全文获取类型
收费全文 | 756篇 |
免费 | 41篇 |
国内免费 | 2篇 |
专业分类
化学 | 681篇 |
晶体学 | 5篇 |
力学 | 4篇 |
数学 | 65篇 |
物理学 | 44篇 |
出版年
2024年 | 2篇 |
2023年 | 10篇 |
2022年 | 21篇 |
2021年 | 23篇 |
2020年 | 18篇 |
2019年 | 24篇 |
2018年 | 19篇 |
2017年 | 13篇 |
2016年 | 25篇 |
2015年 | 30篇 |
2014年 | 30篇 |
2013年 | 42篇 |
2012年 | 50篇 |
2011年 | 74篇 |
2010年 | 36篇 |
2009年 | 28篇 |
2008年 | 45篇 |
2007年 | 52篇 |
2006年 | 51篇 |
2005年 | 35篇 |
2004年 | 44篇 |
2003年 | 29篇 |
2002年 | 25篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1969年 | 1篇 |
1947年 | 1篇 |
1940年 | 2篇 |
1937年 | 1篇 |
1928年 | 1篇 |
1926年 | 3篇 |
1895年 | 1篇 |
排序方式: 共有799条查询结果,搜索用时 15 毫秒
71.
Greaves SJ Flynn EL Futcher EL Wrede E Lydon DP Low PJ Rutter SR Beeby A 《The journal of physical chemistry. A》2006,110(6):2114-2121
The torsional motions of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB), a prototype molecular wire, were studied using cavity ring-down spectroscopy in the first UV absorption band (316-321 nm). The torsional spectrum of 1,4-bis(phenylethynyl)-2,3,5,6-tetradeuteriobenzene was also recorded in the gas phase. Both spectra were successfully simulated using simple cosine potentials to describe the torsional motions. The ground-state barrier to rotation was estimated to be 220-235 cm(-1), which is similar to that of diphenylacetylene (tolane). Complementary DFT calculations were found to overestimate the torsional barrier. 相似文献
72.
73.
How to confirm identified toxicants in effect-directed analysis 总被引:1,自引:0,他引:1
Brack W Schmitt-Jansen M Machala M Brix R Barceló D Schymanski E Streck G Schulze T 《Analytical and bioanalytical chemistry》2008,390(8):1959-1973
Due to the production and use of a multitude of chemicals in modern society, waters, sediments, soils and biota may be contaminated
with numerous known and unknown chemicals that may cause adverse effects on ecosystems and human health. Effect-directed analysis
(EDA), combining biotesting, fractionation and chemical analysis, helps to identify hazardous compounds in complex environmental
mixtures. Confirmation of tentatively identified toxicants will help to avoid artefacts and to establish reliable cause–effect
relationships. A tiered approach to confirmation is suggested in the present paper. The first tier focuses on the analytical
confirmation of tentatively identified structures. If straightforward confirmation with neat standards for GC–MS or LC–MS
is not available, it is suggested that a lines-of-evidence approach is used that combines spectral library information with
computer-based structure generation and prediction of retention behaviour in different chromatographic systems using quantitative
structure–retention relationships (QSRR). In the second tier, the identified toxicants need to be confirmed as being the cause
of the measured effects. Candidate components of toxic fractions may be selected based, for example, on structural alerts.
Quantitative effect confirmation is based on joint effect models. Joint effect prediction on the basis of full concentration–response
plots and careful selection of the appropriate model are suggested as a means to improve confirmation quality. Confirmation
according to the Toxicity Identification Evaluation (TIE) concept of the US EPA and novel tools of hazard identification help
to confirm the relevance of identified compounds to populations and communities under realistic exposure conditions. Promising
tools include bioavailability-directed extraction and dosing techniques, biomarker approaches and the concept of pollution-induced
community tolerance (PICT).
Figure Toxicity confirmation in EDA as a tiered approach 相似文献
74.
Luke J. Batchelor Emma Fitzgerald Dr. Joanna Wolowska Dr. Joseph J. W. McDouall Prof. Eric J. L. McInnes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(36):11082-11088
The synthesis, structural and magnetic characterisation of [VIII3O(tmme)2(diimine)2Cl] [diimine=2,2′‐bipyridine ( 1 ) or 1,10‐phenanthroline ( 2 )] and (HNEt3)2[VIII4O(tmme)4] ( 3 ) is reported, in which H3tmme is tris(mercaptomethyl)ethane, MeC(CH2SH)3, the thiol analogue of the famous tripodal alcohol ligands typified by H3thme [tris(hydroxymethyl)ethane, MeC(CH2OH)3]. Complexes 1 and 3 have “T‐shaped” and square topologies, respectively, and the latter is centred on a rare example of a square‐planar oxide. The tri‐thiolate ligands bind the periphery of the clusters and provide such strong antiferromagnetic exchange pathways that in both cases only a single total spin state is occupied up to room temperature, in the absence of metal–metal bonding. Magnetic data, electronic structure calculations and electrochemical data are reported. 相似文献
75.
