全文获取类型
收费全文 | 6206篇 |
免费 | 140篇 |
国内免费 | 44篇 |
专业分类
化学 | 4613篇 |
晶体学 | 66篇 |
力学 | 143篇 |
数学 | 641篇 |
物理学 | 927篇 |
出版年
2023年 | 26篇 |
2022年 | 48篇 |
2021年 | 51篇 |
2020年 | 76篇 |
2019年 | 94篇 |
2018年 | 65篇 |
2017年 | 45篇 |
2016年 | 128篇 |
2015年 | 107篇 |
2014年 | 119篇 |
2013年 | 274篇 |
2012年 | 371篇 |
2011年 | 460篇 |
2010年 | 219篇 |
2009年 | 190篇 |
2008年 | 392篇 |
2007年 | 445篇 |
2006年 | 439篇 |
2005年 | 432篇 |
2004年 | 399篇 |
2003年 | 313篇 |
2002年 | 278篇 |
2001年 | 88篇 |
2000年 | 68篇 |
1999年 | 72篇 |
1998年 | 80篇 |
1997年 | 55篇 |
1996年 | 83篇 |
1995年 | 63篇 |
1994年 | 58篇 |
1993年 | 43篇 |
1992年 | 42篇 |
1991年 | 47篇 |
1990年 | 41篇 |
1989年 | 36篇 |
1988年 | 36篇 |
1987年 | 30篇 |
1986年 | 30篇 |
1985年 | 53篇 |
1984年 | 52篇 |
1983年 | 48篇 |
1982年 | 46篇 |
1981年 | 47篇 |
1980年 | 44篇 |
1979年 | 43篇 |
1978年 | 49篇 |
1977年 | 40篇 |
1976年 | 37篇 |
1975年 | 23篇 |
1974年 | 23篇 |
排序方式: 共有6390条查询结果,搜索用时 15 毫秒
121.
Mesoporous silica nanoparticles for intracellular delivery of membrane-impermeable proteins 总被引:3,自引:0,他引:3
An MCM-41-type mesoporous silica nanoparticle (MSN) material with a large average pore diameter (5.4 nm) is synthesized and characterized. The in vitro uptake and release profiles of cytochrome c by the MSN were investigated. The enzymatic activity of the released protein was quantitatively analyzed and compared with that of the native cytochrome c in physiological buffer solutions. We found that the enzymes released from the MSNs are still functional and highly active in catalyzing the oxidation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) by hydrogen peroxide. In contrast to the fact that cytochrome c is a cell-membrane-impermeable protein, we discovered that the cytochrome c-encapsulated MSNs could be internalized by live human cervical cancer cells (HeLa) and the protein could be released into the cytoplasm. We envision that these MSNs with large pores could serve as a transmembrane delivery vehicle for controlled release of membrane-impermeable proteins in live cells, which may lead to many important biotechnological applications including therapeutics and metabolic manipulation of cells. 相似文献
122.
Mechanisms associated with the isomerization of the O-methylethylene oxonium ion and its tetramethyl-substituted analogue have been explored using correlated electronic structure calculations. The minima and transition states associated with inversion at the oxygen atom, as well as those associated with opening of the epoxide ring, have been characterized. The calculated barrier to inversion at the oxygen atom for the O-methylethylene oxonium ion, 15.7 kcal/mol, agrees well with the experimentally determined value, 10+/-2 kcal/mol. Our calculations indicate that a significantly higher barrier exists for the ring-opening mechanism that leads to more thermodynamically stable structures. This work includes the first known calculations on the O-methyl-2,3-dimethyl-2-butene oxonium ion along with transition states and intermediates associated with ring opening and inversion at the oxygen atom. Results show that there is a significantly lower barrier to ring opening as compared to the O-methylethylene oxonium ion species, leading to a lower probability of isolating this species. The effects of basis sets and correlation techniques on these ions were also analyzed in this work. Our results indicate that the B3LYP/6-31G* level is reliable for obtaining molecular geometries for both minima and transition states on the C3H7O+ and C7H15O+ potential energy surfaces. 相似文献
123.
