全文获取类型
收费全文 | 4289篇 |
免费 | 202篇 |
国内免费 | 32篇 |
专业分类
化学 | 3239篇 |
晶体学 | 24篇 |
力学 | 119篇 |
数学 | 528篇 |
物理学 | 613篇 |
出版年
2023年 | 38篇 |
2022年 | 58篇 |
2021年 | 79篇 |
2020年 | 100篇 |
2019年 | 102篇 |
2018年 | 72篇 |
2017年 | 57篇 |
2016年 | 138篇 |
2015年 | 121篇 |
2014年 | 153篇 |
2013年 | 229篇 |
2012年 | 302篇 |
2011年 | 371篇 |
2010年 | 162篇 |
2009年 | 133篇 |
2008年 | 322篇 |
2007年 | 316篇 |
2006年 | 308篇 |
2005年 | 254篇 |
2004年 | 216篇 |
2003年 | 192篇 |
2002年 | 158篇 |
2001年 | 35篇 |
2000年 | 35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 | 26篇 |
1989年 | 13篇 |
1988年 | 14篇 |
1987年 | 12篇 |
1986年 | 9篇 |
1985年 | 22篇 |
1984年 | 28篇 |
1983年 | 14篇 |
1982年 | 16篇 |
1981年 | 15篇 |
1980年 | 18篇 |
1979年 | 12篇 |
1978年 | 17篇 |
1977年 | 12篇 |
1976年 | 13篇 |
1975年 | 9篇 |
1974年 | 11篇 |
排序方式: 共有4523条查询结果,搜索用时 15 毫秒
41.
David Kessel Kevin M. Smith R. K. Pandey F.-Y. Shiau Barbara Henderson 《Photochemistry and photobiology》1993,58(2):200-203
Abstract— Biophysical and photobiological properties of a group of bacteriochlorins were compared with efficacy of these products for photodynamic therapy of murine tumors. Predictive factors for selective photosensitization in vivo include affinity binding to lipoproteins greater than albumin, extinction coefficient at the wavelength of irradiation and tumor/skin distribution. Efficacy was correlated with circulating plasma levels of the different sensitizers but not with the photodynamic therapy response in cell culture. 相似文献
42.
An automatic method for the absolute determination of total sulfur, which overcomes the tendency of previous methods to give low sulfur recoveries on samples with high oxygen demand, is described. The technique combusts the sample in oxygen and sweeps the combustion gases through a hydrogen peroxide trap to remove the sulfur oxides from the gas stream. The trap contents are volatilized and swept with nitrogen through reduced copper heated to 890 °C. Sulfur oxides are quantitatively converted to sulfur dioxide and titrated coulometrically with iodine. Halogens are held by the copper and do not interfere with the sulfur determination. Analysis time is 12 min and automation of the method allows unattended operation. Sample size is 0.5 to 20 mg. Sulfur levels of 0.05 to 100% can be determined. 相似文献
43.
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
44.
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
45.
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
46.
We report herein a detailed assessment of the roles of O2, H2O2, *OH, and O2-* in the TiO2 assisted photocatalytic oxidation (PCO) of arsenite. Although both arsenite, As(III), and arsenate, As(V), adsorb extensively onto the surface of TiO2, past studies relied primarily on the analysis of the arsenic species in solution, neglecting those adsorbed onto the surface of TiO2. We used extraction and analyses of the arsenic species adsorbed onto the surface of the TiO2 to illustrate that the oxidation of As(III) to As(V) occurs in an adsorbed state during TiO2 PCO. The TiO2 photocatalytic oxidation (PCO) of surface adsorbed As(III) in deoxygenated solutions with electron scavengers, Cu2+, and polyoxometalates (POM) yields oxidation rates that are comparable to those observed under oxygen saturation, implying the primary role of oxygen is as a scavenger of the conduction band electron. Pulse radiolysis and competition kinetics were employed to determine a rate constant of 3.6 x 10(6) M(-1) s(-1) for the reaction of As(III) with O2-*. Transient absorption studies of adsorbed hydroxyl radicals, generated by subjecting colloidal TiO2 to radiolytic conditions, provide convincing evidence that the adsorbed hydroxyl radical (TiO2+*OH) plays the central role in the oxidation with As(III) during TiO2 assisted photocatalysis. Our results suggest the reaction of superoxide anion radical does not contribute in the conversion of As(III) when compared to the reaction of As(III) with *OH radical during TiO2 PCO. 相似文献
47.
Controlled drug delivery remains a research focus for public health to enhance patient compliance, drug efficiency and reduce
the side effects of drugs. Pectin, an edible plant polysaccharide, has been shown to be useful for the construction of drug
delivery systems for specific drug delivery. Several pectin derived formulations have been developed in our laboratory and
tested in vitro, ex vivo, and in vivo for the ability to deliver bioactive substances for therapeutic purposes in the context of interactions with living tissues.
Pectin derivatives carrying primary amine groups were more mucoadhesive and have shown potential in nasal drug delivery and
other mucosal drug delivery. Pectin derivatives with highly esterified galacturonic acid residues are more hydrophobic and
able to sustain the release of incorporated fragrances for a prolonged duration. Less esterified pectin derivatives are able
to penetrate deeper into the skin and may be useful in aromatherapy formulations. Pectin, in combination with zein, a corn
protein, forms hydrogel beads. The bound zein restricts bead swelling and retains the porosity of the beads; the pectin networks
shield the zein from protease attack. The complex beads are ideal vehicles for colon-specific drug delivery. Studies presented
in this paper indicate the flexibility and possibility to tailor pectin macromolecules into a variety of drug delivery systems
to meet different clinical requirements.
Mention of trade names or commercial products in this article is solely for the purpose of providing specific information
and does not imply recommendation or endorsement by the US Department of Agriculture. 相似文献
48.
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
49.
Kevin Burgess Brian F.G. Johnson Jack Lewis Paul R. Raithby 《Journal of organometallic chemistry》1982,224(4):C40-C44
Organic azides [N3R] react with [Os3(CO)11(NCMe)] and with [Os3(μ-H)2(CO)10] to form [Os3(CO)10(NCMe)(N3COR)] (R Ph) and [Os3(μ-H)(CO)10(HN3R)] (R Ph, n-Bu, CH2Ph, cyclo-C6H11), respectively; the latter may be converted to [Os3(μ-H)2(CO)9(μ3-NR)] by thermolysis; the molecular structure of the phenyl derivative of each class of compound has been confirmed by x-ray analysis. 相似文献
50.
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