76.
77.
Dr. Luke A. Clifton Dr. Stephen A. Holt Dr. Arwel V. Hughes Dr. Emma L. Daulton Dr. Wanatchaporn Arunmanee Dr. Frank Heinrich Dr. Syma Khalid Damien Jefferies Dr. Timothy R. Charlton Dr. John R. P. Webster Dr. Christian J. Kinane Prof. Jeremy H. Lakey 《Angewandte Chemie (International ed. in English)》2015,54(41):11952-11955
Gram‐negative bacteria are an increasingly serious source of antibiotic‐resistant infections, partly owing to their characteristic protective envelope. This complex, 20 nm thick barrier includes a highly impermeable, asymmetric bilayer outer membrane (OM), which plays a pivotal role in resisting antibacterial chemotherapy. Nevertheless, the OM molecular structure and its dynamics are poorly understood because the structure is difficult to recreate or study in vitro. The successful formation and characterization of a fully asymmetric model envelope using Langmuir–Blodgett and Langmuir–Schaefer methods is now reported. Neutron reflectivity and isotopic labeling confirmed the expected structure and asymmetry and showed that experiments with antibacterial proteins reproduced published in vivo behavior. By closely recreating natural OM behavior, this model provides a much needed robust system for antibiotic development. 相似文献
78.
79.
Dr. Yan Li Dr. Yuk-Chi Chan Bi-Xiang Leong Dr. Yongxin Li Dr. Emma Richards Indu Purushothaman Dr. Susmita De Dr. Pattiyil Parameswaran Dr. Cheuk-Wai So 《Angewandte Chemie (International ed. in English)》2017,56(26):7573-7578
The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6-iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− ( 2 ) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1-F-2-IMe-C6H4]+I− ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography. 相似文献
80.
Stephen E Huang D Shaw JL Blake AJ Collison D Davies ES Edge R Howard JA McInnes EJ Wilson C Wolowska J McMaster J Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(37):10246-10258
The NiII complexes [Ni([9]aneNS2‐CH3)2]2+ ([9]aneNS2‐CH3=N‐methyl‐1‐aza‐4,7‐dithiacyclononane), [Ni(bis[9]aneNS2‐C2H4)]2+ (bis[9]aneNS2‐C2H4=1,2‐bis‐(1‐aza‐4,7‐dithiacyclononylethane) and [Ni([9]aneS3)2]2+ ([9]aneS3=1,4,7‐trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal NiIII products, which have been characterized by X‐ray crystallography, UV/Vis and multi‐frequency EPR spectroscopy. The single‐crystal X‐ray structure of [NiIII([9]aneNS2‐CH3)2](ClO4)6?(H5O2)3 reveals an octahedral co‐ordination at the Ni centre, while the crystal structure of [NiIII(bis[9]aneNS2‐C2H4)](ClO4)6?(H3O)3? 3H2O exhibits a more distorted co‐ordination. In the homoleptic analogue, [NiIII([9]aneS3)2](ClO4)3, structurally characterized at 30 K, the Ni? S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn–Teller distorted octahedral stereochemistry. [Ni([9]aneNS2‐CH3)2](PF6)2 shows a one‐electron oxidation process in MeCN (0.2 M NBu4PF6, 293 K) at E1/2=+1.10 V versus Fc+/Fc assigned to a formal NiIII/NiII couple. [Ni(bis[9]aneNS2‐C2H4)](PF6)2 exhibits a one‐electron oxidation process at E1/2=+0.98 V and a reduction process at E1/2=?1.25 V assigned to NiII/NiIII and NiII/NiI couples, respectively. The multi‐frequency X‐, L‐, S‐, K‐band EPR spectra of the 3+ cations and their 86.2 % 61Ni‐enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6 %, 42.8 % and 37.2 % Ni character in [Ni([9]aneNS2‐CH3)2]3+, [Ni(bis[9]aneNS2‐C2H4)]3+ and [Ni([9]aneS3)2]3+, respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S‐thioether centres. EPR spectra for [61Ni([9]aneS3)2]3+ are consistent with a dynamic Jahn–Teller distortion in this compound. 相似文献