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971.
The relaxation time of a polymer chain in an elongational flow field was investigated for hydroxypropylcellulose (HPC) semidilute solution systems by two methods: phenomenological analysis of elongational flow-induced birefringence, and dynamic light scattering (DLS) and rheological measurements. To understand the relaxation time of an entangled semiflexible polymer solution in an elongational flow field, scaling analysis of the elongational flow-induced birefringence curve was performed. The results of both temperature and concentration scaling analyses showed that birefringence curves at different temperatures and at several HPC concentrations were described well by a universal birefringence–strain rate curve. This scaling behavior was compared with the "fuzzy cylinder" model. The critical strain rate corresponded to the correlation time of the slow relaxation mode determined by DLS measurement and the relaxation spectrum obtained by dynamic viscoelasticity measurement. The elongational flow-induced birefringence observed in an HPC semidilute solution was concluded to be attributed to the orientation of the HPC segment in the entangled molecular system, because the dominant relaxation mode is found to be the concentration fluctuation of an entangled molecular cluster in a quiescent state. 相似文献
972.
Dana Kubies Jaroslav Š?udla Rudolf Puffr Antonín Sikora Josef Baldrian Jana Ková?ová Miroslav Šlouf František Rypá?ek 《European Polymer Journal》2006,42(4):888-899
Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σy and yield strain εy, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations. 相似文献
973.
Ulrich Schubert Andreas Schenkel Johannes Müller 《Journal of organometallic chemistry》1985,292(3):c11-c14
In the reaction of Cp2WGl2 with Li[Si(SiMe3)3] the dihydrid tungstenocene derivative [(Me3Si)3SiC5H4]WH2 (3) is formed with a 56% yield. 3 crystallizes in space group P, with a 918.0(4), b 1580.9(4), c 1621.2(7) pm, α 117.63(2), β 89.95(3), γ 94.39(3)° at ?40° C. The dihedral angle between the Cp planes is 140.9°. 相似文献
974.
P. Berastegui S. HullF.J. Garc? Garc? J. Grins 《Journal of solid state chemistry》2002,168(1):294-305
The structures of the oxyorthogermanate La2(GeO4)O and the apatite-structured La9.33(GeO4)6O2 have been refined from powder neutron diffraction data. La2(GeO4)O crystallizes in a monoclinic unit cell (P21/c) and is cation stoichiometric in contrast to previous reports. La9.33(GeO4)6O2 crystallizes in a hexagonal unit cell (P63/m) and the powder diffraction data show anisotropic peak broadening that is observed in electron diffraction patterns as incommensurate diffuse spots at hkq reciprocal planes (with q=1.6-1.7) and can be attributed to a correlated disorder in the “apatite channels”. This compound was doped up to a nominal composition close to M2La8(GeO4)6O2 with M=Ca, Sr, Ba. The dopant ions preferentially occupy the 4f sites as the number of La vacancies decreases. The measured ionic conductivity of La9.33(GeO4)6O2 is about 3 orders of magnitude larger than for La2(GeO4)O at high temperatures and decreases with increasing dopant content from the highest value of about 0.16 S cm−1 at 1160 K. 相似文献
975.
Cornelissen C Erker G Kehr G Fröhlich R 《Dalton transactions (Cambridge, England : 2003)》2004,(23):4059-4063
Treatment of the complexes [(C(5)H(4)PR(2))(2)Zr(CH(3))(2)](b: R = isopropyl; c: R = cyclohexyl) with the reagent HIr(CO)(PPh(3))(3) (2b) yield the heterobimetallic complexes [mu-C(5)H(4)PR(2))(2)(H(3)C-Zr-Ir(CO)(PPh(3)))] (4b, 4c) with evolution of methane. The reaction of the -PPh(2) substituted analogue with initially yields an intermediate [(H(3)C)(2)Zr(mu-C(5)H(4)PPh(2))(2)Ir(H)(CO)(PPh(3))] 5a, that still contains both methyl groups at zirconium and does not contain a metal-metal bond. At room temperature, the intermediate reacts further with methane formation to eventually yield the (Zr-Ir) complex 4a. The corresponding [mu-C(5)H(4)PR(2))(2)(H(3)C-Zr-Rh(CO)(PPh(3)))] complexes 3a (R = Ph) and 3b (R = isopropyl) react cleanly with isopropyl alcohol to liberate methane and yield the corresponding [mu-C(5)H(4)PR(2))(2)(Me(2)CHO-Zr-Rh(CO)(PPh(3)))] products (7a, 7b). Carefully monitoring the reaction of with Me(2)CHOH by NMR revealed that the Zr-Rh functionality is attacked first to give the intermediate [Me(Me(2)CHO)Zr([micro sign]-C(5)H(4)PR(2))(2)Rh(H)(CO)(PPh(3))] (6b). This intermediate then reacts further to cleave off methane and re-form the (Zr-Rh) metal-metal bond to yield the product 7b. The tetrametallic mu-oxo-(Zr-Rh) metallocene derivate 11a was obtained starting from the (Zr-Rh) complex 3a and it was characterized by X-ray diffraction. It may be that this reaction is also initiated by H-OH addition to the [Zr-Rh] metal-metal bond. 相似文献
976.
