全文获取类型
收费全文 | 931篇 |
免费 | 74篇 |
国内免费 | 4篇 |
专业分类
化学 | 753篇 |
晶体学 | 5篇 |
力学 | 22篇 |
数学 | 55篇 |
物理学 | 174篇 |
出版年
2024年 | 2篇 |
2023年 | 32篇 |
2022年 | 29篇 |
2021年 | 33篇 |
2020年 | 48篇 |
2019年 | 45篇 |
2018年 | 34篇 |
2017年 | 22篇 |
2016年 | 61篇 |
2015年 | 42篇 |
2014年 | 52篇 |
2013年 | 68篇 |
2012年 | 82篇 |
2011年 | 77篇 |
2010年 | 42篇 |
2009年 | 26篇 |
2008年 | 40篇 |
2007年 | 49篇 |
2006年 | 36篇 |
2005年 | 20篇 |
2004年 | 18篇 |
2003年 | 19篇 |
2002年 | 12篇 |
2001年 | 14篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1996年 | 4篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1955年 | 1篇 |
1941年 | 1篇 |
1939年 | 1篇 |
排序方式: 共有1009条查询结果,搜索用时 31 毫秒
41.
A new efficient methodology has been developed for the synthesis of para-alkoxyphenols, an important group of anti-melanoma compounds, by heating alcoholic solutions of para-benzoquinones in the presence of amberlyst-15. The most notable feature here is the behaviour of the used primary or secondary alcohol as an effective reducing agent. 相似文献
42.
Durga Charan Panigrahi Patitapaban Sahu Devi Prasad Mishra Vivekanand Jha R. Lokeswara Patnaik 《Journal of Radioanalytical and Nuclear Chemistry》2014,302(1):433-439
This paper presents the assessment of inhalation exposure potential of broken uranium ore piles in different stopes of Jaduguda uranium mines of India. 222Rn emanation coefficient of broken uranium ore was measured in laboratory by collecting air sample from airtight glass jar containing ore sample. An attempt was also made to correlate the emanation coefficient with 226Ra content of the ore. The 222Rn progeny doses estimated based on radon activity concentration of broken ore, occupancy period and equilibrium ratio in different stopes were well below the prescribed limit of International Commission on Radiological Protection. The maximum 222Rn progeny dose contribution from broken ore piles was worked out to be 0.22 mSv year?1. This suggests that the broken ore piles are not the significant contributor of inhalation exposure under the existing ventilation condition of Jaduguda uranium mine. 相似文献
43.
The aromaticity of metal-metal quintuple bonded complexes of the type M2L2 (M=Cr, Mo, and W; L=amidinate) are studied employing gauge including magnetically induced ring current (GIMIC) analysis and electron density of delocalized bonds (EDDB). It is found that the complexes possess two types of aromaticity: i) Hückel aromaticity through delocalization of ligand π electrons with metal-metal δ-bond-forming 6 conjugated electrons (4π and 2δ) ring; ii) Craig-Möbius aromaticity through delocalization of π electrons of both the ligands with metal d-orbitals in Craig type orientation forming 10π electrons ring with a double twist. Extended transition state natural orbital chemical valence (ETS-NOCV) and canonical molecular orbital natural chemical shielding (CMO-NCS) analysis confirm the Craig-Möbius type arrangement of the orbitals. Furthermore, the unprecedented Hückel and Möbius type aromaticity is confirmed from the plot of the current pathways using 3D line integral convolution (3D-LIC) plots. The metal-metal bond order also increases down the group as justified from the complete active space self-consistent field (CASSCF) analysis. Due to an increase in the π and δ electron conjugation, both the Hückel and Möbius aromaticity increase down the group. 相似文献
44.
Structure‐Based Design of Inhibitors of the Aspartic Protease Endothiapepsin by Exploiting Dynamic Combinatorial Chemistry 下载免费PDF全文
Milon Mondal Nedyalka Radeva Dr. Helene Köster Dr. Ahyoung Park Dr. Constantinos Potamitis Dr. Maria Zervou Prof. Dr. Gerhard Klebe Dr. Anna K. H. Hirsch 《Angewandte Chemie (International ed. in English)》2014,53(12):3259-3263
Structure‐based design (SBD) can be used for the design and/or optimization of new inhibitors for a biological target. Whereas de novo SBD is rarely used, most reports on SBD are dealing with the optimization of an initial hit. Dynamic combinatorial chemistry (DCC) has emerged as a powerful strategy to identify bioactive ligands given that it enables the target to direct the synthesis of its strongest binder. We have designed a library of potential inhibitors (acylhydrazones) generated from five aldehydes and five hydrazides and used DCC to identify the best binder(s). After addition of the aspartic protease endothiapepsin, we characterized the protein‐bound library member(s) by saturation‐transfer difference NMR spectroscopy. Cocrystallization experiments validated the predicted binding mode of the two most potent inhibitors, thus demonstrating that the combination of de novo SBD and DCC constitutes an efficient starting point for hit identification and optimization. 相似文献
45.
Cover Picture: Double CaromH Activation Associated with Etheral Oxygen Insertion to Phenazine Architecture in Oxidisable Ruthenium(III) Complexes: A Mechanistic Insight (Chem. Eur. J. 10/2014) 下载免费PDF全文
46.
