全文获取类型
收费全文 | 945篇 |
免费 | 37篇 |
国内免费 | 8篇 |
专业分类
化学 | 775篇 |
晶体学 | 16篇 |
力学 | 3篇 |
数学 | 77篇 |
物理学 | 119篇 |
出版年
2023年 | 12篇 |
2022年 | 13篇 |
2021年 | 24篇 |
2020年 | 37篇 |
2019年 | 30篇 |
2018年 | 14篇 |
2017年 | 9篇 |
2016年 | 31篇 |
2015年 | 29篇 |
2014年 | 17篇 |
2013年 | 68篇 |
2012年 | 77篇 |
2011年 | 76篇 |
2010年 | 30篇 |
2009年 | 30篇 |
2008年 | 58篇 |
2007年 | 78篇 |
2006年 | 75篇 |
2005年 | 53篇 |
2004年 | 38篇 |
2003年 | 34篇 |
2002年 | 32篇 |
2001年 | 8篇 |
2000年 | 8篇 |
1999年 | 9篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1948年 | 1篇 |
1943年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有990条查询结果,搜索用时 15 毫秒
11.
Kennedy AR Stewart H Eremin K Stenger J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):3064-3069
The first systematic series of single-crystal diffraction structures of azo lake pigments is presented (Lithol Red with cations=Mg(II), Ca(II), Sr(II), Ba(II), Na(I) and Cd(II)) and includes the only known structures of non-Ca examples of these pigments. It is shown that these commercially and culturally important species show structural behaviour that can be predicted from a database of structures of related sulfonated azo dyes, a database that was specifically constructed for this purpose. Examples of the successful structural predictions from the prior understanding of the model compounds are that 1) the Mg salt is a solvent-separated ion pair, whereas the heavier alkaline-earth elements Ca, Sr and Ba form contact ion pairs, namely, low-dimensional coordination complexes; 2) all of the Lithol Red anions exist as the hydrazone tautomer and have planar geometries; and 3) the commonly observed packing mode of alternating inorganic layers and organic bilayers is as expected for an ortho-sulfonated azo species with a planar anion geometry. However, the literature database of dye structures has no predictive use for organic solvate structures, such as that of the observed Na Lithol Red DMF solvate. Interestingly, the Cd salt is isostructural with the Mg salt and not with the Ca salt. It is also observed that linked eight-membered [MOSO](2) rings are the basic coordination motif for all of the known structures of Ca, Sr and Ba salts of sulfonated azo pigments in which competing carboxylate groups are absent. 相似文献
12.
Mecinović J Snyder PW Mirica KA Bai S Mack ET Kwant RL Moustakas DT Héroux A Whitesides GM 《Journal of the American Chemical Society》2011,133(35):14017-14026
The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H(2)NSO(2)C(6)H(4)-CONHCH(2)(CX(2))(n)CX(3), n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions). 相似文献
13.
Andre Rosowsky Katherine K. N. Chen Nickolas Papathanasopoulos Edward J. Modest 《Journal of heterocyclic chemistry》1972,9(2):263-273
Eighteen new 1,3-diamino-5,6-dihydrobenzo[f] quinazolines ( 6 , R. = alkyl, Cl, MeO) were synthesized via the condensation of appropriate 2-tetralones with cyanoguanidine under fusion conditions. Methods were developed for the preparation of a number of heretofore undescribed 2-tetralones as precursors. The final products can be viewed as conformationally rigid analogs of pyrimethamine ( 2 ), and are of interest as inhibitors of dihydrofolate reductase and as potential antimalarial and antitumor agents. 相似文献
14.
