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971.
972.
本工作用激光光散射和光学显微镜手段研究了聚甲基丙烯酸甲醋(PMMA)和聚醋酸乙烯酯[PVAc]共混体系相分离过程。结果表明系统的相态结构呈现较强的自相似,结构函数在大波矢处具有q~(-6)的渐近行为,相结构具有分形特征,其分形维数[Fractal Dimension]D约为1,64,初步认为结构函数的标度[Scaling]行为是由于相结构的分形特征所致。 相似文献
973.
Xiaoxue Wang Yujie Qian Hanyu Gao Connor
W. Coley Yiming Mo Regina Barzilay Klavs F. Jensen 《Chemical science》2020,11(40):10959
Computer aided synthesis planning of synthetic pathways with green process conditions has become of increasing importance in organic chemistry, but the large search space inherent in synthesis planning and the difficulty in predicting reaction conditions make it a significant challenge. We introduce a new Monte Carlo Tree Search (MCTS) variant that promotes balance between exploration and exploitation across the synthesis space. Together with a value network trained from reinforcement learning and a solvent-prediction neural network, our algorithm is comparable to the best MCTS variant (PUCT, similar to Google''s Alpha Go) in finding valid synthesis pathways within a fixed searching time, and superior in identifying shorter routes with greener solvents under the same search conditions. In addition, with the same root compound visit count, our algorithm outperforms the PUCT MCTS by 16% in terms of determining successful routes. Overall the success rate is improved by 19.7% compared to the upper confidence bound applied to trees (UCT) MCTS method. Moreover, we improve 71.4% of the routes proposed by the PUCT MCTS variant in pathway length and choices of green solvents. The approach generally enables including Green Chemistry considerations in computer aided synthesis planning with potential applications in process development for fine chemicals or pharmaceuticals.A new MCTS variant with a reinforcement learning value network and solvent prediction model proposes shorter synthesis routes with greener solvents. 相似文献
974.
文章对广西当前控制的矿产112种中,分别用单一指标、双指标和综合指标,以及不同方法评价优势矿产及其优势矿产排序。变矿产优势为经济优势战略发展模式设想。 相似文献
975.
聚β—羟基丁酸酯/聚醋酸乙烯酯共混体系的相容性与结晶行为 总被引:4,自引:0,他引:4
研究了制样过程聚β-羟基丁酸酯/聚醋酸乙烯酯共混体系的相容性和结晶行为的影响。DSC、SAXS、POM等实验结果表明,PHB/PVAc共混物经溶液成膜后处于分相的状态,PVAc对PHB的结晶能力影响不大;而经融处理后,PHB/PVAc共混物则处于相容的均相状态,随PVAc的含量含量的增加。 相似文献
976.
The microemulsification in palm-kernel oil/cetyltrimethylammonium bromide/iso-pentanol/water system is investigated. The effect of iso-pentanol concentration in microemulsions on the size of single-phase
microemulsion region is also discussed. It is found that the maximum microemulsion domain is obtained when iso-pentanol-to-cetyltrimethylammonium bromide mass ratio is 1.75. The diffusion coefficients of electroactive probe (ferrocene)
in microemulsion microenvironment are measured by 1.5-order differential electroanalysis. The microstructure and structural
transition from water-in-oil to oil-in-water microemulsions through a bicontinuous structure is examined. The results are
found to be in agreement with that of conductivity measurements. 相似文献
977.
