全文获取类型
收费全文 | 4278篇 |
免费 | 175篇 |
国内免费 | 32篇 |
专业分类
化学 | 3220篇 |
晶体学 | 24篇 |
力学 | 116篇 |
数学 | 527篇 |
物理学 | 598篇 |
出版年
2023年 | 38篇 |
2022年 | 56篇 |
2021年 | 79篇 |
2020年 | 100篇 |
2019年 | 102篇 |
2018年 | 71篇 |
2017年 | 57篇 |
2016年 | 138篇 |
2015年 | 121篇 |
2014年 | 152篇 |
2013年 | 228篇 |
2012年 | 299篇 |
2011年 | 366篇 |
2010年 | 163篇 |
2009年 | 131篇 |
2008年 | 323篇 |
2007年 | 316篇 |
2006年 | 306篇 |
2005年 | 253篇 |
2004年 | 218篇 |
2003年 | 192篇 |
2002年 | 155篇 |
2001年 | 34篇 |
2000年 | 34篇 |
1999年 | 37篇 |
1998年 | 36篇 |
1997年 | 41篇 |
1996年 | 56篇 |
1995年 | 31篇 |
1994年 | 28篇 |
1993年 | 24篇 |
1992年 | 21篇 |
1991年 | 25篇 |
1990年 | 25篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 8篇 |
1985年 | 22篇 |
1984年 | 27篇 |
1983年 | 11篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 18篇 |
1979年 | 10篇 |
1978年 | 16篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1975年 | 8篇 |
1974年 | 10篇 |
排序方式: 共有4485条查询结果,搜索用时 15 毫秒
21.
22.
1,4-Diamino-2-butyne was prepared from 1,4-dichloro-2-butyne via 1,4-diazido-2-butyne. Bis(amino acid) derivatives of 1,4-diamino-2-butyne having the general structure (Boc-Xxx-NHCH2C[triple bond])2 (Xxx = Ala, Phe and Met) were prepared and examined by 1H NMR spectroscopy. Using chemical shift, coupling constant and DMSO titration data it is found that these compounds adopt a C2-symmetric turn conformation featuring two intramolecular hydrogen bonds. 相似文献
23.
Application of stir bar sorptive extraction for wine analysis 总被引:4,自引:0,他引:4
Yoji?Hayasaka Kevin?MacNamara Gayle?A.?Baldock Randell?L.?Taylor Alan?P.?PollnitzEmail author 《Analytical and bioanalytical chemistry》2003,375(7):948-955
Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used. 相似文献
24.
Tobacco protein separation by aqueous two-phase extraction 总被引:13,自引:0,他引:13
Tobacco has long been considered as a host to produce large quantity of high-valued recombinant proteins. However, dealing with large quantities of biomass is a challenge for downstream processing. Aqueous two-phase extraction (ATPE) has been widely used in purifying proteins from various sources. It is a protein-friendly process and can be scaled up easily. In this paper, ATPE was studied for its applicability to recombinant protein purification from tobacco with egg white lysozyme as the model protein. Separate experiments with poly(ethylene glycol) (PEG)-salt-tobacco extract and PEG-salt-lysozyme were carried out to determine the partition behavior of tobacco protein and lysozyme, respectively. Two-level fractional factorial designs were used to study the effects of factors such as, PEG molecular mass, PEG concentration, the concentration of phase forming salt, sodium chloride concentration and pH, on protein partitioning. The results showed that, among the studied systems, PEG-sodium sulfate system was most suitable for lysozyme purification. Detailed experiments were conducted by spiking lysozyme into the tobacco extract. The conditions with highest selectivity of lysozyme over native tobacco protein were determined using a response surface design. The purification factor was further improved by decreasing the phase ratio along the tie line corresponding to the phase compositions with the highest selectivity. Under selected conditions the lysozyme yield was predicted to be 87% with a purification factor of 4 and concentration factor of 14. From this study, ATPE was shown to be suitable for initial protein recovery and partial purification from transgenic tobacco. 相似文献
25.
Observation of a quadrupole plasmon mode for a colloidal solution of gold nanoprisms 总被引:3,自引:0,他引:3
Millstone JE Park S Shuford KL Qin L Schatz GC Mirkin CA 《Journal of the American Chemical Society》2005,127(15):5312-5313
The synthesis and optical properties of single crystalline gold nanoprisms have been investigated. A three-step mediated seed growth process in an aqueous solution generated gold nanoprisms with a relatively homogeneous size distribution. The purity of these nanostructures has allowed us to observe a weak quadrupole resonance in addition to a strong dipole resonance associated with these novel structures. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of gold nanoprisms produced in this synthesis. 相似文献
26.
