全文获取类型
收费全文 | 3432篇 |
免费 | 205篇 |
国内免费 | 17篇 |
专业分类
化学 | 2389篇 |
晶体学 | 13篇 |
力学 | 76篇 |
数学 | 601篇 |
物理学 | 575篇 |
出版年
2023年 | 29篇 |
2022年 | 23篇 |
2021年 | 61篇 |
2020年 | 79篇 |
2019年 | 76篇 |
2018年 | 71篇 |
2017年 | 76篇 |
2016年 | 177篇 |
2015年 | 138篇 |
2014年 | 122篇 |
2013年 | 223篇 |
2012年 | 266篇 |
2011年 | 281篇 |
2010年 | 163篇 |
2009年 | 117篇 |
2008年 | 229篇 |
2007年 | 193篇 |
2006年 | 167篇 |
2005年 | 169篇 |
2004年 | 151篇 |
2003年 | 137篇 |
2002年 | 125篇 |
2001年 | 40篇 |
2000年 | 34篇 |
1999年 | 37篇 |
1998年 | 40篇 |
1997年 | 24篇 |
1996年 | 31篇 |
1995年 | 14篇 |
1994年 | 19篇 |
1993年 | 29篇 |
1992年 | 18篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 11篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 13篇 |
1985年 | 31篇 |
1984年 | 23篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 18篇 |
1978年 | 12篇 |
1977年 | 11篇 |
1975年 | 9篇 |
1974年 | 13篇 |
1973年 | 12篇 |
排序方式: 共有3654条查询结果,搜索用时 15 毫秒
101.
Hevia E Pérez J Riera V Miguel D Campomanes P Menéndez MI Sordo TL García-Granda S 《Journal of the American Chemical Society》2003,125(13):3706-3707
As depicted in the scheme, the alkylidenamido complex 1, a N-rhenaimine, reacts with ketenes to afford the beta-lactams 2-4, which possess a {Re(CO)3(bpy)} fragment as substituent at nitrogen. Clean demetalations using HOTf or MeOTf yield the free beta-lactams or N-methyl-beta-lactams along with [Re(OTf)(CO)3(bpy)]. DFT calculations help to rationalize why the reaction is faster than those of non transition metal N-substituted imines. 相似文献
102.
Soga O van Nostrum CF Ramzi A Visser T Soulimani F Frederik PM Bomans PH Hennink WE 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9388-9395
Amphiphilic AB block copolymers consisting of thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) and poly(ethylene glycol), pHPMAmDL-b-PEG, were synthesized via a macroinitiator route. Dynamic light scattering measurements showed that these block copolymers form polymeric micelles in water with a size of around 50 nm by heating of an aqueous polymer solution from below to above the critical micelle temperature (cmt). The critical micelle concentration as well as the cmt decreased with increasing pHPMAmDL block lengths, which can be attributed to the greater hydrophobicity of the thermosensitive block with increasing molecular weight. Cryogenic transmission electron microscopy analysis revealed that the micelles have a spherical shape with a narrow size distribution. 1H NMR measurements in D2O showed that the intensity of the peaks of the protons from the pHPMAmDL block significantly decreased above the cmt, indicating that the thermosensitive blocks indeed form the solidlike core of the micelles. Static light scattering measurements demonstrated that pHPMAmDL-b-PEG micelles with relatively large pHPMAmDL blocks possess a highly packed core that is stabilized by a dense layer of swollen PEG chains. FT-IR analysis indicated that dehydration of amide bonds in the pHPMAmDL block occurs when the polymer dissolved in water is heated from below to above its cmt. The micelles were stable when an aqueous solution of micelles was incubated at 37 degrees C and at pH 5.0, where the hydrolysis rate of lactate side groups is minimized. On the other hand, at pH 9.0, where hydrolysis of the lactic acid side groups occurs, the micelles started to swell after 1.5 h of incubation and complete dissolution of micelles was observed after 4 h as a result of hydrophilization of the thermosensitive block. Fluorescence spectroscopy measurements with pyrene loaded in the hydrophobic core of the micelles showed that when these micelles were incubated at pH 8.6 and at 37 degrees C the microenvironment of pyrene became increasingly hydrated in time during this swelling phase. The results demonstrate the potential applicability of pHPMAmDL-b-PEG block copolymer micelles for the controlled delivery of hydrophobic drugs. 相似文献
103.