Abhijit Dutta Amit Kumar Pradhan Fei Qi Paritosh Mondal 《Monatshefte für Chemie / Chemical Monthly》2020,151(2):159-171
Quantum chemical study has been performed on finite-sized bi-metallic Rh3M alloys, M = Ag, Ir, Pd, Pt, Au, derived from magic cluster, Rh4. Bond length of C–O and N–O are noticed to be elongated in the presence of rhodium alloy clusters. CO2 and NO2 gases are found to be highly adsorbed on Rh3M clusters, which is confirmed by stretching frequency of C–O and N–O. DFT evaluated dipole moment and electronic charge redistribution suggests the sensing capability of CO2 and NO2 gases by Rh3M clusters which is further confirmed by the calculated HOMO–LUMO gap. Mixed rhodium alloy clusters supported on single-wall carbon nanotube (SWCNT) exhibits much higher ability to sense CO2 and NO2. On the other hand, SWCNT@Rh3M shows higher catalytic activity for the activation of CO2 and NO2 in comparison to bare Rh3M because of the higher electronic charge redistribution in the case of SWCNT@Rh3M. In case of SWCNT-supported gas adsorbed clusters, p electrons play a major role in bonding. 相似文献
47.
Amit Mondal Biswajit Bhattacharya Susobhan Das Surojit Bhunia Rituparno Chowdhury Somnath Dey C. Malla Reddy 《Angewandte Chemie (International ed. in English)》2020,59(27):10971-10980
Ductility is a common phenomenon in many metals but is difficult to achieve in molecular crystals. Organic crystals bend plastically on one or two face‐specific directions but fracture when stressed in any other arbitrary directions. An exceptional metal‐like ductility and malleability in the isomorphous crystals of two globular molecules, BH3NMe3 and BF3NMe3, is reported, with characteristic tensile stretching, compression, twisting, and thinning. The mechanically deformed samples, which transition to lower symmetry phases, retain good long‐range order amenable to structure determination by single‐crystal X‐ray diffraction. Molecules in these high‐symmetry crystals interact through electrostatic forces (B??N+) to form columnar structures with multiple slip planes and weak dispersive forces between columns. On the other hand, the limited number of facile slip planes and strong dihydrogen bonding in BH3NHMe2 negates ductility. Our study has implications for the design of soft ferroelectrics, solid electrolytes, barocalorics, and soft robotics. 相似文献
48.
Sudip Kumar Bera Sudipta Mondal Arijit Singha Hazari Jos Luis Priego Reyes Jimnez‐Aparicio Wolfgang Kaim Goutam Kumar Lahiri 《化学:亚洲杂志》2020,15(16):2532-2543
The dianion derived from (2Z,6Z)‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐f]indole‐2,6(1H,5H)‐diimine (H2BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL2, L=2,4‐pentanedionato (acac?), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac)2Ru(μ‐BL)Ru(acac)2] ( 1 / 2 ), [Ru(bpy)2Ru(μ‐BL)Ru(bpy)2](ClO4)2 ([ 3 ](ClO4)2) and [Ru(pap)2Ru(μ‐BL)Ru(pap)2](ClO4)2 ([ 4 ](ClO4)2). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV‐vis‐NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD‐DFT calculations the assignment of oxidation states reveals that 1 , 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 2+ and 4 2+ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge ( 3 2+) or are reduced at the ancillary ligands pap ( 4 2+). 相似文献
49.
On Regularization of a Source Identification Problem in a Parabolic PDE and its Finite Dimensional Analysis 下载免费PDF全文
Subhankar Mondal & M. Thamban Nair 《偏微分方程(英文版)》2021,34(3):240-257
We consider the inverse problem of identifying a general source term, which is a function of both time variable and the spatial variable, in a parabolic PDE from the knowledge of boundary measurements of the solution on some portion of the lateral boundary. We transform this inverse problem into a problem of solving a compact linear operator equation. For the regularization of the operator equation with noisy data, we employ the standard Tikhonov regularization, and its finite dimensional realization is done using a discretization procedure involving the space $L^2(0,\tau;L^2(Ω))$. For illustrating the specification of an a priori source condition, we have explicitly obtained the range space of the adjoint of the operator involved in the operator equation. 相似文献
50.
Subhasis Mallick Subala Mondal Arup Mandal Biplab K. Bera Parnajyoti Karmakar Alak K. Ghosh 《国际化学动力学杂志》2011,43(9):498-506
The kinetics of the interaction of three glycine‐containing dipeptides, namely, glycine‐L‐leucine (Gly‐Leu), glycine‐L‐isoleucine (Gly‐Ile), and glycine‐valine (Gly‐Val) with [Pt(en)(H2O)2](ClO4)2 has been studied spectrophotometrically as a function of [substrate complex], [dipeptides] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reaction shows two consecutive steps; the first is the ligand‐assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring's equation. The low ΔH1≠ and large negative value of ΔS1≠ as well as ΔH2≠ and ΔS2≠ indicate an associative mode of activation for both the aqua ligand substitution processes. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 498–506, 2011 相似文献