A modified thiocyanate method without extraction by using rhodamine 6G as a secondary ligand was developed. Molybdenum in 1.0×10−2 M HCl, after the addition of ascorbic acid, was heated for 10 min in a 90 °C water bath for reduction. Suitable amounts of glycerine, Triton X-100, rhodamine 6G solutions and 2+1 (v/v) 9 M H2SO4+3 M KHSO4 were added in this order. This solution was allowed to cool to room temperature and the absorbance at 570 nm was measured against a reagent blank 45 min after the addition of thiocyanate solution and the second aliquot of Triton X-100 solution. The complex was stable for at least 4 h, the order of reagent addition was important, and thiocyanate should be in large excess. Beer’s law was obeyed over the range 0.9×10−6 to 1.1×10−5 M Mo with the molar absorptivity being 1.1×105 l mol−1 cm−1. The R.S.D. for the determination of 0.7 mg Mo l−1 was 1.83% (n=8). Possible interferences of various cations and anions on molybdenum determination were studied. The proposed method was applied to the determination of molybdenum in a dental alloy, Wiron 99. 相似文献
977.
5-Hydroxytryptamino-induced calcium sparks in cultured rat stomach fundus smooth muscle cells 总被引:1,自引:0,他引:1
With the imaging fluorescence probe of Ca2+ (fluo-3) and a laser scanning confocal micro-scope, the spontaneous localized calcium release event was first discovered in resting rat cardiac myocytes by Cheng[1] in 1993. A mathematical simulation is developed with computer in order to reveal the effect, which is immediately suggested that these events are likely to reflect the local-ized release of Ca2+ from a small cluster of ryanodine-sensitive Ca2+ release channels in sar-coplasmic reticulum … 相似文献
978.
Liya?Wang Zhiliang?Liu Chenxi?Zhang Zhanquan?Liu Daizheng?Liao Zonghui?JiangEmail author Shiping?Yan 《中国科学B辑(英文版)》2003,46(6):533-541
A novel one-dimensional manganese(II) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2(μ1,1-N3)(μ1,3-N3) · EtOH]
n
was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(II) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical
and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in
trans axial position. Mn(II) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through μ1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds, π-π interactions and
hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic
interactions between the radical and Mn(II) ion, weak antiferromagnetic interactions between the Mn-R units, and very weak
antiferromagnetic interactions between the R-Mn-Mn-R units. 相似文献
979.
Saalfrank RW Reimann U Göritz M Hampel F Scheurer A Heinemann FW Büschel M Daub J Schünemann V Trautwein AX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3614-3619
Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The M?ssbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses. 相似文献
980.
The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The self-assembled electrode shows obvious electrocatalytic activity for the oxidation of epinephrine (EP). In phosphate buffer (pH 7.73), a sensitive oxidation peak was observed at 0.190V with the PCA modified Au electrode. The peak current is proportional to the concentration of EP in the range of 2.0×10–56.0×10–4molL–1 and 5.0×10–6 2.0×10–4molL–1 for cyclic voltammetry (CV) and differential pulse voltammetry (DPV) with the detection limits of 1.8×10–7 and 1.3×10–7molL–1, respectively. The possible reaction mechanism is also discussed. The PCA self-assembled monolayer modified gold electrode is highly stable and can be applied to the determination of EP in practical injection samples. Application is simple, rapid and produces accurate results. 相似文献