs was observed for the charge‐separated state. A dye‐sensitized solar cell based on one of the complexes showed a short‐circuit photocurrent of 7.12 mA cm?2, an open circuit voltage of 780 mV, and a fill factor of 0.65, thus giving an overall power conversion efficiency of 3.6 %. 相似文献