全文获取类型
收费全文 | 770篇 |
免费 | 23篇 |
国内免费 | 15篇 |
专业分类
化学 | 419篇 |
晶体学 | 17篇 |
力学 | 25篇 |
数学 | 158篇 |
物理学 | 189篇 |
出版年
2023年 | 10篇 |
2022年 | 27篇 |
2021年 | 23篇 |
2020年 | 18篇 |
2019年 | 32篇 |
2018年 | 15篇 |
2017年 | 21篇 |
2016年 | 35篇 |
2015年 | 21篇 |
2014年 | 29篇 |
2013年 | 123篇 |
2012年 | 34篇 |
2011年 | 40篇 |
2010年 | 37篇 |
2009年 | 24篇 |
2008年 | 23篇 |
2007年 | 24篇 |
2006年 | 22篇 |
2005年 | 9篇 |
2004年 | 11篇 |
2003年 | 14篇 |
2002年 | 12篇 |
2001年 | 10篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 11篇 |
1997年 | 16篇 |
1996年 | 12篇 |
1995年 | 6篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1990年 | 4篇 |
1987年 | 3篇 |
1982年 | 3篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1973年 | 4篇 |
1969年 | 3篇 |
1967年 | 6篇 |
1966年 | 5篇 |
1965年 | 7篇 |
1964年 | 4篇 |
1962年 | 9篇 |
1960年 | 4篇 |
1959年 | 3篇 |
1956年 | 3篇 |
1955年 | 4篇 |
1933年 | 4篇 |
1927年 | 2篇 |
1923年 | 2篇 |
排序方式: 共有808条查询结果,搜索用时 46 毫秒
21.
ERGÜN KASAP SÜLEYMAN ÜZCELÍK 《Journal of inclusion phenomena and macrocyclic chemistry》1997,28(3):259-267
IR spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, or Co), and IR and Raman spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Ni or Cd) clathrates are reported. The spectral features suggest that the compounds are similar in structure to the Hofmann-dabn-type clathrates. 相似文献
22.
It is shown that (−)-(S)-N,N-dimethyl-2-(1′-methylallyl)aniline ((−)-(S)- 4 ), on direct irradiation in MeCN at 20°, undergoes in its lowest-lying triplet state an aromatic di-π-methane (ADPM) rearrangement to yield (−)-(1′R,2′R)- and (+)-(1′R,2′S)-N,N-dimethyl-2-(2-methylcyclopropyl)aniline ((−)-trans- and (+)-cis- 7 ) in an initial trans/cis ratio of 4.71 ± 0.14 and in optical yields of 28.8 ± 5.2% and 15 ± 5%, respectively. The ADPM rearrangement of (−)-(S)- 4 to the trans- and cis-configurated products occurs with a preponderance of the path leading to retention of configuration at the pivot atom (C(1′) in the reactant and C(2′) in the products) for (−)-trans- 7 and to inversion of configuration for (+)-cis- 7 , respectively. The results can be rationalized by assuming reaction paths which involve the occurrence of discrete 1,4- and 1,3-diradicals (cf. Schemes 10, 12, and 13). A general analysis of such ADPM rearrangements which allows the classification of these photochemical reactions in terms of borderline cases is presented (Scheme 14). It is found that the optical yields in these ‘step-by-step’ rearrangements are determined by the first step, i.e. by the disrotatory bond formation between C(2) of the aromatic moiety and C(2′) of the allylic side chain leading to the generation of the 1,4-diradicals. Moderation of the optical yields can occur in the ring closure of the 1,3-diradicals to the final products, which may take place with different trans/cis-ratios for the individual 1,3-diradicals. Compounds (−)-trans- 7 as well as (+)-cis- 7 easily undergo the well-known photochemical trans/cis-isomerization. It mainly leads to racemization. However, a small part of the molecules shows trans/cis-isomerization with inversion of configuration at C(1′), which is best explained by a photochemical cleavage of the C(1′)–C(3′) bond. 相似文献
23.
Bianca S. Shemper A. Ersin Acar Lon J. Mathias 《Journal of polymer science. Part A, Polymer chemistry》2002,40(3):334-343
The copper‐catalyzed atom transfer radical polymerization (ATRP) of poly(propylene glycol) methacrylate (PPGM) in solution to produce linear and starlike polymers is reported, using methylethyl ketone as the solvent and a temperature of 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer without protecting hydroxyl end groups of monomer. The polymerizations were consistent with “living” or controlled processes, as revealed by the linear evolution of molecular weight with conversion. Increasing the [M]0:[I]0 ratio resulted in increasing molecular weights, whereas the polydispersity indices remained low (Mw/Mn < 1.4) even at high conversion. Decreasing the [CuBr]0:[I]0 ratio resulted in lower conversions, slightly larger polydispersities, and decreased molecular weights, likely resulting from a lower initiation efficiency. Polymers were characterized by 1H and 13C NMR; molecular weights of polymers with low degrees of polymerization were estimated by end‐group analysis from 13C NMR spectra obtained using distortionless enhancement by polarization transfer and the gated decoupling techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 334–343, 2002 相似文献
24.
