全文获取类型
收费全文 | 97391篇 |
免费 | 934篇 |
国内免费 | 516篇 |
专业分类
化学 | 30719篇 |
晶体学 | 859篇 |
力学 | 7133篇 |
综合类 | 3篇 |
数学 | 33039篇 |
物理学 | 16617篇 |
无线电 | 10471篇 |
出版年
2023年 | 124篇 |
2022年 | 383篇 |
2021年 | 514篇 |
2020年 | 461篇 |
2019年 | 541篇 |
2018年 | 12123篇 |
2017年 | 11670篇 |
2016年 | 7514篇 |
2015年 | 1330篇 |
2014年 | 976篇 |
2013年 | 1506篇 |
2012年 | 4958篇 |
2011年 | 12345篇 |
2010年 | 7348篇 |
2009年 | 7216篇 |
2008年 | 7615篇 |
2007年 | 10034篇 |
2006年 | 540篇 |
2005年 | 1864篇 |
2004年 | 1940篇 |
2003年 | 2354篇 |
2002年 | 1230篇 |
2001年 | 336篇 |
2000年 | 352篇 |
1999年 | 220篇 |
1998年 | 237篇 |
1997年 | 205篇 |
1996年 | 253篇 |
1995年 | 154篇 |
1994年 | 118篇 |
1993年 | 118篇 |
1992年 | 94篇 |
1991年 | 103篇 |
1990年 | 87篇 |
1989年 | 100篇 |
1988年 | 96篇 |
1987年 | 100篇 |
1986年 | 95篇 |
1985年 | 89篇 |
1984年 | 79篇 |
1983年 | 62篇 |
1982年 | 69篇 |
1981年 | 57篇 |
1980年 | 71篇 |
1979年 | 65篇 |
1978年 | 55篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 437 毫秒
961.
Microemulsion-based synthesis of CeO(2) powders with high surface area and high-temperature stabilities 总被引:2,自引:0,他引:2
Bumajdad A Zaki MI Eastoe J Pasupulety L 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):11223-11233
Pure ceria powders, CeO(2), were synthesized in heptane-microemulsified aqueous solutions of CeCl(3) or Ce(NO(3))(3) stabilized by AOT (sodium bis(2-ethylhexyl) sulfosuccinate), DDAB (di-n-didodecyldimethylammonium bromide), or DDAB + Brij 35 surfactant mixtures. Micellar DTAB (n-dodecyltrimethylammonium bromide) and vesicular DDAB systems were also used as media for generating CeO(2). Characterization of the powders by X-ray powder diffractometry, laser-Raman spectroscopy, and Fourier transform infrared spectroscopy revealed that in the presence of surfactants almost-agglomerate-free nanosized crystallites (6-13 nm) of anionic vacancy-free cubic CeO(2) were produced. In the absence of surfactants 21-nm-sized crystallites were formed, comparing with the 85-nm-sized crystallites when cubic CeO(2) was created via thermal decomposition of cerium oxalate. Surface characterization, by X-ray photoelectron spectroscopy, N(2) sorptiometry, and high-resolution electron microscopy showed AOT- or (DDAB + Brij 35)-stabilized microemulsions to assist in formation of crystallites exposing surfaces of large specific areas (up to ca. 250 m(2)/g) but of low stability to high-temperature calcination (28-13 m(2)/g at 800 degrees C). In contrast, the double-chained DDAB was found to generate cubic CeO(2) crystallites of lower initial surface areas (144 (microemulsion) to 125 (vesicles) m(2)/g)) but of higher thermal stability (55-45 m(2)/g at 800 degrees C). Hence, the latter cerias could be considered as appropriate components for total oxidation (combustion) catalysts. 相似文献
962.
Kenji Maeda Ross A. Miller Ali Shafiee Joseph D. Armstrong III 《Tetrahedron letters》2005,46(9):1545-1549
Highly diastereoselective (>20:1) bromo-lactonization of N-sulfonyl-2-allyl-2-phenylglycine methyl ester (11) was observed. Successive treatment of the chiral lactone with MeONa gave the desired (2S,4R)-4-hydroxy-2-phenylproline derivative in high yield without erosion of the diastereoselectivity. The starting chiral non-racemic compound (5) was prepared from the racemic 2-phenylglycine using a classical kinetic resolution (crystallization), an asymmetric phase transfer alkylation, and an enzyme-catalyzed kinetic resolution. 相似文献
963.
The inducing method for preparing Ag-micelle solution with the use of mixed solvent/nonsolvent, and the morphological characterization of the generated metal–micelles were investigated and reported in this paper. In this method, an Ag containing metal chelate polymer (MCP) raw solution was preprepared by dissolving poly(vinyl acetate) (PVAc)–silver nitrate (AgNO3) MCP in conc. formic acid, and a mixed solvent of HCOOH/H2O with specific water composition was then added to induce the micellization of the MCP chain. The critical water concentration (CWC) that was needed for inducing the formation of the Ag-micelles, and the water concentration at which the flocculation of the Ag-micelles occurred in micellar solution, were studied by measuring the transmittance of the dilute MCP solution; the results showed that a long-lasting MCP solution with stable micelles might be prepared by using a H2O/HCOOH solvent of specific weight ratio 1:1.2. The effect of the AgNO3 concentration on the morphology of the Ag-micelles was also investigated by transmission electron microscopy (TEM). At AgNO3 concentration below 0.5 wt%, the Ag-micelles displayed a variety of core-shell structure; but as the AgNO3 concentration was increased to 1.0–2.0 wt%, micelles that had Ag-solid embedded in the micellar core were observed. 相似文献
964.