Frank Marken Yu-Chen Tsai Andrew J. Saterlay Barry A. Coles Daniel Tibbetts Katherine Holt Christiaan H. Goeting John S. Foord Richard G. Compton 《Journal of Solid State Electrochemistry》2001,5(5):313-318
Microwave activation of electrochemical processes has recently been introduced as a new technique for the enhancement and
control of processes at electrode|solution (electrolyte) interfaces. This methodology is extended to processes at glassy carbon
and boron-doped diamond electrodes. Deposition of both Pb metal and PbO2 from an aqueous solution of Pb2+ (0.1 M HNO3) are affected by microwave radiation. The formation of PbO2 on anodically pre-treated boron-doped diamond is demonstrated to change from kinetically sluggish and poorly defined at room
temperature to nearly diffusion controlled and well defined in the presence of microwave activation. Calibration of the temperature
at the electrode|solution (electrolyte) interface with the Fe3+/2+ (0.1 M HNO3) redox system allows the experimentally observed effects to be identified as predominantly thermal in nature and therefore
consistent with a localized heating effect at the electrode|solution interface. The microwave-activated deposition of PbO2 on boron-doped diamond remains facile in the presence of excess oxidizable organic compounds such as ethylene glycol. An
increase of the current for the electrocatalytic oxidation of ethylene glycol at PbO2/boron-doped diamond electrodes in the presence of microwave radiation is observed. Preliminary results suggest that the electrodissolution
of solid microparticles of PbO2 abrasively attached to the surface of a glassy carbon electrode is also enhanced in the presence of microwave radiation.
Electronic Publication 相似文献
15.
Steven J. Langford Marcia A.-P. Lee Katherine J. Macfarlane Josephine A. Weigold 《Journal of inclusion phenomena and macrocyclic chemistry》2001,41(1-4):135-139
A series of complexes of the type [Sn(TTP)L2] have been prepared by the condensation of [Sn(TTP)OH2] (TTP = meso-tetratolylporphyrin) with a range of substituted phenols. The resulting complexes were characterised using 1H NMR and single crystal X-ray diffraction techniques. In each case, the condensation of the phenols with the Sn(IV)porphyrin in CDCl3 solution is slow (h) but essentially quantitative. The slow kinetics of the formation of the diaxial phenolate complexes allows for the identification, by 1H NMR spectroscopy, of three independent complexes within this process, namely an outer-sphere (H-bonded) complex as well as two independent phenolate complexes. The rate of condensation is in the order phenol 4-methoxyphenol > 4-nitrophenol and suggests a steric rather than pKa dependency. 相似文献
16.
M. J. Welch Jennifer C. Colbert Lisa M. Gill Curtis S. Phinney Katherine E. Sharpless Lorna T. Sniegoski Laura J. Wood 《Analytical and bioanalytical chemistry》2001,370(1):42-47
In response to reference material needs expressed by the food industry and government regulators, the National Institute
of Standards and Technology (NIST) has developed a new Standard Reference Material (SRM) consisting of a canned meat product
with certified and reference values for a large number of constituents. SRM 1546 Meat Homogenate consists of a mixture of
finely ground pork and chicken prepared and canned by a commercial process. NIST determined the concentration levels of cholesterol,
sodium, calcium, iron, and seven fatty acids in this SRM using well defined methods and procedures. These analytes as well
as 34 other constituents or properties were determined in an interlaboratory comparison exercise involving 21 laboratories,
most of which are associated with the National Food Processors Association (NFPA) Food Industry Analytical Chemists Subcommittee
(FIACS). From statistical analysis of the data, NIST assigned certified concentrations for the eleven analytes measured at
NIST and reference concentrations for the proximates, six additional fatty acids, seven minerals, and seven water-soluble
vitamins. Information values without uncertainties are provided for the concentrations of six additional constituents for
which the uncertainties could not adequately be assessed. SRM 1546 will provide laboratories with a means to evaluate the
accuracy of the methods they use to assign nutrient levels to processed meats and similar products.
Received: 11 October 2000 / Revised: 15 December 2000 / Accepted: 21 December 2000 相似文献
17.