Immobilization of Mercuric reductase from aPseudomonas putida strain on different activated carriers
F. B. Anspach M. Huckel M. Brunke H. SChÜTte W. D. Deckwer 《Applied biochemistry and biotechnology》1994,44(2):135-150
Mercuric reductase was isolated fromPseudomonas putida KT2442::mer-73 and immobilized on Chromatographic carriers activated by various methods. The immobilization methods for covalent coupling were compared with regard to preservation of enzymatic activity and coupling yields. Highest yields were obtained with carriers bearing the most reactive functional groups. Best results were achieved with tresyl chloride-activated carriers. The optimum binding conditions were found at pH 8. Application of the immobilized mercuric reductase for continuous treatment of Hg(II)-containing water was examined in a fixed bed reactor. Space-time yields up to 510 nmol/min-mL were attained. The kinetics of immobilized enzyme systems were not diffusion-controlled. 相似文献
25.
Beşli S Coles SJ Davies DB Eaton RJ Hursthouse MB Kiliç A Shaw RA Yenilmez Ciftçi G Yeşilot S 《Journal of the American Chemical Society》2003,125(16):4943-4950
A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA. 相似文献
26.
27.
In this study, well-defined, high density poly(2-(dimethylamino)ethyl methacrylate) [poly(DMAEMA)] brushes were fabricated by the combination of the self-assembly of a monolayer of RAFT agent and surface-mediated RAFT polymerization. The whole fabrication process of the poly(DMAEMA) was followed by water contact angles, grazing angle-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. Kinetic studies revealed a linear increase in poly(DMAEMA) film thickness with polymerization time, indicating that the chain growth from the surface was a controlled process. Characterization of the poly(DMAEMA) brushes, such as molecular weight and thickness determination, were measured by gel permeation chromatography, and ellipsometry, and the grafting density was estimated. The pH response of the poly(DMAEMA) brushes was further investigated and the results verified the “brush-like” to “mushroom-like” transition of the poly(DMAEMA) chains due to the reversible protonation/deprotonation upon changing the solution pH. 相似文献
28.
Research on Chemical Intermediates - Palladium (II) complex with 4-tert-butylbenzoic hydrazide (TBBH)/triphenylphosphine (PPh3) ligands was successfully synthesized and characterized by X-ray,... 相似文献
29.
The electronic absorption spectrum of 1-chloromethyl hypochlorite ClCH2OCl is computed with multi-reference configuration interaction (MRD-CI) methods and compared to isomeric dichloromethanol. While the first dipole-allowed transitions of dichloromethanol Cl2CHOH are obtained above 7 eV, the corresponding transitions of ClCH2OCl are obtained at much lower energy, namely 3.66eV (11A″ ←[Xtilde]1A′), 4.96eV (21A′←[Xtilde]1A′), 6.04eV (21A″←[Xtilde]1A′) and 6.67eV (31A′ ← [Xtilde]1 A′). A further strong transition is computed at 7.82eV (41A′ ← [Xtilde]1A′) with a relatively large oscillator strength of ? = 0.4. 相似文献
30.
Altan Kara Perihan Ünak Cenk Selçuki Özlet Akça E. İlker Medine Serhan Sakarya 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(1):807-813
This research aims to investigate the interaction between phytohemagglutinin-L (PHA-L) and sialic acid, which is abundant on the breast cancer cell (MCF-7) surface and displays monosaccharide characteristics, by experimental and computational methods. Experimentally, CdSe/CdS nanoparticles (QDs) were synthesized; PHA-L was conjugated with QDs and labeled with 125I. Radiolabeling yield was found to be 97 ± 1.2 %. Afterwards, in vitro bioaffinities of radiolabeled PHA-L conjugated QDs have been investigated on MCF-7 cells and it has been observed that the cell incorporation increased with time. The results indicated that 125I labeled QD-PHA-L conjugates represent significant affinity on MCF-7 cells. In the second step of the study, the crystal structure of carbohydrate interaction surface of PHA-L was extracted from the crystal structure of PHA-L. The interactions between this surface and sialic acid were calculated by computational tools. These calculations revealed specific interactions between PHA-L and sialic acid. Semi-empirical methods, PM3 and AM1, were used in these calculations. Significant outcomes have been obtained from the experimental and computational studies and these results demonstrated that PHA-L may be an effective agent for imagining MCF-7 cells. 相似文献