全文获取类型
收费全文 | 590篇 |
免费 | 43篇 |
国内免费 | 3篇 |
专业分类
化学 | 401篇 |
晶体学 | 6篇 |
力学 | 17篇 |
数学 | 67篇 |
物理学 | 145篇 |
出版年
2023年 | 8篇 |
2022年 | 11篇 |
2021年 | 16篇 |
2020年 | 15篇 |
2019年 | 12篇 |
2018年 | 16篇 |
2017年 | 10篇 |
2016年 | 31篇 |
2015年 | 29篇 |
2014年 | 31篇 |
2013年 | 34篇 |
2012年 | 37篇 |
2011年 | 58篇 |
2010年 | 25篇 |
2009年 | 18篇 |
2008年 | 26篇 |
2007年 | 34篇 |
2006年 | 26篇 |
2005年 | 24篇 |
2004年 | 26篇 |
2003年 | 12篇 |
2002年 | 11篇 |
2001年 | 12篇 |
2000年 | 4篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 11篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1987年 | 3篇 |
1985年 | 8篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1975年 | 7篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1966年 | 1篇 |
1959年 | 1篇 |
1958年 | 1篇 |
排序方式: 共有636条查询结果,搜索用时 6 毫秒
111.
Meccanica - Designing protective armors is important for varied civil and defense applications. Ceramic-polymer composite armors are particularly interesting for their high strength and light... 相似文献
112.
113.
Ananta Karmakar Mushkin Basha G.T. Venkatesh Babu Murali Botlagunta Noormohamed Abdul Malik Richard Rampulla Arvind Mathur Arun Kumar Gupta 《Tetrahedron letters》2018,59(48):4267-4271
A number of cyanomethyl esters of natural/unnatural aminoacids with un-protected amino functionality were synthesized because of their synthetic and medicinal importance. Critical N-Boc deprotection methods in the presence of labile (hydrolytic sensitivity) cyanomethyl functionality were screened thoroughly and it was found that readily available 4M HCl in 1,4-dioxane solution (2–4 equiv); acetonitrile, 0?°C, 2–4?h was a suitable condition. This condition was generalized and successfully applied to a variety of alkyl, alkynyl, aryl, heteroaryl, benzyl, azido, spiro amino acid cyanomethylesters irrespective of the nature of the amine (primary or secondary) and the distance between the amine and ester group to achieve final deprotected amino esters with high yield, and purity compared to other commonly known N-protecting groups (Cbz, Fmoc, Ac, Bn, Bz etc.). It was also demonstrated that N-Boc protected aminoacid cyanomethylesters are stable enough to carry out further functionalization compared to N-unprotected counterparts. 相似文献
114.
Dr. Xiangyan Shi Chinmayi Prasanna Dr. Toshio Nagashima Dr. Toshio Yamazaki Prof. Konstantin Pervushin Prof. Lars Nordenskiöld 《Angewandte Chemie (International ed. in English)》2018,57(31):9734-9738
Eukaryotic chromatin structure and dynamics play key roles in genomic regulation. In the current study, the secondary structure and intramolecular dynamics of human histone H4 (hH4) in the nucleosome core particle (NCP) and in a nucleosome array are determined by solid‐state NMR (SSNMR). Secondary structure elements are successfully localized in the hH4 in the NCP precipitated with Mg2+. In particular, dynamics on nanosecond to microsecond and microsecond to millisecond timescales are elucidated, revealing diverse internal motions in the hH4 protein. Relatively higher flexibility is observed for residues participating in the regulation of chromatin mobility and DNA accessibility. Furthermore, our study reveals that hH4 in the nucleosome array adopts the same structure and show similar internal dynamics as that in the NCP assembly while exhibiting relatively restricted motions in several regions consisting of residues in the N‐terminus, Loop 1, and the α3 helix region. 相似文献
115.
Vacuum-deposited, nonpolymeric flexible organic light-emitting devices 总被引:12,自引:0,他引:12
We demonstrate mechanically flexible, organic light-emitting devices (OLED's) based on the nonpolymetric thin-film materials tris-(8-hydroxyquinoline) aluminum (Alq(3)) and N, N(?) -diphenyl- N, N(?) -bis(3-methylphenyl)1- 1(?) biphenyl-4, 4(?) diamine (TPD). The single heterostructure is vacuum deposited upon a transparent, lightweight, thin plastic substrate precoated with a transparent, conducting indium tin oxide thin film. The flexible OLED performance is comparable with that of conventional OLED's deposited upon glass substrates and does not deteriorate after repeated bending. The large-area (~1 - cm>(2)) devices can be bent without failure even after a permanent fold occurs if they are on the convex substrate surface or over a bend radius of ~0.5>cm if they are on the concave surface. Such devices are useful for ultralightweight, flexible, and comfortable full-color flat panel displays. 相似文献
116.
A general expression has been obtained for the polarisation of an assembly of two-level systems irradiated by a sequence of N radiation pulses. The times and amplitudes of the echo-polarisation have been obtained. The method is an extension of the T-matrix method for the exact solution of the problem of interaction of radiation with two-level systems. The number of polarisation echoes is 3 N?1?N. The echo times are given by $$t' = (1 + a)t_N + (b - a)t_{N - 1} + (c - b)t_{N - 2} + \cdots + (q - p)t_1 $$ wheret k are the pulse times anda, b, c take on values 1, 0, ? 1. From the general expression the amplitudes of echoes due to sequences of 2, 3 and 4 pulses are obtained as special cases. Distinct echo sequences determined by time relations among the incident pulses are discussed. The echo sequences exhibit interesting features which are of significance in the application of the phenomenon in holophony, etc. 相似文献
117.
