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151.
R. Acevedo T. Meruane E. Cortés S. O. Vasquez C. D. Flint 《Theoretical chemistry accounts》1994,88(2):99-110
Summary A theoretical model to calculate the vibronic intensities induced by the odd vibrational modes in centrosymmetric lanthanide complexes is developed and applied to octahedral complex ions, LnX
6
3–
, such as occur in the hexachloroelpasolites Cs2NaLnCl6. Both the crystal field and the ligand polarisation contributions are evaluated using a standard set of symmetry coordinates. For the crystal field term a truncated expansion of the intermediates states is employed rather than the more conventional closure approximation. Special care is necessary to ensure that the phases of the contributions are correctly determined since the cross-term between the ligand polarisation and crystal field contributions is signed. General equations applicable to anyf
n
complex ion are derived and an example of their application to the PrCl
6
3–
ion is given The agreement with experiment is satisfactory. 相似文献
152.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
153.
A. V. Sinitsky M. B. Darhovskii A. L. Tchougreff I. A. Misurkin 《International journal of quantum chemistry》2002,88(4):370-379
In the present work the semiempirical effective crystal field (ECF) method previously designed for electronic structure calculations of transition metal complexes and utilizing non‐Hartree–Fock trial wave function and parameterized for complexes of doubly charged Cr2+, V2+, Mn2+, Fe2+, Co2+, and Ni2+ cations is extended to complexes of triply charged cations of 3d‐elements. With the parameters adjusted the ECF method is applied to calculations of ground states and low‐energy spectra of the d‐shells of fluoro‐, chloro‐, aqua‐, amino‐, and cyano‐complexes of the triply charged cations. Obtained total spin and symmetry of the ground states match the experimentally observed ones. Satisfactory agreement between the calculated and experimental d‐shell electronic transition energies is achieved as well. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
154.
文中直接取硫酸样品3ml于装有约10ml水的25ml比色管中,加入碘化钾溶液2ml,用水稀至刻度。加入甲基异丁酮5ml,萃取lmin,分层后,在有机相中测定铅、镉、铜含量;在水相中测定锌含量。方法的加标回收率为98.9%~103%,精密度1.8%~4.3%,标准曲线法和标准加入法结果相近,倍比试验结果亦相吻合,方法快速简便、准确,适合于工业中的快速分析。 相似文献
155.
将40只雄性SD大鼠随机分成两组,采用猪油(L)或玉粮米油(M)加胆固醇饲料诱导出大高血脂模型后,再分出两组、分别加入亚硒酸钠(L-Se,M-Se),观察大鼠补硒后血清中锌铜、锌、钙、镁等元素的变化。结果表明,高血脂大鼠补硒后血 锌的含量明显下降,铜/锌比值长高。相关分析显示:血硒水平与血清锌含量呈负相关,各组大鼠血清铜、钙、镁的浓度未观察到显著性差异。 相似文献
156.
J. Borrs R. Carballo A. Castieiras M. C. Gmez‐Conde M. C. Fernndez‐Vidal J. Nicls 《无机化学与普通化学杂志》2005,631(11):2221-2226
Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′‐bis(carboxymethyl)dithiooxamide], ALADTO [N,N′‐bis(carboxyethyl)dithiooxamide], VALDTO [N,N′‐bis(1‐carboxy‐2‐methylpropyl)dithiooxamide] and LEUDTO [N,N′‐bis(1‐carboxy‐3‐methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with ?J values greater than 300 cm?1. Thermal decomposition behaviour of the complexes was studied by thermogravimetry. 相似文献
157.
Bright orange (CuBr)3P4Se4 is obtained from the reaction of CuBr, P, and Se in stoichiometric amounts (CuBr : P : Se = 3 : 4 : 4). The composition and the crystal structure of the compound were determined from single crystal X‐ray diffraction data. Lattice constants are a = 33.627(2) Å, b = 6.402(1) Å, c = 19.059(1) Å, β = 90.19(3) °, V = 4103.2(3) Å3, and Z = 12. The compound crystallizes in a structure that is related to (CuI)3P4Se4. Cages of β‐P4Se4 are stacked along the b‐axis and are separated by columns of copper(I) bromide. However, the coordination of the β‐P4Se4 cage molecules to the copper atoms in the CuBr columns in (CuBr)3P4Se4 is quite different from (CuI)3P4Se4. The monoclinic compound (space group: P21, no. 4) has an almost orthorhombic metric in combination with a threefold superstructure in [100]. Structural aspects of (CuBr)3P4Se4 are discussed with respect to the heavier homologue (CuI)3P4Se4. 相似文献
158.
本文研究了Cu(Ⅱ)-PEG(聚乙二醇-2000)-Zincon(锌试剂)-(NH4)2SO4体系的析相光度法并应用于测定Cu(Ⅱ)。最宜酸度为pH5.5~8.5(KH2PO4-K2HPO4)缓冲溶液)其络合物的最大吸收位于610nm,表观摩尔吸光系数为4.0×10^4L.mol^-1.cm^-1,Cu(Ⅱ)浓度在0~1.5mg/L范围内服从比尔定律,铜与Zincon形式组成为1:2的稳定的蓝色络 相似文献
159.
The design and synthesis of a porphyrin-appended terpyridine, 5-(4-([2,2′:6′,2″]-terpyridin-4-yl-carboxyamidyl)phenyl)-10,15,20-triphenylporphyrin (H2TPPTPy) and its application as potential fluoroionophore for recognition of metal ions are reported. For preparation of the fluoroionophore, a novel simple strategy with improved total yield has been applied for the synthesis of 2,2′:6′,2″-terpyridine-4′-carboxylic acid as a ligand. H2TPPTPy shows chelation-enhanced fluorescence effect with cadmium ion via the interruption of photoinduced electron transfer (PET) process, which has been utilized as the basis of the fabrication of the Cd(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd(II)-sensitive chemosensor were investigated. It shows a linear response toward Cd(II) in the concentration range of 3.2 × 10−6 to 3.2 × 10−4 M with a limit of detection of 1.2 × 10−6 M. The chemosensor shows good selectivity for Cd(II) over a large number of cations, such as alkali, alkali earth and transitional metal ions except Cu(II) and Zn(II). The sensor has been used for determination of Cd(II) in water samples with satisfactory recoveries. 相似文献
160.
The preliminary results described here show the complete transfer of Hg(II) ions, in the absence of a chelating agent in 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids; the lag time required to gain the quantitative metal ion partition turned out to be strongly dependent both on alkyl chain length on the imidazolium ring and on the working temperature. 相似文献