全文获取类型
收费全文 | 1867篇 |
免费 | 107篇 |
国内免费 | 10篇 |
专业分类
化学 | 1410篇 |
晶体学 | 27篇 |
力学 | 52篇 |
数学 | 94篇 |
物理学 | 401篇 |
出版年
2024年 | 4篇 |
2023年 | 16篇 |
2022年 | 41篇 |
2021年 | 47篇 |
2020年 | 46篇 |
2019年 | 51篇 |
2018年 | 31篇 |
2017年 | 35篇 |
2016年 | 75篇 |
2015年 | 60篇 |
2014年 | 89篇 |
2013年 | 147篇 |
2012年 | 155篇 |
2011年 | 173篇 |
2010年 | 102篇 |
2009年 | 83篇 |
2008年 | 124篇 |
2007年 | 103篇 |
2006年 | 97篇 |
2005年 | 76篇 |
2004年 | 91篇 |
2003年 | 62篇 |
2002年 | 53篇 |
2001年 | 39篇 |
2000年 | 35篇 |
1999年 | 15篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 18篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 14篇 |
1992年 | 15篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有1984条查询结果,搜索用时 0 毫秒
91.
Lee KJ Kim HA Kim PH Lee HS Ma KR Park JH Kim DJ Hahn JH 《Experimental & molecular medicine》2004,36(6):534-544
During chronic inflammatory response, mono- cytes/macrophages produce 92-kDa matrix metalloproteinase-9 (MMP-9), which may contribute to their extravasation, migration and tissue remodeling. Activation of peroxisome proliferator- activated factor receptor-g (PPAR-g) has been shown to inhibit MMP-9 activity. To evaluate whether ox-LDL, a PPAR-g activator, inhibits PMA-induced MMP-9 expression and activity, and if so, whether CD36 and PPAR-g are involved in this process, we investigated the effect of ox-LDL on MMP-9 expression and activity in PMA-activated human monocytic cell line U937. PMA-induced MMP-9 expression and activity were suppressed by the treatment with ox-LDL (50 mg/ml) or PPAR-g activators such as troglitazone (5 mM), ciglitazone (5 mM), and 15d- PGJ2 (1 mM) for 24 h. This ox-LDL or PPAR-g activator-mediated inhibition of MMP-9 activity was diminished by the pre-treatment of cells with a blocking antibody to CD36, or PGF2a (0.3 mM), which is a PPAR-g inhibitor, as well as overexpression of a dominant-negative form of CD36. Taken together, these results suggest that ox-LDL suppresses PMA-induced MMP-9 expression and activity through CD36-mediated activation of PPAR-g. 相似文献
92.
Alkali metal cations easily form complexes with proteins in biological systems; understanding amino acid clusters with these cations can provide useful insight into their behaviors at the molecular level including diagnosis and therapy of related diseases. For the purpose of characterization of basic interaction between amino acids and alkali metal, each of the 20 naturally occurring amino acids were ionized in the presence of lithium, sodium and potassium cations by electrospray ionization, and the resulting product ions were analyzed. We focus our attention on the gas phase alkali metal ion-proton exchanged complexes in current study, specifically complexes with serine, threonine, asparagine and glutamine, which share characteristic pattern unlike other amino acids. All amino acids generated [M + H](+) and [M + Na](+) ions, where M stands for the neutral amino acid. Serine, threonine, asparagine and glutamine generated cluster ions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) , where n = 1-7. While the (M - H + Li) and (M - H + K) species were not observed, the neutral (M - H + Na) species formed by proton-sodium cation exchange had a highly stable cyclic structure with ketone and amine ligand sites, suggesting that (M - H + Na) serves as a building block in cluster ion formation. Cluster ion intensity distributions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) showed a magic number at n = 3 and 4, respectively. Extensive B3LYP-DFT quantum mechanical calculations were carried out to elucidate the geometry and energy of the cluster ions, and they provided a reasonable explanation for the stability and structure of the cluster ions. 相似文献
93.
