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181.
Junrui Duan Jie Ji Lili Ye Yitong Zhai Lidong Zhang 《Proceedings of the Combustion Institute》2021,38(1):681-689
The low-temperature oxidation mechanism of n?butyl radicals (n-C4H9) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO2 elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes. 相似文献
182.
针对冷库运行过程中出现的压缩机排气温度高、系统性能衰减等问题,设计并搭建了基于平行流换热器的低压补气冷藏系统实验台对冷藏系统在低压补气和不补气状态下压缩机转速对冷藏系统综合性能的影响进行了分析.结果 表明:随着压缩机转速的增加,两种工况下压缩机排气温度都会增加,在补气模式下排气温度增加了5%,在不补气模式下增加了7.8%;冷藏系统的制冷量也会随之增大,在补气模式下制冷量增加了43%,在不补气模式下增加了25.9%,低压补气模式下增加的制冷量更大一些;压缩机功率随转速的增加而增大,且两种模式下增幅接近,在补气模式下压缩机功率增加了27.44%,在不补气模式下增加了27.34%;另外随着转速的增大系统COP呈现先增大后减小的趋势,在转速为3500 r/min处趋于稳定. 相似文献
183.
Inspired by structures of antenna-reaction centers in photosynthesis, the complex micelle was prepared from zinc tetra-phenyl porphyrin (ZnTPP), fullerene derivative (PyC60) and poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL). The core-shell structure made the hydrophobic donor-acceptor system work in aqueous. In micellar core, coordination interaction occurred between ZnTPP and PyC60 molecules which ensured the enhanced energy migration from the donor to the acceptor. The enhanced interaction between porphyrin and fullerene was confirmed by absorption, steady-state fluorescence and transient fluorescence. The generation of singlet oxygen and superoxide radical was detected by iodide method and reduction of nitro blue tetrazolium, respectively, which confirmed that electron transfer reaction in the complex micellar core occurred. Moreover, the complex micelle exhibited effective electron transfer performance in photodebromination of 2,3-dibromo-3-phenylpropionic acid. The complex micellar structure endowed the donor-acceptor system with improved stability under irradiation. This strategy could be helpful for designing new electron transfer platform and artificial photosynthetic system. 相似文献
184.
本文采用离散涡方法计算了大雷诺数下线性剪切流绕圆柱的分离流动,计算结果给出阻力系数、横向力系数、边界层分离点、斯特罗哈数及尾流中旋涡的分布图案,计算数据与已有的实验数据相吻合。 相似文献
185.
The density functional method is used to study the structure, electronic properties, static linear polarizabilities, and optical absorption spectra of two seven‐membered unconventional fullerene derivatives C58F17CF3 and C58F18. It is calculated that three sites chosen to locate the CF3 are isoenergetic. The energy gaps of C58F18 and C58F17CF3 are much larger than that of C58, indicating the fluorination and trifluoromethylation of C58 can remarkably enhance the kinetic stability. The density of states explore that the influence of CF3 to the energy levels is mainly distributed in the energy range from ?10 to ?2 eV. However, when the CF3 substitutes for F in C58F18, the bond lengths, energy gaps, static linear polarizabilities, and optical absorption spectra all show small variety. 相似文献
186.
Zong‐Wei Xuan Xiao‐Ying Sun Guo‐Song Jiao Zi‐Qin Zhai Wei Sun Lu‐De Lu 《中国化学会会志》2010,57(6):1262-1267
A new carbon ionic liquid paste bioelectrode was fabricated by mixing hemoglobin (Hb) with graphite powder, ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF4) and liquid paraffin homogeneously. Nafion film was cast on the electrode surface to improve the stability of bioelectrode. Direct electrochemistry of Hb in the bioelectrode was carefully investigated. Cyclic voltammetric results indicated that a pair of well‐defined and quasi‐reversible electrochemical responses appeared in pH 7.0 phosphate buffer solution (PBS), indicating that direct electron transfer of Hb was realized in the modified electrode. The formal potential (E0′) was calculated as ?0.316 V (vs. SCE), which was the typical characteristic of the electrochemical reaction of heme Fe(III)/Fe(II) redox couple. Based on the cyclic voltammetric results the electrochemical parameters of the electrode reaction were calculated. This bioelectrode showed high electrocatalytic activity towards the reduction of trichloroacetic acid (TCA) with good stability and reproducibility. 相似文献
187.