Binary excess molar volumes, V
m
E, have been evaluated from density measurements, using a vibrating tube densimeter over the entire composition range for binary
liquid mixtures of ionic liquids 1-ethyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [EMIM]+[CH3(OCH2CH2)2OSO3]− or 1-butyl-3-methyl-imidazolium diethyleneglycol monomethylethersulphate [BMIM]+[CH3(OCH2CH2)2OSO3]− or 1-methyl-3-octyl-imidazolium diethyleneglycol monomethylethersulphate [MOIM]+[CH3(OCH2CH2)2OSO3]−+methanol and [EMIM]+[CH3(OCH2CH2)2OSO3]−+water at 298.15, 303.15 and 313.15 K. The V
m
E values were found to be negative for all systems studied. The V
m
E results are explained in terms of intermolecular interactions and packing effects. The experimental data were fitted by the
Redlich-Kister polynomial. 相似文献
965.
Coordination reactions of copper(II) ions and their effect on non-covalent interactions in uridine (Urd) or uridine 5′-monophosphate (UMP) systems with nucleosides (Ado, Cyd, Thd) and nucleotides (AMP and CMP) in aqueous solutions have been studied. At high pH the effective coordination centers are deprotonated N(3) atoms from Urd and Thd, whereas at low pH, the N(3) atoms of pyrimidine nucleosides are blocked for coordination and the metallation sites are endocyclic
nitrogen atoms from Ado, Cyd, AMP and CMP. Moreover, at low pH, the main reaction center in nucleotide solutions is the phosphate group. The NMR study has proven the
occurrence of non-covalent ion-dipole interactions and stacking interactions in the systems considered. Introduction of a
copper ion in the majority of systems causes the disappearance of weak interactions between ligands. The structures of the
complexes in solution have been inferred from the equilibrium study: an analysis of the pH range of their occurrence with
respect to the pH range of deprotonation of particular groups in the compounds studied, using Vis, EPR and 13C as well as 31P NMR spectral analysis. 相似文献
966.
We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant
to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution
of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be
interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical
system of interest. 相似文献
967.
Jeong Hwan Kim Ji Hoon Ko Byeong-Soo Bae 《Journal of Sol-Gel Science and Technology》2007,41(3):249-255
Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix
were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized
by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was
confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist
in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids
in the nano-hybrid materials show enhanced mechanical and thermal characteristics. 相似文献
968.
The geometry of the 4′-cyano-(4′-CNPTB) and the 4′-methoxy-(4′-MePTB) phenylthiolbenzoates were obtained by ab initio calculations
employing 6–31G basis set at Hartee-Fock level of theory. The results predict an extended form of the molecules and torsional
angle between the phenyl rings at 90.85(6)0 and 90.87(3)0, respectively. On the basis of vibrational analysis the frequency assignment was carried out. The calculated frequencies
were compared with the experimental IR spectral data in carbon tetrachloride, carbon disulfide solutions and in solid state. 相似文献
969.
Monitoring nitrite with optical sensing films 总被引:1,自引:0,他引:1
Ali A. EnsafiA. Kazemzadeh 《Microchemical Journal》2002,72(2):193-199
A new, low-cost nitrite sensor was developed by immobilizing a direct indicator dye in an optical sensing film for food and environmental monitoring. This sensor was fabricated by binding Safranine O to a cellulose acetate film that had previously been subjected to an exhaustive base hydrolysis. The membrane has good durability (>12 months) and a short response time (<8 s). Nitrite can be determined for the range of 0.005-2.00 μg ml−1 with 3δ detection limits of 0.001 μg ml−1. The method is easy to perform and uses acetylcellulose as a carrier. The reagents used for the activity of the cellulose support are inexpensive, non-toxic and widely available. 相似文献
970.
František Kvasnička Rudolf Ševčík Michal Voldřich Jana Krátká 《Central European Journal of Chemistry》2004,2(3):417-424
A simple and rapid capillary zone electrophoresis (CZE) method for the determination of aristolochic acid (AA) in dietary
supplements and selected herbs is described. A clear separation of AA from other sample constituents was achieved within 5
minutes without any sample clean up. A mixture of 20 mM-morpholinethanesulphonic acid+10 mM-BisTrisPropane+0.2% hydroxyethylcelullose
in 10% methanol serves as a background electrolyte. The linearity, accuracy, intra-assay and detection limit of the developed
method are 200–6000 ng/mL, 95–103%, 3.5%, and 50 ng/ml, respectively. Ease of use, sufficient sensitivity and low running
cost are the most important attributes of the CZE method. The proposed CZE method was compared with HPLC. 相似文献