Choi JK Jang S Kim KJ Sohn H Jeong HD 《Journal of the American Chemical Society》2011,133(20):7764-7785
A new kind of organic-inorganic hybrid polymer, poly(tetraphenyl)silole siloxane, was invented and synthesized for realization of its unique charge trap properties. The organic portions consisting of (tetraphenyl)silole rings were responsible for negative charge trapping, while the Si-O-Si inorganic linkages provided the intrachain energy barrier for controlling electron transport. The polysilole siloxane dielectric thin films were fabricated by spin-coating and curing of the polymers, followed by characterization with spectroscopic ellipsometry (SE), near edge X-ray absorption fine structure spectroscopy (NEXAFS), and photoemission spectroscopy (PES). The abrupt increase in density and decrease in thickness of the thin film at a curing temperature of 100 °C was attributed to a thermodynamically preferred state in the nanoscopic arrangement of the polymer chains; this was due to cofacial π-π interactions in a skewed manner between peripheral phenyl groups of the (tetraphenyl)silole rings of the adjacent polymer chains. Using the NEXAFS spectrum to assess high electron affinity, the LUMO energy level of the dielectric thin film cured at 150 °C was positioned 1 eV above the Fermi energy level (E(F)). The electron trapping of the dielectric thin films was confirmed from the positive flat band shift (ΔV(FB)) in the capacitance-voltage (C-V) measurements performed within the metal-insulator-semiconductor (MIS) device structure, which strongly verified the polymer design concept. From the simple kinetics model of the electron transport, it was proposed that the flat band shift (ΔV(FB)) or trap density of the negative charges (|ρ|) was logarithmically proportional to the decay constant (β) for the electron-tunneling process. When a phenyl group of a silole ring in a polymer chain was inserted into the two available phenyl groups of another silole ring in another polymer chain, the electron transfer between the groups was enhanced, decreasing the trap density of the negative charges (|ρ|). For the thermodynamically preferred state generating the high refractive index, the distance between the two phenyl groups of the adjacent polymer chains was estimated to be in the range of 0.27-0.36 nm. 相似文献
94.
Lee S Kim J In S Choi H Oh SM Jang CG Chung KH 《Analytical and bioanalytical chemistry》2012,403(5):1385-1394
Owing to the tight control of methamphetamine, it is presumed that phentermine, an amphetamine-type anorectic, has recently
been considered a supplement for methamphetamine abusers in Korea. In addition, the abuse of other anorectics obtained by
inappropriate means has become a social issue. Hair is a useful specimen to prove chronic drug use. Therefore, an analytical
method for the simultaneous detection of phentermine, phendimetrazine, amfepramone, fenfluramine, mazindol, methamphetamine,
and 3,4-methylenedioxymethamphetamine (MDMA), as well as their metabolites, which covers the major amphetamines and anorectic
agents in Korea, in hair was established and validated using liquid chromatography–tandem mass spectrometry (LC-MS/MS). The
drugs and their metabolites in hair were extracted using 1 % HCl in methanol and then filtered and analyzed by LC-MS/MS with
electrospray ionization in positive mode. The validation results for selectivity, linearity, matrix effect, recovery, process
efficiency, intra- and interassay precision and accuracy, and processed sample stability were satisfactory. The limits of
detection ranged from 0.025 to 1 ng/10 mg hair and the limits of quantification were 0.25 ng/10 mg hair for every analyte
except mazindol and phentermine, for which they were 10 ng/10 mg hair. The method was successfully applied for the segmental
determination of selected anorectics, methamphetamine, MDMA, and their metabolites in hair from 39 drug suspects. Among the
anorectics, phentermine and/or phendimetrazine were identified with or without methamphetamine in the hair samples. Closer
supervision of the inappropriate use of anorectics is necessary. Also, hair analysis is useful for monitoring the abuse potential
of unnoticed drugs. 相似文献
95.
Hanna GohMin Joung Kim Preeti SalujaNarinder Singh Doo Ok Jang 《Tetrahedron letters》2012,53(30):3900-3902
A dipodal receptor was synthesized by condensation of isophthalaldehyde and p-toluenesulfonylhydrazide. The receptor was found to be selective for Cu2+ recognition in CH3CN. The resultant Cu2+ receptor complex selectively recognized iodide through cation displacement assay in a CH3CN/H2O (8:2, v/v) solvent system. 相似文献
96.