Redox-active tyrosine residues play important roles in long-distance electron reactions in enzymes, including prostaglandin H synthase, galactose oxidase, ribonucleotide reductase, and photosystem II. Magnetic resonance and vibrational spectroscopy provide methods with which to study the structures of redox-active amino acids in proteins. In this report, ultraviolet photolysis was used to generate tyrosyl radicals from polycrystalline tyrosinate or dipeptides, and the structure of the radical was investigated with EPR and reaction-induced FT-IR spectroscopy at 77 K. Photolysis at 77 K is expected to generate a neutral tyrosyl radical through oxidation of the aromatic ring. EPR and FT-IR results obtained from (13)C-labeled tyrosine were consistent with that expectation. Surprisingly, labeling of the tyrosyl amino group with (15)N also resulted in isotope-shifted bands in the photolysis spectrum. The force constant of a NH deformation mode increased when the tyrosyl radical was generated. These data suggest an interaction between the pi system of the tyrosyl radical and the amino group. In spectra acquired from the dipeptides, evidence for a sequence-dependent interaction between the tyrosyl radical and the amide bond of the dipeptide was also obtained. We postulate that perturbation of the amino or the amide/imide groups may occur through a spin polarization mechanism, which is indirectly detected as a change in NH force constant. This conclusion is supported by density functional calculations, which suggest a conformationally sensitive delocalization of spin density onto the amino and carboxylate groups of the tyrosyl radical. These experiments provide a step toward a detailed spectral interpretation for protein-based tyrosyl radicals. 相似文献
27.
O atom transfer from epoxides cis-stilbene oxide and styrene oxide to triphenylphosphine catalyzed by Tp'ReO(3) (Tp' = hydridotris(3,5-dimethylpyrazolyl)borate) is shown to proceed via an unexpectedly complex combination of mechanisms. Reduction of Tp'ReO(3) with PPh(3) in THF is rapid above room temperature to form a highly reactive species suggested to be Tp'ReO(2). Spectroscopic examination and attempts to isolate this by chromatography lead only to Tp'Re(O)(OH)(2) (1); exposure of the crude reduction mixture to ethanol results in formation of Tp'Re(O)(OEt)(OH) (3). Both 1 and 3 are as efficient catalysts for O atom transfer as the unpurified mixture resulting from reaction of PPh(3) with Tp'ReO(3); all three rhenium reactants give the same turnover frequency to within 10% at identical [Re](total) and [epoxide]. The kinetic behavior of the catalytic system (epoxide:Re = 20) is complex; an initial "burst" of alkene production is seen, which quickly tapers off and falls into a pseudo-zero-order reaction. The majority of rhenium is observed to exist as the syn-Tp'Re(O)(diolate) complex, formed by ring expansion of the epoxide. However, cycloreversion of this diolate is incapable of accounting for the observed catalytic turnover frequency. An additional intermediate, a coordinated epoxide, is proposed to form and partition between ring expansion and direct fragmentation to alkene; eventually a steady-state concentration of diolate forms. Competition between direct atom transfer and ring expansion followed by diolate cycloreversion is demonstrated by reaction of 3 with excess cis-stilbene oxide and styrene oxide in the absence of reductant to give a 4:1 mixture of alkene and syn-diolate from cis-stilbene oxide or a 5.5:1 mixture of alkene and syn-diolate from styrene oxide under conditions where diolate cycloreversion is a negligible contributor. 相似文献
28.
A bicyclo[3.1.0]hexane, with one cyclopropane carbon flanked by a ketone and an ester or an aldehyde, undergoes methanolysis with cleavage of one of the two activated cyclopropane bonds, depending on the reaction conditions. Acidic conditions yield primarily or exclusively a 4-methoxycyclohexane, while basic conditions yield a 3-methoxymethylcyclopentanone. 相似文献
29.
Menger FM Zhang H Caran KL Seredyuk VA Apkarian RP 《Journal of the American Chemical Society》2002,124(7):1140-1141
A gemini surfactant is able to promote columnar jointing in vitreous ice where long pillars, often of hexagonal cross section, are formed. This jointing is visible by cryo-high-resolution scanning electron microscopy (cryo-HRSEM), in which colloidal suspensions in bulk water are cooled rapidly in liquid ethane, thereby avoiding the potential artifacts with other types of EM. The jointing is proposed to arise from a new type of colloidal morphology where the surfactant self-assembles into hexagonal columns. Evidence for this mechanism comes from a cryo-HRSEM photo of an ice-free hexagonal "skeleton" composed of surfactant. Cryo-HRSEM, a method that is just beginning to realize its potential, would seem to have a promising future in the discovery of additional and as yet unimagined colloidal structures. 相似文献
30.
Harding WW Tidgewell K Schmidt M Shah K Dersch CM Snyder J Parrish D Deschamps JR Rothman RB Prisinzano TE 《Organic letters》2005,7(14):3017-3020
[reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. 相似文献