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101.
The efficiency of fluorescence resonance energy transfer (FRET) between two chromophores positioned at opposite ends of DNA base pair domains has been investigated. The base pair domain serves as a helical scaffold which defines both the distance between chromophores and the dihedral angle between their electronic transition dipole moments, each incremental base pair increasing the distance and stepping the dihedral angle. Fluorescence quantum yields and lifetimes have been determined for both the donor and acceptor chromophores. The experimental data are found to be in excellent accord with an oriented dipole model, rather than with the averaged dipole model conventionally assumed for FRET. 相似文献
102.
Zachary M. Schulte Yeon Hye Kwon Yi Han Chong Liu Lin Li Yahui Yang Austin Gamble Jarvi Sunil Saxena Gtz Veser J. Karl Johnson Nathaniel L. Rosi 《Chemical science》2020,11(47):12807
Metal–organic frameworks constructed from multiple (≥3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn–Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H2/CO2 separation ability of bMOF-200. We examine the H2/CO2 separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H2/CO2 separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H2 and CO2 and a significantly improved H2/CO2 separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H2/CO2 separations.Tailorable multicomponent MOFs and MOF membranes for efficient H2/CO2 separation. 相似文献
103.
Jiang‐Tao Chen Hai‐Zhou Li Dong Wang Ying‐Jun Zhang Chong‐Ren Yang 《Helvetica chimica acta》2006,89(7):1442-1448
Three new dammarane monodesmosides, named notoginsenosides Ft1 ( 1 ), Ft2 ( 2 ), and Ft3 ( 3 ), together with three known ginsenosides, were obtained from a mild acidic hydrolysis of the saponins from notoginseng (Panax notoginseng (Burk .) F. H. Chen ) leaves. Their structures were elucidated to be (3β,12β,20R)‐12,20‐dihydroxydammar‐24‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 1 ), (3β,12β)‐12,20,25‐trihydroxydammaran‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 2 ), and (3β,12β,24ξ)‐12,20,24‐trihydroxydammar‐25‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 3 ), by means of spectroscopic evidences. The known ginsenosides Rh2 and Rg3 4 – 6 were obtained as the major products from this acidic deglycosylation. 相似文献
104.
Mixing enhancement has drawn great attention from designers of micromixers, since the flow in a microchannel is usually characterized by a low Reynolds number (Re) which makes the mixing quite a difficult task to accomplish. In this paper, a novel integrated efficient micromixer named serpentine laminating micromixer (SLM) has been designed, simulated, fabricated and fully characterized. In the SLM, a high level of efficient mixing can be achieved by combining two general chaotic mixing mechanisms: splitting/recombination and chaotic advection. The splitting and recombination (in other terms, lamination) mechanism is obtained by the successive arrangement of "F"-shape mixing units in two layers. The advection is induced by the overall three-dimensional serpentine path of the microchannel. The SLM was realized by SU-8 photolithography, nickel electroplating, injection molding and thermal bonding. Mixing performance of the SLM was fully characterized numerically and experimentally. The numerical mixing simulations show that the advection acts favorably to realize the ideal vertical lamination of fluid flow. The mixing experiments based on an average mixing color intensity change of phenolphthalein show a high level of mixing performance was obtained with the SLM. Numerical and experimental results confirm that efficient mixing is successfully achieved from the SLM over the wide range of Re. Due to the simple and mass producible geometry of the efficient micromixer, SLM proposed in this study, the SLM can be easily applied to integrated microfluidic systems, such as micro-total-analysis-systems or lab-on-a-chip systems. 相似文献
105.
[reaction; see text] Picosecond and nanosecond time-resolved resonance Raman (TR(3)) spectroscopy was employed to investigate the deprotonation/ionization reaction of p-hydroxyacetophenone (HA) after ultraviolet photolysis in water solution. The TR(3) spectra in conjunction with density functional theory (DFT) calculations were used to characterize the structure and dynamics of the excited-state HA deprotonation to form HA anions in near neutral water solvent. DFT calculations based on a solute-solvent intermolecular H-bonded complex model containing up to three water molecules were used to evaluate the H-bond interactions and their influence on the deprotonation reaction and the structures of the intermediates. The deprotonation reaction was found to occur on the triplet manifold with a planar H-bonded HA triplet complex as the precursor species. The HA triplet species is generated within several picoseconds and then decays with a approximately 10 ns time constant to produce the HA triplet anion species after 267 nm photolysis of HA in water solution. The triplet anion species was observed to decay with a time constant of about 90 ns into the ground-state anion species that was found to have a lifetime of about 200 ns. The DFT calculations on the H-bonded complexes of the anion triplet and ground-states species suggest that these anion species are H-bonded complexes with planar quinonoidal structures containing two water molecules H-bonded, respectively, with oxygen lone pairs of the carbonyl and deprotonated hydroxyl moieties. A deactivation scheme of the photoexcited HA in regard to the deprotonation reaction in neutral water solutions was proposed. With the above dynamic and structural information available, we briefly discuss the possible implications of the model HA photochemistry in water solutions for the photodeprotection reactions of related p-HP phototrigger compounds in aqueous solutions. 相似文献
106.
Thiam Seong Chong 《Journal of organometallic chemistry》2005,690(18):4132-4138
Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO)2L and Cp*M(CO)2L (M = Mo, W; L = CO, PR3) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)4L (M = Mn, Re; L = CO, PR3, AsPh3, SbPh3) and CpM(CO)n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO)3 radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO)2PR3 radicals from CpMo(CO)3 in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed. 相似文献
107.
细胞膜在细胞与外界环境间的物质运输、能量转换和信息传递等过程中起着重要作用,研究和控制细胞膜上的分子的相互作用,对理解和操控细胞的生理功能具有重要意义。脱氧核糖核酸(Deoxyribonucleic acid, DNA)分子具有精确自组装和可编程的特性,是一种研究生物膜分子相互作用的新工具。本综述中,我们概括了DNA分子修饰细胞膜的方法,随后介绍了基于DNA分子的监测、控制细胞膜分子相互作用的工作以及DNA分子介导细胞连接的研究,并分析了上述研究的局限性。最后,我们对基于DNA的细胞膜功能化研究进行总结与展望,以期促进对细胞膜功能的新认识,获得控制细胞功能的新方法。 相似文献
108.
Ogawa AK DeMattei JA Scarlato GR Tellew JE Chong LS Armstrong RW 《The Journal of organic chemistry》1996,61(18):6153-6161
We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product. 相似文献
109.
IntroductionItiswellknownthatmetallocenesactivatedwithmethylaluminoxane (MAO)arehighlyactivehomogeneousZiegler Nattacatalyststhatproducepolyolefinwithcon trolledstereoregularityandnarrowmolecularweightdistri bution ,1 4 however,themolecularweightofthepolym… 相似文献
110.
Charge-discharge Behavior of Surface-coated LiMn2O3.95F0.05 Cathode Materials at High Temperature 总被引:1,自引:0,他引:1
ZhaoYongCHEN YanRongLI ZuoLongYU 《中国化学快报》2003,14(12):1296-1298
With inorganic salts such as LiNO3, Li2CO3, surface-coated LiMn2O3.95F0.05 were prepared by melt-impregnation method. When these surface-coated LiMn2O3.95F0.05 were used as cathode materials, their charge-discharge characters were carefully compared. As a result, they exhibited good charge-discharge properties at 50℃ high temperature. Especially, LiNO3 surface-coated LiMn2O3.9F50.05 retained nearly 80% initial reversible capacity after 130 cycles at 50℃. 相似文献