Song YJ Hyun MY Lee JH Lee HG Kim JH Jang SP Noh JY Kim Y Kim SJ Lee SJ Kim C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(19):6094-6101
A mononuclear nonheme cobalt(III) complex of a tetradentate ligand containing two deprotonated amide moieties, [Co(bpc)Cl(2)][Et(4)N] (1; H(2)bpc = 4,5-dichloro-1,2-bis(2-pyridine-2-carboxamido)benzene), was prepared and then characterized by elemental analysis, IR, UV/Vis, and EPR spectroscopy, and X-ray crystallography. This nonheme Co(III) complex catalyzes olefin epoxidation upon treatment with meta-chloroperbenzoic acid. It is proposed that complex 1 shows partitioning between the heterolytic and homolytic cleavage of an O-O bond to afford Co(V)=O (3) and Co(IV)=O (4) intermediates, proposed to be responsible for the stereospecific olefin epoxidation and radical-type oxidations, respectively. Moreover, under extreme conditions, in which the concentration of an active substrate is very high, the Co-OOC(O)R (2) species is a possible reactive species for epoxidation. Furthermore, partitioning between heterolysis and homolysis of the O-O bond of the intermediate 2 might be very sensitive to the nature of the solvent, and the O-O bond of the Co-OOC(O)R species might proceed predominantly by heterolytic cleavage, even in the presence of small amounts of protic solvent, to produce a discrete Co(V) ?O intermediate as the dominant reactive species. Evidence for these multiple active oxidants was derived from product analysis, the use of peroxyphenylacetic acid as the peracid, and EPR measurements. The results suggest that a less accessible Co(V)=O moiety can form in a system in which the supporting chelate ligand comprises a mixture of neutral and anionic nitrogen donors. 相似文献
97.
Jang JY Kim MK Jeon YK Joung YK Park KD Kim CW 《Experimental & molecular medicine》2012,44(4):251-259
Cancer stem cells (CSCs) are resistant to chemo- and radio-therapy, and can survive to regenerate new tumors. This is an important reason why various anti- cancer therapies often fail to completely control tumors, although they kill and eliminate the bulk of cancer cells. In this study, we determined whether or not adenine nucleotide translocator-2 (ANT2) suppression could also be effective in inducing cell death of breast cancer stem-like cells. A sub-population (SP; CD44+/ CD24-) of breast cancer cells has been reported to have stem/progenitor cell properties. We utilized the adeno- ANT2 shRNA virus to inhibit ANT2 expression and then observed the treatment effect in a SP of breast cancer cell line. In this study, MCF7, MDA-MB-231 cells, and breast epithelial cells (MCF10A) mesenchymally-transdifferentiated through E-cadherin knockdown were used. ANT2 expression was high in both stem-like cells and non-stem-like cells of MCF7 and MDA-MB-231 cells, and was induced and up-regulated by mesenchymal transdifferentiation in MCF10A cells (MCF10A(EMT)). Knockdown of ANT2 by adeno-shRNA virus efficiently induced apoptotic cell death in the stem-like cells of MCF7 and MDA-MB-231 cells, and MCF10A(EMT). Stem-like cells of MCF7 and MDA-MB-231, and MCF10A(EMT) cells exhibited increased drug (doxorubicin) resistance, and expressed a multi-drug resistant related molecule, ABCG2, at a high level. Adeno-ANT2 shRNA virus markedly sensitized the stem-like cells of MCF7 and MDA-MB-231, and the MCF10A(EMT) cells to doxorubicin, which was accompanied by down-regulation of ABCG2. Our results suggest that ANT2 suppression by adeno-shRNA virus is an effective strategy to induce cell death and increase the chemosensitivity of stem-like cells in breast cancer. 相似文献
98.
99.
In pursuit of photo‐curable adhesive for optical communication, dual‐curable acrylic oligomers (AOs) having alkoxy silane group, fluorine atoms and vinyl group as a pendent group were synthesized by two‐stage reactions. The isocyanate group containing oligomers were firstly synthesized via radical polymerization of acrylic monomers, and followed by urethane reaction with 2‐hydroxy ethyl methacrylate. The dual curing behaviors, e.g. thermal and photo‐cure, were studied by using photo‐differential scanning calorimetry (DSC) and real‐time IR. An optimum adhesive formulation, based on AO (15 g), epoxy acrylate (80 g), isobonyl methacrylate (17 g) and photo‐initiator (3 g), was obtained. As the content of AO was increased in the optical adhesive formulation, refractive index decreased but transmittance increased due to the increase in fluorine content. The optical transmittance at the range of 1.3 to 1.55 μm was higher than 90%. The addition of colloidal silica with the earlier mentioned formulation was helpful in decreasing crosslinking volume shrinkage and the increasing of glass fiber adhesion. The required properties for the optical adhesive, including chemical resistance and thermal resistance, dimension stability, etc. were also investigated. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
100.
Ju-Won Tae Byung-Sik Jang Kyung-Hoon Kim Dae-Won Park 《Reaction Kinetics and Catalysis Letters》2005,84(1):167-174
Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1>C3>C2>C4>C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities. 相似文献