全文获取类型
收费全文 | 1285篇 |
免费 | 49篇 |
国内免费 | 4篇 |
专业分类
化学 | 942篇 |
晶体学 | 2篇 |
力学 | 32篇 |
数学 | 203篇 |
物理学 | 159篇 |
出版年
2023年 | 10篇 |
2022年 | 30篇 |
2021年 | 32篇 |
2020年 | 29篇 |
2019年 | 28篇 |
2018年 | 24篇 |
2017年 | 17篇 |
2016年 | 56篇 |
2015年 | 34篇 |
2014年 | 46篇 |
2013年 | 76篇 |
2012年 | 96篇 |
2011年 | 99篇 |
2010年 | 68篇 |
2009年 | 39篇 |
2008年 | 77篇 |
2007年 | 63篇 |
2006年 | 52篇 |
2005年 | 63篇 |
2004年 | 56篇 |
2003年 | 42篇 |
2002年 | 48篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 9篇 |
1998年 | 18篇 |
1997年 | 17篇 |
1996年 | 11篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1977年 | 4篇 |
1974年 | 3篇 |
1971年 | 3篇 |
1967年 | 7篇 |
1870年 | 2篇 |
排序方式: 共有1338条查询结果,搜索用时 15 毫秒
61.
A novel chemical sensor for the colorimetric detection of mercuric salts is described. The sensor is based on a mesoporous nanocrystalline TiO2 film sensitised with a ruthenium dye; immersion of this film in an aqueous solution of Hg2+ results in a rapid colorimetric response, with both a high selectivity and a sub-micromolar sensitivity. 相似文献
62.
E Pardo C Train H Liu LM Chamoreau B Dkhil K Boubekeur F Lloret K Nakatani H Tokoro S Ohkoshi M Verdaguer 《Angewandte Chemie (International ed. in English)》2012,51(33):8356-8360
Multiferroic materials: A novel class of multiferroics based on organic-inorganic hybrid materials is synthesized. The ferromagnetic properties originate from the coordination network, whereas the ferroelectricity results from the polar organic ions (see picture, M=magnetization and P=polarization). 相似文献
63.
Juan‐José Cid Dr. Miguel García‐Iglesias Jun‐Ho Yum Dr. Amparo Forneli Josep Albero Eugenia Martínez‐Ferrero Dr. Purificación Vázquez Prof. Michael Grätzel Prof. Mohammad K. Nazeeruddin Prof. Emilio Palomares Prof. Tomás Torres Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(20):5130-5137
Let it shine! The impact of the anchoring group on photovoltaic performance by a series of phthalocyanine sensitisers (see figure) has been demonstrated.
64.
Félix Freire Dr. Enrique Lallana Emilio Quiñoá Prof. Dr. Ricardo Riguera Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11963-11975
The conformational compositions of the tris(α‐methoxy‐α‐phenylacetic acid) ester derivatives of 1,2,3‐prim,sec,sec‐triols are presented. These conformations have been determined by theoretical and experimental data (i.e., energy‐ and chemical‐shift calculations, circular dichroism (CD) experiments, coupling‐constant analysis, enantioselective deuteration experiments, and low‐temperature NMR spectroscopic studies). A detailed analysis of the anisotropic effects due to the most significant conformers in the 1H NMR spectra supported the correlation between the 1H NMR spectra (ΔδRS value of H(3′) and |Δ(ΔδRS)| parameters) and the absolute configuration of the substrate. The study also allows the identification of the pro‐R and pro‐S methylene protons from their vicinal coupling constants and relative chemical shifts. 相似文献
65.
Haque SA Palomares E Cho BM Green AN Hirata N Klug DR Durrant JR 《Journal of the American Chemical Society》2005,127(10):3456-3462
In this paper we focus upon the electron injection dynamics in complete dye-sensitized nanocrystalline metal oxide solar cells (DSSCs). Electron injection dynamics are studied by transient absorption and emission studies of DSSCs and correlated with device photovoltaic performance and charge recombination dynamics. We find that the electron injection dynamics are dependent upon the composition of the redox electrolyte employed in the device. In a device with an electrolyte composition yielding optimum photovoltaic device efficiency, electron injection kinetics exhibit a half time of 150 ps. This half time is 20 times slower than that for control dye-sensitized films covered in inert organic liquids. This retardation is shown to result from the influence of the electrolyte upon the conduction band energetics of the TiO2 electrode. We conclude that optimum DSSC device performance is obtained when the charge separation kinetics are just fast enough to compete successfully with the dye excited-state decay. These conditions allow a high injection yield while minimizing interfacial charge recombination losses, thereby minimizing "kinetic redundancy" in the device. We show furthermore that the nonexponential nature of the injection dynamics can be simulated by a simple inhomogeneous disorder model and discuss the relevance of our findings to the optimization of both dye-sensitized and polymer based photovoltaic devices. 相似文献
66.
Carlos Camacho-Camacho Maria E. Castillo-Ramos Aurora Vásquez-Badillo Angelina Flores-Parra Rosalinda Contreras 《Journal of organometallic chemistry》2010,695(6):833-9863
The syntheses of [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]diphenyltin (1) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]dichloro-phenyl-stannate (2) by template reactions using 3,5-di-tert-butylcatechol, aqueous ammonia and SnPh2Cl2 are reported. We also report the syntheses of compounds 2, [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]trichloro-stannate (4), [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)methylamine]chloro-methyltin (5), and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)-n-butylamine]n-butyl-chlorotin (6) and [bis(3,5-di-tert-butyl-2-hydroxy-2-phenyl)amine]n-butyl-dichloro-stannate (7), performed by transmetallation reactions of the octahedral zinc coordination compound Zn[3,5-di-tert-butyl-1,2-quinone-(3,5-di-tert-butyl-2-hydroxy-1-phenyl)imine]2 (3) with SnPhCl3 or SnPh2Cl2, SnCl4, SnMe2Cl2, Sn(nBu)2Cl2 and Sn(nBu)Cl3, respectively. The X-ray diffraction structures of compounds 1, 2, 4 and 6 are reported. The transmetallation reactions with Sn(alkyl)2Cl2 afforded pentacoordinated tin compounds, where an alkyl group migrated from tin to nitrogen, while similar reactions with Sn-Ph compounds did not present any phenyl group migration. 相似文献
67.