124.
The spectroscopic, electronic, and DNA-binding characteristics of two novel ruthenium complexes based on the dialkynyl ligands 2,3-bis(phenylethynyl)-1,4,8,9-tetraaza-triphenylene (bptt, 1) and 2,3-bis(4-tert-butyl-phenylethynyl)-1,4,8,9-tetraaza-triphenylene (tbptt, 2) have been investigated. Electronic structure calculations of bptt reveal that the frontier molecular orbitals are localized on the pyrazine-dialkynyl portion of the free ligand, a property that is reflected in a red shift of the lowest energy electronic transition (1: λ(max) = 393 nm) upon substitution at the terminal phenyl groups (2: λ(max) = 398 nm). Upon coordination to ruthenium, the low-energy ligand-centered transitions of 1 and 2 are retained, and metal-to-ligand charge transfer transitions (MLCT) centered at λ(max) = 450 nm are observed for [Ru(phen)(2)bptt](2+)(3) and [Ru(phen)(2)tbptt](2+)(4). The photophysical characteristics of 3 and 4 in ethanol closely parallel those observed for [Ru(bpy)(3)](2+) and [Ru(phen)(3)](2+), indicating that the MLCT excited state is primarily localized within the [Ru(phen)(3)](2+) manifold of 3 and 4, and is only sparingly affected by the extended conjugation of the bptt framework. In an aqueous environment, 3 and 4 possess notably small luminescence quantum yields (3: ?(H(2)O) = 0.005, 4: ?(H(2)O) = 0.011) and biexponential decay kinetics (3: τ(1) = 40 ns, τ(2) = 230 ns; 4: τ(1) ~ 26 ns, τ(2) = 150 ns). Addition of CT-DNA to an aqueous solution of 3 causes a significant increase in the luminescence quantum yield (?(DNA) = 0.045), while the quantum yield of 4 is relatively unaffected (?(DNA) = 0.013). The differential behavior demonstrates that tert-butyl substitution on the terminal phenyl groups inhibits the ability of 4 to intercalate with DNA. Such changes in intrinsic luminescence demonstrate that 3 binds to DNA via intercalation (K(b) = 3.3 × 10(4) M(-1)). The origin of this light switch behavior involves two competing (3)MLCT states similar to that of the extensively studied light switch molecule [Ru(phen)(2)dppz](2+). The solvent- and temperature-dependence of the luminescence of 3 reveal that the extended ligand aromaticity lowers the energy of the (3)ππ* excited state into competition with the emitting (3)MLCT state. Interconversion between these two states plays a significant role in the observed photophysics and is responsible for the dual emission in aqueous environments. 相似文献
125.
Dynamics of ice nucleation on water repellent surfaces 总被引:3,自引:0,他引:3
Alizadeh A Yamada M Li R Shang W Otta S Zhong S Ge L Dhinojwala A Conway KR Bahadur V Vinciquerra AJ Stephens B Blohm ML 《Langmuir : the ACS journal of surfaces and colloids》2012,28(6):3180-3186
Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications. 相似文献
126.
Tyrsted C Pauw BR Jensen KM Becker J Christensen M Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5759-5766
Understanding nanoparticle-formation reactions requires multi-technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y(2)O(3) equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub-nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit-cell dimensions. At yttria-doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time-resolved nanoparticle size distributions are calculated based on whole-powder-pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle-size distributions occur. In situ total scattering provides structural insight into the sub-nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six-coordinated zirconium atoms in the initial amorphous clusters to eight-coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration. 相似文献
127.