Efficient CO2 Removal for Ultra‐Pure CO Production by Two Hybrid Ultramicroporous Materials 下载免费PDF全文
Dr. Kai‐Jie Chen Dr. Qing‐Yuan Yang Dr. Susan Sen Dr. David G. Madden Amrit Kumar Dr. Tony Pham Katherine A. Forrest Dr. Nobuhiko Hosono Prof. Dr. Brian Space Prof. Dr. Susumu Kitagawa Prof. Dr. Michael J. Zaworotko 《Angewandte Chemie (International ed. in English)》2018,57(13):3332-3336
Removal of CO2 from CO gas mixtures is a necessary but challenging step during production of ultra‐pure CO as processed from either steam reforming of hydrocarbons or CO2 reduction. Herein, two hybrid ultramicroporous materials (HUMs), SIFSIX‐3‐Ni and TIFSIX‐2‐Cu‐i , which are known to exhibit strong affinity for CO2, were examined with respect to their performance for this separation. The single‐gas CO sorption isotherms of these HUMs were measured for the first time and are indicative of weak affinity for CO and benchmark CO2/CO selectivity (>4000 for SIFSIX‐3‐Ni ). This prompted us to conduct dynamic breakthrough experiments and compare performance with other porous materials. Ultra‐pure CO (99.99 %) was thereby obtained from CO gas mixtures containing both trace (1 %) and bulk (50 %) levels of CO2 in a one‐step physisorption‐based separation process. 相似文献
18.
19.
We discuss the top-secret Manhattan Project site established at the Bonebrake Theological Seminary in 1943 in Dayton, Ohio, where research on polonium and its production was carried out. The polonium produced there was then transported to Los Alamos to be used in a polonium–beryllium neutron source whose purpose was to ignite the plutonium implosion bomb that would be dropped on Nagasaki, Japan, on August 9, 1945. Our account is based primarily on the recollections of John J. Sopka, research physicist at the Bonebrake laboratory. 相似文献
20.
Hui Ye Limei Hui Katherine Kellersberger Lingjun Li 《Journal of the American Society for Mass Spectrometry》2013,24(1):134-147
Considerable effort has been devoted to characterizing the crustacean stomatogastric nervous system (STNS) with great emphasis on comprehensive analysis and mapping distribution of its diverse neuropeptide complement. Previously, immunohistochemistry (IHC) has been applied to this endeavor, yet with identification accuracy and throughput compromised. Therefore, molecular imaging methods are pursued to unequivocally determine the identity and location of the neuropeptides at a high spatial resolution. In this work, we developed a novel, multi-faceted mass spectrometric strategy combining profiling and imaging techniques to characterize and map neuropeptides from the blue crab Callinectes sapidus STNS at the network level. In total, 55 neuropeptides from 10 families were identified from the major ganglia in the C. sapidus STNS for the first time, including the stomatogastric ganglion (STG), the paired commissural ganglia (CoG), the esophageal ganglion (OG), and the connecting nerve stomatogastric nerve (stn) using matrix-assisted laser desorption/ionization tandem time-of-flight (MALDI-TOF/TOF) and the MS/MS capability of this technique. In addition, the locations of multiple neuropeptides were documented at a spatial resolution of 25 μm in the STG and upstream nerve using MALDI-TOF/TOF and high-mass-resolution and high-mass-accuracy MALDI-Fourier transform ion cyclotron resonance (FT-ICR) instrument. Furthermore, distributions of neuropeptides in the whole C. sapidus STNS were examined by imaging mass spectrometry (IMS). Different isoforms from the same family were simultaneously and unambiguously mapped, facilitating the functional exploration of neuropeptides present in the crustacean STNS and exemplifying the revolutionary role of this novel platform in neuronal network studies. Figure
55 neuropeptides from 10 families were mapped in the crustacean stomatogastric nervous system with high spatial and spectral resolution via MALDI-TOF/TOF and MALDI-FT-ICR IMS 相似文献