Luis Palomo Rafael Rodríguez Samara Medina Emilio Quio Juan Casado Flix Freire Francisco J. Ramírez 《Angewandte Chemie (International ed. in English)》2020,59(23):9080-9087
Poly(phenylacetylene)s are a family of helical polymers constituted by conjugated double bonds. Raman spectra of these polymers show a structural fingerprint of the polyene backbone which, in combination with its helical orientation, makes them good candidates to be studied by Raman optical activity (ROA). Four different well‐known poly(phenylacetylene)s adopting different scaffolds and ten different helical senses have been prepared. Raman and ROA spectra were recorded and allowed to establish ROA‐spectrum/helical‐sense relationships: a left/right‐handed orientation of the polyene backbone (Mhelix/Phelix) produces a triplet of positive/negative ROA bands. Raman and ROA spectra of each polymer exhibited the same profile, and the sign of the ROA spectrum was opposite to the lowest‐energy electronic circular dichroism (ECD) band, indicating a resonance effect. Resonance ROA appears then as an indicator of the helical sense of poly(phenylacetylene)s, especially for those with an extra Cotton band in the ECD spectrum, where a wrong helical sense is assigned based on ECD, while ROA alerts of this misassignment. 相似文献
68.
Nanjie Deng William F. Flynn Junchao Xia R. S. K. Vijayan Baofeng Zhang Peng He Ahmet Mentes Emilio Gallicchio Ronald M. Levy 《Journal of computer-aided molecular design》2016,30(9):743-751
We describe binding free energy calculations in the D3R Grand Challenge 2015 for blind prediction of the binding affinities of 180 ligands to Hsp90. The present D3R challenge was built around experimental datasets involving Heat shock protein (Hsp) 90, an ATP-dependent molecular chaperone which is an important anticancer drug target. The Hsp90 ATP binding site is known to be a challenging target for accurate calculations of ligand binding affinities because of the ligand-dependent conformational changes in the binding site, the presence of ordered waters and the broad chemical diversity of ligands that can bind at this site. Our primary focus here is to distinguish binders from nonbinders. Large scale absolute binding free energy calculations that cover over 3000 protein–ligand complexes were performed using the BEDAM method starting from docked structures generated by Glide docking. Although the ligand dataset in this study resembles an intermediate to late stage lead optimization project while the BEDAM method is mainly developed for early stage virtual screening of hit molecules, the BEDAM binding free energy scoring has resulted in a moderate enrichment of ligand screening against this challenging drug target. Results show that, using a statistical mechanics based free energy method like BEDAM starting from docked poses offers better enrichment than classical docking scoring functions and rescoring methods like Prime MM-GBSA for the Hsp90 data set in this blind challenge. Importantly, among the three methods tested here, only the mean value of the BEDAM binding free energy scores is able to separate the large group of binders from the small group of nonbinders with a gap of 2.4 kcal/mol. None of the three methods that we have tested provided accurate ranking of the affinities of the 147 active compounds. We discuss the possible sources of errors in the binding free energy calculations. The study suggests that BEDAM can be used strategically to discriminate binders from nonbinders in virtual screening and to more accurately predict the ligand binding modes prior to the more computationally expensive FEP calculations of binding affinity. 相似文献
69.
The equilibrium electric double layer (EDL) that surrounds colloidal particles is essential for the response of a suspension under a variety of static or alternating external fields. An ideal salt-free suspension is composed of charged colloidal particles and ionic countercharges released by the charging mechanism. Existing macroscopic theoretical models can be improved by incorporating different ionic effects usually neglected in previous mean-field approaches, which are based on the Poisson-Boltzmann equation (PB). The influence of the finite size of the ions seems to be quite promising because it has been shown to predict phenomena like charge reversal, which has been out of the scope of classical PB approximations. In this work we numerically obtain the surface electric potential and the counterion concentration profiles around a charged particle in a concentrated salt-free suspension corrected by the finite size of the counterions. The results show the high importance of such corrections for moderate to high particle charges at every particle volume fraction, especially when a region of closest approach of the counterions to the particle surface is considered. We conclude that finite ion size considerations are obeyed for the development of new theoretical models to study non-equilibrium properties in concentrated colloidal suspensions, particularly salt-free ones with small and highly charged particles. 相似文献
70.
This paper reports the synthesis, passivation and functionalization of luminescent carbon dots (CDs) possessing surface thiol ending groups. A simple procedure involving amidation of passivated carbon dots (p-CDs) with cysteamine boosts their photoluminescent properties and enables their use as easily controlled fluorescent nanosensors for determining citrate–gold nanoparticles (AuNPs). The mechanism behind the quenching phenomenon was established from fluorescence measurements at high temperatures and lifetime tests, and found to involve static quenching leading to the formation of CD–AuNP nanohybrids. A method for determining AuNPs in complex matrices was developed and validated by application to spiked drinking water and mussel tissues. The limits of detection and quantitation for AuNPs thus obtained were 0.20 and 0.66 nmol L–1, respectively. 相似文献