Bright molecules with sense, logic, numeracy and utility 总被引:1,自引:0,他引:1
Using cartoons as an organizational aid, we illustrate how the 'fluorophore-spacer-receptor' format of fluorescent PET (photoinduced electron transfer) sensors and switches can be logically extended in many different directions. These include emissive sensors for various chemical species and properties, and exploit various kinds of emission. Common sensing issues such as dynamic range, internal referencing, selectivity, mapping and space resolution are addressed. The sensory output function is also developed into more complex forms, molecular logic/computation being one such example. Molecular logic leads to molecular arithmetic. Real-life applications to physiological monitoring, medical diagnostics and molecular computational identification of small objects are included. 相似文献
118.
Benzo[c]phenanthridine alkaloid, 7-hydroxynitidine, was synthesized from readily available 2-benzyloxy-6-bromo-3,4-dimethoxybenzaldehyde 5 and napthylamine 6 using reductive amination followed by radical cyclization in eight steps. This method is highly efficient and better way to synthesize fully aromatized benzo[c]phenanthridine compounds. 相似文献
119.
The FeII complexes of two isomeric pentadentate bispidine ligands in the presence of H2O2 are catalytically active for the epoxidation and 1,2-dihydroxylation of cyclooctene (bispidine = 3,7-diazabicyclo[3.3.1]nonane; the two isomeric pentadentate bispidine ligands discussed here have two tertiary amine and three pyridine donors). The published spectroscopic and mechanistic data, which include an extensive set of 18O labeling experiments, suggest that the FeIV=O complex is the catalytically active species, which produces epoxide as well as cis- and trans-1,2-dihydroxylated products. Several observations from the published experimental study are addressed with hybrid density functional methods and, in general, the calculations support the proposed, for nonheme iron model systems novel mechanism, where the formation of a radical intermediate emerges from the reaction of the FeIV=O oxidant and cyclooctene. The calculations suggest that the S = 1 ground state of the FeIV=O complex reacts with cyclooctene in a stepwise reaction, leading to the formation of a carbon-based radical intermediate. This radical is captured by O2 from air to produce the majority of the epoxide products in an aerobic atmosphere. Under anaerobic conditions, the produced epoxide product is due to the cyclization of the radical intermediate. Several possible spin states (ST = 3, 2, 1, 0) of the radical intermediate are close in energy. As a result of the substantial energy barrier, calculated for the ST = 3 spin ground state, a spin-crossover during the cyclization step is assumed, and a possible two-state scenario is found, where the S = 2 state of the FeIV=O complex participates in the catalytic mechanism. The 1,2-dihydroxylation proceeds, as suggested by experiment, via an unprecedented pathway, where the radical intermediate is captured by a hydroxyl radical, the source of which is FeIII-OOH, and this reaction is barrierless. The calculations suggest that dihydroxylation can also occur by a direct oxidation pathway from FeIII-OOH. The strikingly different reactivities observed with the two isomeric bispidine FeII complexes are rationalized on the basis of structural and electronic differences. 相似文献
120.
Herein, we report a detailed periodic DFT investigation of Mn(II)-based [(Mn4Cl)3(BTT)8]3− (BTT3−=1,3,5-benzenetristetrazolate) metal-organic framework (MOF) to explore various hydrogen binding pockets, nature of MOF…H2 interactions, magnetic coupling and, H2 uptake capacity. Earlier experiments found an uptake capacity of 6.9 wt % of H2, with the heat of adsorption estimated to be ∼10 kJ/mol, which is one among the highest for any MOFs reported. Our calculations unveil different binding sites with computed binding energy varying from −6 to −15 kJ/mol. The binding of H2 at the Mn2+ site is found to be the strongest (site I), with H2 found to bind Mn2+ ion in a η2 fashion with a distance of 2.27 Å and binding energy of −15.4 kJ/mol. The bonding analysis performed using NBO and AIM reveal a strong donation of σ (H2) to the dz2 orbital of the Mn2+ ion responsible for such large binding energy. The other binding pockets, such as −Cl (site II) and BTT ligands (site III and IV) were found to be weaker, with the binding energy decreasing in the order I>II>III>IV. The average binding energy computed for these four sites put together is 9.6 kJ/mol, which is in excellent agreement with the experimental value of ∼10 kJ/mol. We have expanded our calculations to compute binding energy for multiple sites simultaneously, and in this model, the binding energy per site was found to decrease as we increased the number of H2 molecules suggesting electronic and steric factors controlling the overall uptake capacity. The calculated adsorption isotherm using the GCMC method reproduces the experimental observations. Further, the magnetic coupling computed for the unbound MOF reveals moderate ferromagnetic and strong antiferromagnetic coupling within the tetrameric {Mn4} unit leading to a three-up-one-down spin configuration as the ground state. These were then coupled ferromagnetically to other tetrameric units in the MOF network. The magnetic coupling was found to alter only marginally upon gas binding, suggesting that both exchange interaction and the spin-states are unlikely to play a role in the H2 uptake. This is contrary to the O2 uptake studied lately, where strong dependence on exchange-coupling/spin state was witnessed, suggesting exchange-coupling/magnetic field dependent binding as a viable route for gas separation. 相似文献