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61.
Yu. A. Borisov Yu. A. Zolotarev E. V. Laskatelev N. F. Myasoedov 《Russian Chemical Bulletin》1997,46(3):407-409
The simplest quantum-chemical models of hydrogen spillover over a graphite-like surface as a proton or radical have been considered.
The condensed planar C24H12 molecule was used as a model surface. Theab initio calculations of the interaction of hydrogen with the model surface were carried out by the restricted Hartree-Fock (HF) method
in the STO-3G and 6-31 G* basis sets. The radical hydrogen can not bind to such a surface, whereas the proton binds to it with an energy release of
186 kcal mol−1. The activation energy of the transfer of the proton between two neighboring carbon atoms (10 kcal mol−1) has been determined. The simplest model of the hydrogen migration as a proton over the model surface can be used for describing
the spillover of hydrogen over the graphite surface.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 428–430, March, 1997. 相似文献
62.
The dependence of the frequency factor on the temperature (A=A
0
T
m) has been examined and the errors involved in the activation energy calculated from some integral methods without considering
such dependence have been estimated. Investigated integral methods are the Coats-Redfern method, the Gorbachev-Lee-Beck method,
the Wanjun-Yuwen method and the Junmeng-Fusheng method. The results have shown that the error in the determination of the
activation energy calculated ignoring the dependence of the frequency factor on the temperature can be rather large and it
is dependent on x=E/RT and the exponent m. 相似文献
63.
Green Chemistry and Modern Technology 总被引:4,自引:0,他引:4
The basic principles, approaches, and early achievements of green chemistry are considered. The definition of green chemistry as a branch of chemistry that studies the laws of passing of chemical reactions and the properties of substances participating in such reactions, with the aim of acquiring basic knowledge that provides a basis for designing chemical technologies that eliminate (sharply curtail) the use and production of materials that pose a risk to the environment. 相似文献
64.
碳纤维微电极已被广泛应用于电化学研究和分析测定,该电极尺寸极小,在分析性能上与常规电极有显著不同,在不镀汞的情况下,用碳纤维电极直接测定金属离子几乎没有明显的伏安响应,本文提出用+2.5 V恒电位预先活化碳纤维电极,使测定灵敏度大为提高,在双电极体系和静止溶液中,采用溶出伏安法可测定10~(-9)级金属离子,以同样的方法清洗电极,测定结果重现性良好,由于分析过程中不使用汞,该电极的测定范围大大增加,特别是用于氧化还原电位较正的金属离子测试,根据循环伏安法、扫描电镜和电子能谱的研究,发现碳纤维表面状况在处理前后有很大变化,并与测定灵敏度密切相关。 相似文献
65.
Shyh‐Jong Chen Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,103(2):198-214
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
66.
《中国化学快报》2020,31(5):1168-1172
Near-infrared (NIR) light-triggered photothermal therapy (PTT) is a promising treatment strategy for treating cancer. The combination of nanotechnology and NIR has been widely applied. However, the therapeutic efficacy of the drug-delivery system depends on their ability to avoid phagocytosis of endothelial system, cross the biological barriers, prolong circulation life, localize and rapidly release the therapeutic at target sites. In this work, we designed a platelet membrane (PM)-camouflaged hollow mesoporous bismuth selenide nanoparticles (BS NPs) loading with indocyanine green (ICG) (PM@BS-ICG NPs) to achieve the above advantages. PM-coating has active tumor-targeting ability which could prevent drug leakage and provide drug long circulation, causing drug delivery systems to accumulate in tumor sites effectively. Moreover, as a type of the photothermal sensitizers, BS NPs are used as the inner cores to improve ICG stability and are served as scaffolds to enhance the hardness of this drug delivery system. For one hand, the thermal vibration of BS NPs under NIR laser irradiation causes tumor inhibition through hyperthermia. For another hand, this hyperthermia process could damage PM and let ICG rapid release from PM@BS-ICG NPs. The in vitro and in vivo results showed that this biomimetic nano-drug delivery system exhibits obvious antitumor activity which has good application prospect. 相似文献
67.
BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. An overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework have been provided. 相似文献
68.
Lam WH Jia G Lin Z Lau CP Eisenstein O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2775-2782
Theoretical calculations on the metathesis process, [Tp(PH3)MR(eta 2-H[bond]CH3)] --> [Tp(PH3)M(CH3)(eta 2-H[bond]R)] (M=Fe, Ru, and Os; R=H and CH3), have been systematically carried out to study their detailed reaction mechanisms. Other than the one-step mechanism via a four-center transition state and the two-step mechanism through an oxidative addition/reductive elimination pathway, a new one-step mechanism, with a transition state formed under oxidative addition, has been found. Based on the intrinsic reaction coordinate calculations, we found that the trajectories of the transferring hydrogen atom in the metathesis processes studied are similar to each other regardless of the nature of reaction mechanisms. 相似文献
69.
Activation of CO2 at Transition Metal Centres: The Route of the CO2 Reduction at Nikel(0) Moieties A competing reaction in the catalytic cyclooligomerization of hex-3-yne and CO2 at the (TMED)Ni(0)-fragment (TMED = N,N,N′,N′-tetramethylethylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO3). So it is possible to explain the generation of II (TMED)Ni(diethylmalicacidanhydride) and III (a nickel trimer with two (TMED)Ni(CO3) units). Both complexes are characterized by X-ray analysis. The reduction of CO2 to CO most likely proceeds via an intermediate in which two molecules of carbon dioxide are coupled head-to-tail to form a metallacycle. An ab initio scf geometry optimization supports the existence of such an intermediate. 相似文献
70.
The vaterite—calcite transition above 630 K has been studied by isothermal and non-isothermal differential scanning calorimetry. Vaterite samples prepared under different conditions were investigated. The transition temperature is strongly dependent on the sample preparation. The observed transition enthalpy Htr is nearly equal for different samples and experimental conditions. From 28 measurements a value of Htr–(3.12±0.11) kJ mol–1 was obtained. The activation energy for the polymorphic transition was calculated from the Arrhenius plot and by use of isoconversional methods, as a function of the degree of conversion. The influence of the kinetic model distortion and experimental uncertainties on the obtained data was discussed. The actual value of the activation energy was assessed at Ea=(250±10) kJ mol–1 for nearly all examined samples. Functions, corresponded to the model mechanism of nuclei formation and growth, provide the unambiguous consideration of the transition kinetic for the investigated vaterite samples. Differences in the dynamic behaviour of several samples at the transition are established.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献