全文获取类型
收费全文 | 90892篇 |
免费 | 4998篇 |
国内免费 | 11961篇 |
专业分类
化学 | 71640篇 |
晶体学 | 1164篇 |
力学 | 2346篇 |
综合类 | 853篇 |
数学 | 12731篇 |
物理学 | 19117篇 |
出版年
2024年 | 84篇 |
2023年 | 687篇 |
2022年 | 1195篇 |
2021年 | 1806篇 |
2020年 | 2216篇 |
2019年 | 2211篇 |
2018年 | 1872篇 |
2017年 | 2766篇 |
2016年 | 2873篇 |
2015年 | 2412篇 |
2014年 | 3345篇 |
2013年 | 6634篇 |
2012年 | 6357篇 |
2011年 | 5095篇 |
2010年 | 4286篇 |
2009年 | 5844篇 |
2008年 | 6068篇 |
2007年 | 6292篇 |
2006年 | 5689篇 |
2005年 | 4822篇 |
2004年 | 4493篇 |
2003年 | 3692篇 |
2002年 | 4924篇 |
2001年 | 2848篇 |
2000年 | 2645篇 |
1999年 | 2489篇 |
1998年 | 2155篇 |
1997年 | 1697篇 |
1996年 | 1434篇 |
1995年 | 1370篇 |
1994年 | 1221篇 |
1993年 | 1015篇 |
1992年 | 955篇 |
1991年 | 647篇 |
1990年 | 539篇 |
1989年 | 511篇 |
1988年 | 361篇 |
1987年 | 283篇 |
1986年 | 264篇 |
1985年 | 209篇 |
1984年 | 229篇 |
1983年 | 125篇 |
1982年 | 198篇 |
1981年 | 166篇 |
1980年 | 184篇 |
1979年 | 167篇 |
1978年 | 145篇 |
1977年 | 88篇 |
1976年 | 74篇 |
1973年 | 43篇 |
排序方式: 共有10000条查询结果,搜索用时 217 毫秒
41.
42.
Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Didier Gigmes Jean Pierre Fouassier Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(5):665-674
Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674 相似文献
43.
《Physics letters. A》2019,383(17):2090-2092
In this paper, we have used Monte Carlo (MC) method to simulate and study the temperature and doping effects on the electric conductivity of fullerene (C60). The results show that the band gap has reduced by the doping and the charge carrier transport is facilitated from valence band to conduction band by the temperature where is touched a 300 K. In this case, the conductivity reached a value of . The electric conductivity of C60 can increase by the triphenylmethane dye crystal violet (CV) alkali metal to reach at 303 K. Our results of MC simulation have a good agreement with those extracted from literature [10], [33]. 相似文献
44.
This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but ) nonlinearities. 相似文献
45.
Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants 下载免费PDF全文
Michael A. Brook Frances Lasowski Heather Sheardown 《Journal of polymer science. Part A, Polymer chemistry》2015,53(9):1082-1093
The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093 相似文献
46.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
47.
Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks 下载免费PDF全文
Prof. Hongzhi Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4731-4738
Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission. 相似文献
48.
New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl4 salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, 1H NMR, 13C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d6 systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO2, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO2 was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs. 相似文献
49.
聚山梨酯80又名吐温80,为一种亲水型非离子表面活性剂,是食品、保健品和药品中常用的辅料,作为增溶剂和澄清剂广泛用于中药注射剂。近年来,不良反应的发生使得聚山梨酯80的质量和应用愈加受到重视,有研究认为其加入可能引起注射剂不良反应增加。为避免超量使用,有必要对该辅料的投料加以严格控制。中药注射剂中聚山梨酯80的含量测定是当下研究的热点和难点,可以通过分光光度法、分子排阻-蒸发光散射检测法(SEC-ELSD)、液质联用法(LC-MS)直接测定,也可以水解后法经液相色谱-紫外检测法(HPLC-UV)或气相色谱法(GC)间接测定。但由于聚山梨酯80为聚氧乙烯聚合数目不同的混合物、不同厂家生产的聚山梨酯80化学组分及比例存在较大差异,难以采用统一的转换公式或对照品准确定量。此外,中药注射剂的复杂基质造成的假阳性干扰也对定量提出了挑战。为解决以上问题,以生脉注射液为例,提出基于吸收系数的中药注射剂中聚山梨酯80含量测定新方法。优化检测波长、显色剂种类、液液萃取过程振荡和静置时间,在6个不同品牌仪器上测得聚山梨酯80-硫氰酸钴配合物的吸收系数(E1%1 cm)为104.23,相对标准偏差(RSD)为2.08%。生脉注射液稀释10倍后,精密量取供试品溶液1.0 mL,精密加入硫氰酸钴溶液10 mL,二氯甲烷20 mL,涡旋振荡3 min。将混合液移至分液漏斗中,静置30 min,取下层二氯甲烷液,将前1 mL弃去,接收约15 mL,在320 nm处测定吸光度,再根据Lambert-Beer定律,利用获得的吸收系数计算得到聚山梨酯80的含量。方法阴性无干扰,精密度和重复性相对标准偏差均低于3%,平均回收率为98.42%。为进一步验证方法的准确性,分别采用吸收系数法和标准曲线法测定了2个厂家的10批生脉注射液,并与实际投料量比较。配对t检验结果表明,当置信度为95%时,两种方法无显著性差异,吸收系数法测得结果与企业生产中聚山梨酯的实际投料量也无显著性差异。研究采用前人未采用的、灵敏度更高的320 nm为检测波长,显著降低了基质干扰,克服了中药注射剂中聚山梨酯80测定结果与实际投料量难以吻合的问题。吸收系数法无需使用对照品,亦不用制备标准曲线,可为中药注射剂中聚山梨酯80的检查标准提供切实可行的解决方案。所建方法灵敏、准确、快速、简便,为含聚山梨酯80制剂的质量控制提供了关键常数及新的思路。 相似文献
50.
The interactions of bubbles and coal particles in 600 kHz ultrasonic standing waves (USW) field has been investigated. A high-speed camera was employed to record the phenomena occurred under the USW treatment. The formation and behaviors of cavitation bubbles were analyzed. Under the driving of these cavitation bubbles, whose size is from several microns to dozens of microns, coal particles were aggregated and then attracted by large bubbles due to the acoustic radiation forces. The results of USW-assisted flotation show a significant improvement in recoveries at 600 kHz, which indicates that the interactions of bubbles and particles in the USW field are more efficient than that in the conventional gravitational field. Furthermore, the sound pressure distribution of the USW was measured and predicted by a hydrophone. The analysis of gravity and buoyancy, primary and secondary Bjerknes forces shows that bubble-laden particles can be attracted by the rising bubbles under large acoustic forces. This study highlights the potential for USW technology to achieve efficient bubble-particle interactions in flotation. 相似文献