The influence of pressure on the nucleation rate of insulin under fibril‐forming conditions was studied and subsequently analysed using classical nucleation theory. The aim was a better understanding and quantification of the influence of pressure on protein aggregation/fibrillation reactions. The application of pressure has a drastic accelerating effect on the nucleation and growth process of insulin fibrils. We show that this effect arises from a volume decrease upon nucleus formation, due to formation of a less hydrated and more compact transition state that can be quantified extending nucleation theory by a pressure–volume term. Conversely, the absolute values of the lag time and the critical size of the nucleus cannot be satisfactorily described by the classical nucleation theory, which might be due to the presence of secondary effects, such as parallel aggregation pathways or fragmentation processes. 相似文献
188.
A concise synthetic approach for constructing the oxapentacyclic framework of cortistatin A is described. The synthesis features a furan-oxyallyl [4 + 3] cycloaddition and double-intramolecular aldol reactions. In addition, an interesting core structure was obtained in 11 steps from furan by using our method. 相似文献
189.
Novel drug‐loaded hydrogel beads for intestine‐targeted controlled release were developed by using pH‐ and temperature‐sensitive carboxymethyl chitosan‐graft‐poly(N,N‐diethylacrylamide) (CMCTS‐g‐PDEA) hydrogel as carriers and vitamin B2 (VB2) as a model drug. The hydrogel beads were prepared based on Ca2+ ionic crosslinking in acidic solution and formed dual crosslinked network structure. The structure of hydrogel and morphology of drug‐loaded beads were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The study about swelling characteristics of hydrogel beads indicated that the beads had obvious pH‐ and temperature‐sensitivity. In vitro release studies of drug‐loaded beads were carried out in pH 1.2 HCl buffer solution and pH 7.4 phosphate buffer solution at 37°C, respectively. The results indicated that the dual crosslinked method could effectively control the drug release rate under gastrointestinal tract (GIT) conditions, which was superior to traditional single crosslinked beads. In addition, the effects of grafting percentage, pH value, and temperature on the release behavior of the VB2 were investigated. The drug release mechanism of CMCTS‐g‐PDEA drug‐loaded beads was analyzed by Peppa's potential equation. According to this study, the dual crosslinked hydrogel beads based on CMCTS‐g‐PDEA could serve as suitable candidate for drug site‐specific carrier in intestine. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
190.
During photoelectron spectroscopy experiments, the spectra of B(11)O(-) and B(10)Au(-) clusters are found to exhibit similar patterns except for a systematic spectral shift of ~0.5 eV, hinting that they possess similar geometric structures. The electron affinities are measured to be 4.02 ± 0.04 eV for B(11)O and 3.55 ± 0.02 eV for B(10)Au. DFT calculations at the B3LYP level show that B(11)O(-) and B(10)Au(-) adopt similar C(1) ((1)A) ground states, which are based on the quasiplanar B(10) cluster interacting with a BO unit and Au, respectively. The B(11)O(-) and B(10)Au(-) clusters are thus valent isoelectronic because both BO and Au can be viewed as monovalent units, forming highly covalent B-BO and B-Au bonds analogous to the B-H bond in B(10)H(-). For B(10)Au(-), we also find a highly symmetric D(10h) ((1)A(1g)) planar molecular wheel as a minimum on the potential energy surface. However, it is 45 kcal/mol above the ground state at the B3LYP level and not viable for experimental observation. Natural bond orbital analyses reveal interesting covalent versus ionic B-Au bonding in the C(1) B(10)Au(-) and D(10h) B(10)Au(-) structures, respectively, providing insight for the design of D(nh) MB(n) molecular wheels. 相似文献