全文获取类型
收费全文 | 2271篇 |
免费 | 88篇 |
国内免费 | 32篇 |
专业分类
化学 | 1387篇 |
晶体学 | 12篇 |
力学 | 63篇 |
数学 | 550篇 |
物理学 | 379篇 |
出版年
2023年 | 27篇 |
2022年 | 58篇 |
2021年 | 62篇 |
2020年 | 54篇 |
2019年 | 43篇 |
2018年 | 51篇 |
2017年 | 38篇 |
2016年 | 81篇 |
2015年 | 94篇 |
2014年 | 96篇 |
2013年 | 146篇 |
2012年 | 153篇 |
2011年 | 149篇 |
2010年 | 109篇 |
2009年 | 97篇 |
2008年 | 139篇 |
2007年 | 126篇 |
2006年 | 123篇 |
2005年 | 110篇 |
2004年 | 88篇 |
2003年 | 50篇 |
2002年 | 71篇 |
2001年 | 18篇 |
2000年 | 23篇 |
1999年 | 16篇 |
1998年 | 22篇 |
1997年 | 16篇 |
1996年 | 16篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 22篇 |
1992年 | 15篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 10篇 |
1985年 | 9篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 22篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 9篇 |
1975年 | 5篇 |
1973年 | 5篇 |
1956年 | 6篇 |
排序方式: 共有2391条查询结果,搜索用时 15 毫秒
71.
Silva NL Betancur GJ Vasquez MP Gomes Ede B Pereira N 《Applied biochemistry and biotechnology》2011,163(7):928-936
Current research indicates the ethanol fuel production from lignocellulosic materials, such as residual wood chips from the
cellulose industry, as new emerging technology. This work aimed at evaluating the ethanol production from hemicellulose of
eucalyptus chips by diluted acid pretreatment and the subsequent fermentation of the generated hydrolysate by a flocculating
strain of Pichia stipitis. The remaining solid fraction generated after pretreatment was subjected to enzymatic hydrolysis, which was carried out simultaneously
with glucose fermentation [saccharification and fermentation (SSF) process] using a strain of Saccharomyces cerevisiae. The acid pretreatment was evaluated using a central composite design for sulfuric acid concentration (1.0–4.0 v/v) and solid to liquid ratio (1:2–1:4, grams to milliliter) as independent variables. A maximum xylose concentration of 50 g/L
was obtained in the hemicellulosic hydrolysate. The fermentation of hemicellulosic hydrolysate and the SSF process were performed
in bioreactors and the final ethanol concentrations of 15.3 g/L and 28.7 g/L were obtained, respectively. 相似文献
72.
73.
Perez-Peralta N Contreras M Tiznado W Stewart J Donald KJ Merino G 《Physical chemistry chemical physics : PCCP》2011,13(28):12975-12980
We have explored in silico the potential energy surfaces of the C(5)Li(n)(n-6) (n = 5, 6, and 7) clusters using the Gradient Embedded Genetic Algorithm (GEGA) and other computational strategies. The most stable forms of C(5)Li(5)(-) and C(5)Li(6) are two carbon chains linked by two lithium atoms in a persistent seven membered ring capped by two Li atoms. The other Li atoms are arrayed on the edge of the seven membered ring. In contrast, the global minimum structure for C(5)Li(7)(+) is a bicapped star of D(5h) symmetry. The molecular orbital analysis and computed magnetic field data suggest that electron delocalization, as well as the saturation of the apical positions of the five-membered carbon ring with lithium atoms in C(5)Li(7)(+) plays a key role in the stabilization of the carbon-lithium star. In fact, the planar star sub-structure for the carbon ring are unstable without the apical caps. This is also what has been found for the Si analogues. The split of the B(ind)(z) in its σ- and π-contribution indicates that C(5)Li(7)(+) is a π-aromatic and σ-nonaromatic system. 相似文献
74.
Dr. Zheng Deng Dr. Chang-Jong Kang Prof. Dr. Mark Croft Dr. Wenmin Li Dr. Xi Shen Dr. Jianfa Zhao Prof. Dr. Richeng Yu Prof. Dr. Changqing Jin Prof. Dr. Gabriel Kotliar Dr. Sizhan Liu Prof. Dr. Trevor A. Tyson Dr. Ryan Tappero Prof. Dr. Martha Greenblatt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(21):8317-8323
Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order–disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y2CoIrO6 and Y2CoRuO6 polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6 and Y2CoRuO6. 相似文献
75.
Evangelia‐Eirini N. Vlachou Catherine Gabriel Konstantinos E. Litinas 《Journal of heterocyclic chemistry》2019,56(1):99-107
Dipetalolactone and 4‐methyldipetalolactone are prepared in excellent yield by a one‐pot tandem propargylation/Claisen rearrangement/cyclization reaction of the corresponding 5,7‐dihydroxycoumarins with 3‐chloro‐3‐methylbut‐1‐yne in the presence of Cs2CO3 under microwave irradiation. The analogous reactions of propargyl chloride with esculetins or 5,7‐dihydroxycoumarins led to dipropargyloxy derivatives. The later by treatment with gold nanoparticles supported on TiO2 or BF3.Et2O in N,N‐dimethylformamide (DMF) under microwave irradiation resulted in very good to excellent yield to the corresponding fused dipyranocoumarins. The reactions of esculetins with 3‐chloro‐3‐methylbut‐1‐yne gave mainly exomethylene fused dioxino[g]coumarins. 相似文献
76.
