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971.
In order to improve the photosensitizing activity of HB further, the complex of 5,8-di-Br-HB with Al(3+) was first designed and synthesized in high yield. 5,8-di-Br-HB forms a 2:1 type (metal-ligand ratio) complex with Al(3+) measured by molar ratio and continuous variation methods. The new photosensitizer was characterized by UV-Vis, IR, 1H NMR and elemental analysis measurements. Based on the above experimental results, we first proposed a polymer-like structural model of the complex. The water-solubility and red absorption of the [Al(2)(5,8-di-Br-HB)Cl(4)](n) complex are both enhanced over hypocrellin B. In addition, the EPR and spectrophotometric measurements demonstrate that semiquinone anion radical of [Al(2)(5,8-di-Br-HB)Cl(4)](n) can be produced by [Al(2)(5,8-di-Br-HB)Cl(4)](n) photosensitization. The generation efficiency of ([Al(2)(5,8-di-Br-HB)Cl(4)](n))(.-) is almost equal to that of HB(.-). These results obtained indicated that [Al(2)(5,8-di-Br-HB)Cl(4)](n)was at least a favorable Type I phototherapeutic agent. 相似文献
972.
973.
Qing‐Lun Wang Mao Liang Dai‐Zheng Liao Shi‐Ping Yan Zong‐Hui Jiang Peng Cheng 《无机化学与普通化学杂志》2004,630(4):613-616
A unique neodymium(III) complex, {[Nd(BTC)(H2O)4] · H2O}n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO4)3 · xH2O and Na3BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively. 相似文献
974.
Determination of cadmium in water samples by graphite furnace atomic absorption spectrometry after cloud point extraction 总被引:3,自引:0,他引:3
The formation of a complex with 2-(5-brom-2-pyridylazo)-5-(diethylamino)-phenol (5-Br-PADAP) and cloud point extraction have
been applied to the preconcentration of cadmium followed by its determination by graphite furnace atomic absorption spectrometry
(GFAAS) using octylphenoxypolyethoxyethanol (TritonX-114) as surfactant. The chemical variables affecting the separation were
optimized. At pH 7.0, preconcentration of only 10 mL of sample in the presence of 0.05% TritonX-114 and 2.5 × 10−6 M 5-Br-PADAP enabled the detection of 0.04 μg/L cadmium. The enrichment factor was 21 for cadmium. The regression equation
was A = 0.0439C(μg/L) + 7.2 × 10−3. The correlation coefficient was 0.9995. The precision for 10 replicate determinations at 10 μg/L Cd was 2.7% relative standard
deviation (RSD). The proposed method has been applied to the determination of cadmium in water samples.
The text was submitted by the authors in English. 相似文献
975.
Chihiro Kachi‐Terajima Dr. Takamasa Akatsuka Masa‐aki Kohbara Satoshi Takamizawa Dr. 《化学:亚洲杂志》2007,2(1):40-50
The crystalline one‐dimensional compound, [RhII2(bza)4(pyz)]n ( 1 ) (bza=benzoate, pyz=pyrazine) demonstrates gas adsorbency for N2, NO, NO2, and SO2. These gas‐inclusion crystal structures were characterized by single‐crystal X‐ray crystallography as 1 ?1.5 N2 (298 K), 1 ?2.5 N2 (90 K), and 1 ?1.95 NO (90 K) under forcible adsorption conditions and 1 ?2 NO2 (90 K) and 1 ?3 SO2 (90 K) under ambient pressure. Crystal‐phase transition to the P space group that correlates with gas adsorption was observed under N2, NO, and SO2 conditions. The C2/c space group was observed under NO2 conditions without phase transition. All adsorbed gases were stabilized by the host lattice. In the N2, NO, and SO2 inclusion crystals at 90 K, short interatomic distances within van der Waals contacts were found among the neighboring guest molecules along the channel. The adsorbed NO molecules generated the trans‐NO???NO associated dimer with short intermolecular contacts but without the conventional chemical bond. The magnetic susceptibility of the NO inclusion crystal indicated antiferromagnetic interaction between the NO molecules and paramagnetism arising from the NO monomer. The NO2 inclusion crystal structure revealed that the gas molecules were adsorbed in the crystal in dimeric form, N2O4. 相似文献
976.
In order to explore the transfer mechanism of chromium(III) in mammals, a novel complex [Cr(ASA)(en)2]Cl· 2H2O, bis(ethylenediamine‐ κ 2 N,N′)(4‐aminosalicylic acid‐ κ 2 O,O′) chromium(III) monochloride dihydrate was synthesized (4‐aminosalicylic acid=H2ASA, ethylenediamine=en). The crystal structure belongs to orthorhombic system with the space group P212121 by means of X‐ray diffraction. The characteristic for transfer of Cr3+ from the compound to the low‐molecular‐mass chelator EDTA and the iron‐binding protein apoovotransferrin (apoOTf) was followed by UV‐visible (UV‐Vis) and fluorescence spectra in 0.01 mol·L?1 Hepes at pH 7.4. The second order rate constants were calculated. Those spectra in conjunction were used to obtain more accurate information about the interaction of chromium complex with apoOTf. The experimental results indicate that Cr3+ can be transferred from the complex to apoOTf with the retention of the 4‐aminosalicylic acid acting as a synergistic anion. 相似文献
977.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
978.
The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction. 相似文献
979.
本文报道了一种新型三维亚磷酸锌[HO(CH2)2NH3]2•[Zn3(HPO3)4]的合成和晶体结构。在它的结构中,ZnO4和HPO3严格按照顶点连接的方式交替相连。骨架结构存在两个沿着不同方向无限延伸的由ZnO4和HPO3组成的四元环链,在[0 1 0]、[0 4 15]和[0 -4 15]三个方向形成了三个交叉8元环孔道,有机胺阳离子起着平衡电荷和稳定骨架的结构。它的晶体数据为:[HO(CH2)2NH3]2•[Zn3(HPO3)4],M=640.21, 正交晶系, Fdd2空间群, a=2.8528, b=0.8426, c=1.6159nm, Z=8, V=3.884nm3, R1=0.0219, wR2=0.0544。 相似文献
980.
Xiang Ming He Jian Jun Li Yan Cai Yaowu Wang Jierong Ying Changyin Jiang Chunrong Wan 《Journal of Solid State Electrochemistry》2005,9(6):438-444
A novel process is proposed for synthesis of spinel LiMn2O4 with spherical particles from the inexpensive materials MnSO4, NH4HCO3, and NH3H2O. The successful preparation started with carefully controlled crystallization of MnCO3, leading to particles of spherical shape and high tap density. Thermal decomposition of MnCO3 was investigated by both DTA and TG analysis and XRD analysis of products. A precursor of product, spherical Mn2O3, was then obtained by heating MnCO3. A mixture of Mn2O3 and Li2CO3 was then sintered to produce LiMn2O4 with retention of spherical particle shape. It was found that if lithium was in stoichiometric excess of 5% in the calcination of spinel LiMn2O4, the product had the largest initial specific capacity. In this way spherical particles of spinel LiMn2O4 were of excellent fluidity and dispersivity, and had a tap density as high as 1.9 g cm–3 and an initial discharge capacity reaching 125 mAh g–1. When surface-doped with cobalt in a 0.01 Co/Mn mole ratio, although the initial discharge capacity decreased to 118 mAh g–1, the 100th cycle capacity retention reached 92.4% at 25°C. Even at 55°C the initial discharge capacity reached 113 mAh g–1 and the 50th cycle capacity retention was in excess of 83.8%. 相似文献