K. Rybáček L. Wilhelmová M. Tomášek 《Journal of Radioanalytical and Nuclear Chemistry》1994,186(3):245-255
Radiocesium in ground layer atmospheric aerosol and fallout in Prague has been examined. After a decline in 1986–1988, controlled by a sum of two negative exponentials,137Cs aerosol concentration reached a constant level based on an equilibrium between its deposition and resuspension. Deposition velocity was compared to that of7Be and226Ra. It confirmed the supposed source of137Cs as resuspension from the ground. Resuspension factor of the order of magnitude of 10–9 was determined, reminding similar values found earlier in Prague as well as those found in Munich. It also agrees well with the USAEC resuspension model. Solubility of137Cs was measured in combined wet and dry fallout. The average undissolved fraction of137Cs was found to be about 70% which can be explained by the conditions of the137Cs aerosol formation in Chernobyl. 相似文献
104.
Huijser A Savenije TJ Kroeze JE Siebbeles LD 《The journal of physical chemistry. B》2005,109(43):20166-20173
The photoinduced charge separation efficiency in porphyrin/TiO2 bilayers has been determined using the time-resolved microwave conductivity (TRMC) technique. Porphyrins investigated are unsubstituted meso-tetraphenylporphyrin (TPP) and meso-tetra(4-ethylphenyl)porphyrin (TEPP). TEPP/TiO2 bilayers exhibit a charge separation efficiency per incident photon at the Soret band maximum of 6.2%, which is considerably higher than the efficiency of 1.2% found for TPP/TiO2 bilayers. Exciton diffusion lengths of 7 A for TPP and 75 A for TEPP are obtained from fitting a model for the charge separation efficiency to the experimental data. Optical measurements on the porphyrin derivatives on quartz yield a 20 times higher fluorescence quantum yield and a 7 times higher fluorescence rate constant for TEPP layers as compared to TPP layers. The exciton lifetime of 800 ps found for TEPP layers is considerably longer than the lifetime of 260 ps in TPP layers. The exciton diffusion coefficients, determined from the exciton diffusion length and the exciton lifetime, are found to be 2.10(-9) m(2)/s for TPP and 7.10(-8) m(2)/s for TEPP. The difference is discussed in terms of the presence of face-to-face dimers or larger aggregates in TPP layers. 相似文献
105.
McCarthy TJ Plog MA Floy SA Jansen JA Soukup JK Soukup GA 《Chemistry & biology》2005,12(11):1221-1226
Natural RNA catalysts (ribozymes) perform essential reactions in biological RNA processing and protein synthesis, whereby catalysis is intrinsic to RNA structure alone or in combination with metal ion cofactors. The recently discovered glmS ribozyme is unique in that it functions as a glucosamine-6-phosphate (GlcN6P)-dependent catalyst believed to enable "riboswitch" regulation of amino-sugar biosynthesis in certain prokaryotes. However, it is unclear whether GlcN6P functions as an effector or coenzyme to promote ribozyme self-cleavage. Herein, we demonstrate that ligand is absolutely requisite for glmS ribozyme self-cleavage activity. Furthermore, catalysis both requires and is dependent upon the acid dissociation constant (pKa) of the amine functionality of GlcN6P and related compounds. The data demonstrate that ligand is integral to catalysis, consistent with a coenzyme role for GlcN6P and illustrating an expanded capacity for biological RNA catalysis. 相似文献
106.