Kim E Kamaraj K Galliker B Rubie ND Moënne-Loccoz P Kaderli S Zuberbühler AD Karlin KD 《Inorganic chemistry》2005,44(5):1238-1247
Recent spectroscopic, kinetics, and structural studies on cytochrome c oxidases (CcOs) suggest that the histidine-tyrosine cross-link at the heme a3-CuB binuclear active site plays a key role in the reductive O2-cleavage process. In this report, we describe dioxygen reactivity of copper and heme/Cu assemblies in which the imidazole-phenol moieties are employed as a part of copper ligand LN4OH (2-{4-[2-(bis-pyridin-2-ylmethyl-amino)-ethyl]-imidazol-1-yl}-4,6-di -tert-butyl-phenol). Stopped-flow kinetic studies reveal that low-temperature oxygenation of [CuI(LN4OH)]+ (1) leads to rapid formation of a copper-superoxo species [CuII(LN4OH)(O2-)]+ (1a), which further reacts with 1 to form the 2:1 Cu:O2 adduct, peroxo complex [{CuII(LN4OH)}2(O2(2-))]2+ (1b). Complex 1b is also short-lived, and a dimer Cu(II)-phenolate complex [CuII(LN4O-)]2(2+) (1c) eventually forms as a final product in the later stage of the oxygenation reaction. Dioxygen reactivities of 1 and its anisole analogue [CuI(LN4OMe)]+ (2) in the presence of a heme complex (F8)FeII (3) (F8 = tetrakis(2,6,-difluorotetraphenyl)-porphyrinate) are also described. Spectroscopic investigations including UV-vis, 1H and 2H NMR, EPR, and resonance Raman spectroscopies along with spectrophotometric titration reveal that low-temperature oxygenation of 1/3 leads to formation of a heme-peroxo-copper species [(F8)FeIII-(O2(2-))-CuII(LN4OH)]+ (4), nu(O-O) = 813 cm(-1). Complex 4 is an S = 2 spin system with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) through a bridging peroxide ligand. A very similar complex [(F8)FeIII-(O2(2-))-CuII(LN4OMe)]+ (5) (nu(O-O) = 815 cm(-1)) can be generated by utilizing the anisole compound 2, which indicates that the cross-linked phenol moiety in 4 does not interact with the bridging peroxo group between heme and copper. This investigation thus reveals that a stable heme-peroxo-copper species can be generated even in the presence of an imidazole-phenol group (i.e., possible electron/proton donor source) in close proximity. Future studies are needed to probe key factors that can trigger the reductive O-O cleavage in CcO model compounds. 相似文献
978.
COMPATIBILITY IN POLYMER BLENDS OF POLY (VINYL ACETATE) AND POLY (METHYL METHACRYLATE)STUDIED BY NMR
Compatibility of poly (vinyl acetate) (PVAc) with poly (methyl methacrylate) (PMMA) mixtures has been studied by using nuclear magnetic relaxation, differential scanning calorimeter and small-angle X-ray scattering techniques. The nuclear magnetic relaxation time T_1's were measured as a function of composition in blends of PMMA and PVAc prepared from chloroform solution. The results show that the system is miscible for casting from chloroform solution. 相似文献
979.
Zhusong Cao Jianye Li Youwen Sun Hanwen Zhang Xueling Mo Xin Cao Guozhu Zhang 《Chemical science》2021,12(13):4836
A method for remote radical C–H alkynylation and amination of diverse aliphatic alcohols has been developed. The reaction features a copper nucleophile complex formed in situ as a photocatalyst, which reduces the silicon-tethered aliphatic iodide to an alkyl radical to initiate 1,n-hydrogen atom transfer. Unactivated secondary and tertiary C–H bonds at β, γ, and δ positions can be functionalized in a predictable manner.Remote C−H alkynylation and amination of aliphatic alcohols. 相似文献
980.
Kim E Helton ME Lu S Moënne-Loccoz P Incarvito CD Rheingold AL Kaderli S Zuberbühler AD Karlin KD 《Inorganic chemistry》2005,44(20):7014-7029
In cytochrome c oxidase synthetic modeling studies, we recently reported a new mu-eta2:eta2-peroxo binding mode in the heteronuclear heme/copper complex [(2L)Fe(III)-(O2(2-))-CuII]+ (6) which is effected by tridentate copper chelation (J. Am. Chem. Soc. 2004, 126, 12716). To establish fundamental coordination and O2-reactivity chemistry, we have studied and describe here (i) the structure and dioxygen reactivity of the copper-free compound (2L)FeII (1), (ii) detailed spectroscopic properties of 6 in comparisons with those of known mu-eta2:eta1 heme-peroxo-copper complexes, (iii) formation of 6 from the reactions of [(2L)FeIICuI]+ (3) and dioxygen by stopped-flow kinetics, and (iv) reactivities of 6 with CO and PPh3. In the absence of copper, 1 serves as a myoglobin model compound possessing a pyridine-bound five-coordinate iron(II)-porphyrinate which undergoes reversible dioxygen binding. Oxygenation of 3 below -60 degrees C generates the heme-peroxo-copper complex 6 with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) to yield an S = 2 spin system. Stopped-flow kinetics in CH2Cl2/6% EtCN show that dioxygen reacts with iron(II) first to form a heme-superoxide moiety, [(EtCN)(2L)FeIII-(O2-)...CuI(EtCN)]+ (5), which further reacts with Cu(I) to generate 6. Compared to those properties of a known mu-eta2:eta1-heme-peroxo-copper complex, 6 has a significantly diminished resonance Raman nu(O-O) stretching frequency at 747 cm(-1) and distinctive visible absorptions at 485, 541, and 572 nm, all of which seem to be characteristics of a mu-eta2:eta2-heme-peroxo-copper system. Addition of CO or PPh3 to 6 yields a bis-CO adduct of 3 or a PPh(3) adduct of 5, the latter with a remaining FeIII-(O2-) moiety. 相似文献