Schwizer D Patton JT Cutting B Smieško M Wagner B Kato A Weckerle C Binder FP Rabbani S Schwardt O Magnani JL Ernst B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(5):1342-1351
A new class of N-acetyl-D-glucosamine (GlcNAc) mimics for E-selectin antagonists was designed and synthesized. The mimic consists of a cyclohexane ring substituted with alkyl substituents adjacent to the linking position of the fucose moiety. Incorporation into E-selectin antagonists led to the test compounds 8 and the 2'-benzoylated analogues 21, which exhibit affinities in the low micromolar range. By using saturation transfer difference (STD)-NMR it could be shown that the increase in affinity does not result from an additional hydrophobic contact of the alkyl substituent with the target protein E-selectin, but rather from a steric effect stabilizing the antagonist in its bioactive conformation. The loss of affinity found for antagonists 10 and 35 containing a methyl substituent in a remote position (and therefore unable to support to the stabilization of the core) further supports this hypothesis. Finally, when a GlcNAc mimetic containing two methyl substituents (52 and 53) was used, in which one methyl was positioned adjacent to the fucose linking position and the other was in a remote position, the affinity was regained. 相似文献
128.
Oxidation of CpCr[(XylNCMe)(2)CH] (Xyl = 2,6-Me(2)C(6)H(3)) with pyridine N-oxide or air generated the μ-oxo dimer, {CpCr[(XylNCMe)(2)CH]}(2)(μ-O). The μ-oxo dimer was converted to paramagnetic Cr(III) CpCr[(XylNCMe)(2)CH](X) complexes (X = OH, O(2)CPh, Cl, OTs) via protonolysis reactions. The related Cr(III) alkoxide complexes (X = OCMe(3), OCMe(2)Ph) were prepared by salt metathesis and characterized by single crystal X-ray diffraction. The interconversion of the Cr(III) complexes and their reduction back to Cr(II) with Mn powder were monitored using UV-vis spectroscopy. The related CpCr[(DepNCMe)(2)CH] (Dep = 2,6-Et(2)C(6)H(3)) Cr(II) complex was studied for catalytic oxygen atom transfer reactions with PPh(3) using O(2) or air. Both Cr(II) complexes reacted with pyridine N-oxide and γ-terpinene to give the corresponding Cr(III) hydroxide complexes. When CpCr[(DepNCMe)(2)CH] was treated with pyridine N-oxide in benzene in the absence of hydrogen atom donors, a dimeric Cr(III) hydroxide product was isolated and structurally characterized, apparently resulting from intramolecular hydrogen atom abstraction of a secondary benzylic ligand C-H bond followed by intermolecular C-C bond formation. The use of very bulky hexaisopropylterphenyl ligand substituents did not preclude the formation of the analogous μ-oxo dimer, which was characterized by X-ray diffraction. Attempts to develop a chromium-catalyzed intermolecular hydrogen atom transfer process based on these reactions were unsuccessful. The protonolysis and reduction reactions of the μ-oxo dimer were used to improve the previously reported Cr-catalyzed radical cyclization of a bromoacetal. 相似文献
129.
The first total synthesis of (+)-dragmacidin F has been accomplished, establishing the absolute configuration of this biologically important, antiviral marine alkaloid. The convergent route described features a palladium-mediated oxidative pyrrole carbocylization reaction to construct the [3.3.1] bicycle, as well as a highly selective Suzuki coupling to build the carbon skeleton of the natural product. A late-stage Neber rearrangement allows for the facile installation of the aminoimidazole moiety to provide (+)-dragmacidin F. 相似文献
130.
A general method for the synthesis of β-substituted and unsubstituted cycloheptenones bearing enantioenriched all-carbon γ-quaternary stereocenters is reported. Hydride or organometallic addition to a seven-membered ring vinylogous ester followed by finely tuned quenching parameters achieves elimination to the corresponding cycloheptenone. The resulting enones are elaborated to bi- and tricyclic compounds with potential for the preparation of non-natural analogs and whose structures are embedded in a number of cycloheptanoid natural products. 相似文献