Inmaculada Escorihuela Larry R. Falvello Milagros Tomás 《Journal of Cluster Science》2004,15(4):425-435
The reaction of the tetranuclear cyanide aquo complex [{Pt(CN)4Cu(bipy)(H2O)}2]· 2H2O with aqueous ammonia produces the new tetranuclear ammino-containing product [{Pt(CN)4Cu(bipy)(NH3)}2] (1), with terminal cyanide groups and with NH3 coordinated to the Cu atom. The distorted trigonal bipyramidal coordination about copper in 1 differs from the square-pyramidal coordination present in the starting material. The bipyridine ligand in 1 is nearly perpendicular to the tetranuclear core of the molecule, as opposed to its coplanar disposition in the aquo complex. The two platinum atoms of the tetranuclear core in 1 form Pt···Pt interactions of 3. 2390(8) Å with platinum atoms of neighboring molecules, producing an echelon-shaped supramolecular chain held together by staggered (CN)4Pt···Pt(CN)4 linkages, an aggregate structure which does not have a precedent in chemistry derived from the Pt(CN)4 building block. 相似文献
107.
Guldi DM Gouloumis A Vázquez P Torres T Georgakilas V Prato M 《Journal of the American Chemical Society》2005,127(16):5811-5813
Induction of self-organization between zinc phthalocyanine (ZnPc) and C60 moieties in a novel amphiphilic ZnPc-C60 salt results in uniformly nanostructured 1-D nanotubules. Their photoreactivity, in terms of ultrafast charge separation (i.e., approximately 1012 s-1) and ultraslow charge recombination (i.e., approximately 103 s-1), is remarkable. In addition, the observed ZnPc*+-C60*- lifetime of 1.4 ms implies, relative to that of the monomeric ZnPc-C60 ( approximately 3 ns), an impressive stabilization of 6 orders of magnitude. 相似文献
108.
Proton transfer reaction ion trap mass spectrometer 总被引:1,自引:0,他引:1
Prazeller P Palmer PT Boscaini E Jobson T Alexander M 《Rapid communications in mass spectrometry : RCM》2003,17(14):1593-1599
Proton transfer reaction mass spectrometry is a relatively new field that has attracted a great deal of interest in the last few years. This technique uses H(3)O(+) as a chemical ionization (CI) reagent to measure volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) to parts per trillion by volume (pptv) range. Mass spectra acquired with a proton transfer reaction mass spectrometer (PTR-MS) are simple because proton transfer chemical ionization is "soft" and results in little or no fragmentation. Unfortunately, peak identification can still be difficult due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). The use of an ITMS is appealing because of its ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates are possible that will allow for detection of multiple compounds. Here we present the first results from a proton transfer reaction ion trap mass spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype instrument in order to estimate possible detection limits of a second-generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated. Modifications are suggested that will enable further reduction in detection limits to the low-ppbv to high-pptv range. Furthermore, the applicability of MS/MS in differentiating between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making differentiation possible, even when a mixture of both species is present in the same sample. However, MS/MS spectra of acetone and propanal produce fragments with the same molecular masses but with different intensity ratios. This allows quantitative distinction only if one species is predominant. Fragmentation mechanisms are proposed to explain the results. 相似文献
109.
Vladimír Kočí Tomáš Ocelka Martin Mlejnek Roman Grabic 《Central European Journal of Chemistry》2004,2(1):91-112
The efficiency of treatment processes forboth municipal and industrial wastewater (treatment plant-Ostrava, Czech Republic)
focused on persistent organic pollutants (POPs) was assessed. Semipermeable membrane devices (SPMDs) as a sampling system
were applied. Exposed SPMDs were analyzed both for chemical contaminants of POPs and toxicity response. The chemical analyses
of PAHs were made by HPLC-FLD, PCDD/Fs and PCBs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Ecotoxicity data
on chlorococcal alga Desmodesmus subspicatus (Scenedesmus subspicatus) and luminescent bacteria Vibrio fischeri are presented here. All toxicity data as effective volume Vtox are expressed. The results show good treatment ability of
the treatment plant and proved used system as an appropriate tool for efficiency assessment of treatment and/or decontamination
processes. 相似文献
110.
Eric W. Ainscough Tom A. James Stephen D. Robinson Jonathan N. Wingfield 《Journal of organometallic chemistry》1973,60(2):C63-C66
Osmium triphenylphosphine complexes, OsH4(PPh3)3, OsH2 (CO)(PPh3)3 and OsHCl(CO)(PPh3)3 react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions. 相似文献