Ancély F. dos Santos Daria Raquel Q. de Almeida Letícia F. Terra Rosangela A.M. Wailemann Vinícius M. Gomes Gabriel S. Arini Felipe G. Ravagnani Maurício S. Baptista Leticia Labriola 《Photochemistry and photobiology》2020,96(3):658-667
Photodynamic therapy (PDT) appears as a promising alternative in the treatment of breast cancer since it can be highly effective in curing cancer while preserving normal tissue. However, predicting outcomes in PDT still constitutes a great challenge. One of the parameters that are usually empirically determined is the rate of photon flux delivered to the tissue (light fluence rate). In the present study, we intended to understand why monolayers of human cells derived from mammary adenocarcinomas (MDA-MB-231 and MCF-7) respond quite differently to fluence rates (cells were irradiated either for 6 or for 16 min) at a fixed light dose (4.5 J cm−2) delivered with an array of LEDs in a typical methylene blue PDT protocol. While death rates of MDA-MB-231 cells were insensitive to the fluence rate, MCF-7 cells showed a quite impressive (three times) decrease in cell death levels in the shorter irradiation protocol. Independent on cell type cell death was invariably correlated with the depletion of reduced glutathione intracellular levels and consequently with widespread redox misbalance. Our data show the potential to optimize fluence rates to provide exhaustion of the cell antioxidant responses in order to circumvent therapy resistance of breast tumors. 相似文献
77.
Andreina Reyes Rosa M. Dominguez Maria Tosta Armando Herize Gabriel Chuchani 《国际化学动力学杂志》2007,39(5):268-275
The rates of elimination of several ethyl esters of 2‐oxo‐carboxylic acid were determined in a seasoned static reaction vessel over the temperature range 350–430°C and pressure range 33–240 Torr. The reactions, in the presence of a free‐radical inhibitor, are homogeneous, unimolecular, and follow a first‐order rate law. The overall and partial rate coefficients are expressed by the Arrhenius equation. Ethyl glyoxalate Ethyl 2‐oxo‐propionate Ethyl 3‐methyl‐2‐oxo‐butyrate The mechanisms of these elimination reactions are described in terms of concerted cyclic transition state structures. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 268–275, 2007 相似文献
78.
Electrocatalytic proton reduction leading to the formation of adsorbed molecular hydrogen on gold nanoparticles of 1-3 and 14-16 nm diameter stabilized by 1-mercapto-undecane-11-tetra(ethyleneglycol) has been demonstrated by cyclic voltammetry using a hanging mercury drop electrode. The nanoparticles were adsorbed to the electrode from aqueous dispersion and formed robust surface layers transferrable to fresh base electrolyte solutions. Unique electrocatalytic proton redox chemistry was observed that has no comparable counterpart in the electrochemistry of bulk gold electrodes. Depending on size, the nanoparticles have a discrete number of electrocatalytically active sites for the two-electron/two-proton reduction process. The adsorbed hydrogen formed is oxidized with the reverse potential sweep. These findings represent a new example of qualitative different behavior of nanoparticles in comparison with the corresponding bulk material. 相似文献
79.
Nucleation and Growth Synthesis of Siloxane Gels to Form Functional,Monodisperse, and Acoustically Programmable Particles 下载免费PDF全文
C. Wyatt Shields IV Danping Sun Dr. Kennita A. Johnson Korine A. Duval Aura V. Rodriguez Dr. Lu Gao Prof. Paul A. Dayton Prof. Gabriel P. López 《Angewandte Chemie (International ed. in English)》2014,53(31):8070-8073
Nucleation and growth methods offer scalable means of synthesizing colloidal particles with precisely specified size for applications in chemical research, industry, and medicine. These methods have been used to prepare a class of silicone gel particles that display a range of programmable properties and narrow size distributions. The acoustic contrast factor of these particles in water is estimated and can be tuned such that the particles undergo acoustophoresis to either the pressure nodes or antinodes of acoustic standing waves. These particles can be synthesized to display surface functional groups that can be covalently modified for a range of bioanalytical and acoustophoretic sorting applications. 相似文献
80.
Eric Iván Sánchez‐Flores Rodrigo Chávez‐Calvillo Todd A. Keith Gabriel Cuevas Tomás Rocha‐Rinza Fernando Cortés‐Guzmán 《Journal of computational chemistry》2014,35(10):820-828
The topological analysis of the electron density for electronic excited states under the formalism of the quantum theory of atoms in molecules using time‐dependent density functional theory (TDDFT) is presented. Relaxed electron densities for electronic excited states are computed by solving a Z‐vector equation which is obtained by means of the Sternheimer interchange method. This is in contrast to previous work in which the electron density for excited states is obtained using DFT instead of TDDFT, that is, through the imposition of molecular occupancies in accordance with the electron configuration of the excited state under consideration. Once the electron density of the excited state is computed, its topological characterization and the properties of the atoms in molecules are obtained in the same manner that for the ground state. The analysis of the low‐lying singlet and triplet vertical excitations of CO and C6H6 are used as representative examples of the application of this methodology. Altogether, it is shown how this procedure provides insights on the changes of the electron density following photoexcitation and it is our hope that it will be useful in the study of different photophysical and photochemical processes. © 2014 Wiley Periodicals, Inc. 相似文献