全文获取类型
收费全文 | 34199篇 |
免费 | 2514篇 |
国内免费 | 2971篇 |
专业分类
化学 | 22016篇 |
晶体学 | 175篇 |
力学 | 695篇 |
综合类 | 640篇 |
数学 | 6578篇 |
物理学 | 9580篇 |
出版年
2023年 | 279篇 |
2022年 | 473篇 |
2021年 | 1286篇 |
2020年 | 876篇 |
2019年 | 895篇 |
2018年 | 662篇 |
2017年 | 729篇 |
2016年 | 961篇 |
2015年 | 1042篇 |
2014年 | 1286篇 |
2013年 | 2277篇 |
2012年 | 1574篇 |
2011年 | 1834篇 |
2010年 | 1684篇 |
2009年 | 2162篇 |
2008年 | 2205篇 |
2007年 | 2431篇 |
2006年 | 1896篇 |
2005年 | 1183篇 |
2004年 | 1134篇 |
2003年 | 1111篇 |
2002年 | 1050篇 |
2001年 | 1044篇 |
2000年 | 734篇 |
1999年 | 564篇 |
1998年 | 580篇 |
1997年 | 416篇 |
1996年 | 483篇 |
1995年 | 438篇 |
1994年 | 432篇 |
1993年 | 472篇 |
1992年 | 453篇 |
1991年 | 306篇 |
1990年 | 251篇 |
1989年 | 205篇 |
1988年 | 242篇 |
1987年 | 199篇 |
1986年 | 203篇 |
1985年 | 320篇 |
1984年 | 228篇 |
1983年 | 140篇 |
1982年 | 289篇 |
1981年 | 467篇 |
1980年 | 426篇 |
1979年 | 463篇 |
1978年 | 368篇 |
1977年 | 279篇 |
1976年 | 237篇 |
1974年 | 74篇 |
1973年 | 149篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
11.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
12.
The sonocatalytic degradation of EDTA (C0 = 5 10−3 M) in aqueous solutions was studied under 345 kHz (Pac = 0.25 W mL−1) ultrasound at 22–51 °C, Ar/20%O2, Ar or air, and in the presence of metallic titanium (Ti0) or core-shell Ti@TiO2 nanoparticles (NPs). Ti@TiO2 NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti0 NPs in pure water. Ti0 is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti3O. SHT treatment at 150–214 °C leads to the oxidation of Ti3O and partial oxidation of Ti0 and formation of nanocrystalline shell (10–20 nm) composed of TiO2 anatase. It was found that Ti0 NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti0 NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti0 NPs and Ar/20%O2 gas mixture. Coating of Ti0 with TiO2 nanocrystalline shell reduces sonocatalytic activity. Pristine TiO2 anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO2 radicals in solution and (ii) EDTA oxidation at the surface of Ti0 NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti0/O2 species at cavitation bubble/solution interface. 相似文献
13.
为了使超材料完美吸收器(metamaterial perfect absorber,MPA)能够同时实现吸收效率和吸收波长的控制,本文提出利用二氧化钒(VO2)和石墨烯作为MPA的材料,通过对MPA的结构设计,在红外波段实现了高吸收,吸收效率最高可达99%.研究发现通过改变VO2的温度和石墨烯的化学势,可同时实现MPA吸收效率和吸收波长的控制,吸收效率调制深度和吸收波长调谐范围分别可达97.08%和3.2μm.通过对MPA在吸收波长处的磁场分布分析可以得出,MPA能够产生高吸收是由于其形成了法布里-帕罗(Fabry-Pérot,FP)干涉腔共振,研究发现MPA的结构参数对FP腔的共振波长具有显著的影响. 相似文献
14.
《Arabian Journal of Chemistry》2022,15(10):104145
In the present study, novel representatives of the important group of biologically-active, dehydroabietic acid-bearing dithiocarbamate moiety, were synthesized and characterized by 1H NMR, 13C NMR, HR-MS. The in vitro antiproliferative activity evaluation (MTT) indicated that these compounds exhibited potent inhibitory activities in various cancer cell lines (HepG-2, MCF-7, HeLa, T-24, MGC-803). Particularly, compound III-b possessed extraordinary cytotoxicity with low micromolar IC50 values ranging from 4.07 to 38.84 µM against tested cancer cell lines, while displayed weak cytotoxicity on two normal cell lines (LO-2 and HEK 293 T). Subsequently, the potential mechanisms of representative compound III-b were elementarily investigated by Transwell experiment, which showed III-b can inhibit cancer cells migration. Annexin-V/PI dual staining showed that the compound can induce HepG-2 cells apoptosis in a dose-dependent manner. Meanwhile this apoptosis may be related to the upregulated protein expression of cleaved-caspase 3, cleaved-caspase 9, Bax and downregulated of Bcl-2 indicated by Western Blot. Later study further confirmed that ROS levels in HepG-2 cells increased significantly with the rise of concentrations. In addition, through the network pharmacology data analyzing, the core targets and signaling pathways of compound III-b for treatment of liver neoplasms were forecasted. Molecular docking model showed that compound III-b had high affinity with hub targets (CASP3, EGFR, HSP90AA1, MAPK1, ERBB2, MDM2), suggesting that compound III-b might target the hub protein to modulate signaling activity. Taken together, these data indicated that dehydroabietic acid structural modification following the “Molecular hybridization” principle is a feasible way to discover the potential multi-targeted antitumor compounds. 相似文献
15.
S.V. Ivanov M.Yu. Chernov V.A. Solovev P.N. Brunkov D.D. Firsov O.S. Komkov 《Progress in Crystal Growth and Characterization of Materials》2019,65(1):20-35
High-efficiency semiconductor lasers and light-emitting diodes operating in the 3–5?μm mid-infrared (mid-IR) spectral range are currently of great demand for a wide variety of applications, in particular, gas sensing, noninvasive medical tests, IR spectroscopy etc. III-V compounds with a lattice constant of about 6.1?Å are traditionally used for this spectral range. The attractive idea to fabricate such emitters on GaAs substrates by using In(Ga,Al)As compounds is restricted by either the minimum operating wavelength of ~8?μm in case of pseudomorphic AlGaAs-based quantum cascade lasers or requires utilization of thick metamorphic InxAl1-xAs buffer layers (MBLs) playing a key role in reducing the density of threading dislocations (TDs) in an active region, which otherwise result in a strong decay of the quantum efficiency of such mid-IR emitters. In this review we present the results of careful investigations of employing the convex-graded InxAl1-xAs MBLs for fabrication by molecular beam epitaxy on GaAs (001) substrates of In(Ga,Al)As heterostructures with a combined type-II/type-I InSb/InAs/InGaAs quantum well (QW) for efficient mid-IR emitters (3–3.6?μm). The issues of strain relaxation, elastic stress balance, efficiency of radiative and non-radiative recombination at T?=?10–300?K are discussed in relation to molecular beam epitaxy (MBE) growth conditions and designs of the structures. A wide complex of techniques including in-situ reflection high-energy electron diffraction, atomic force microscopy (AFM), scanning and transmission electron microscopies, X-ray diffractometry, reciprocal space mapping, selective area electron diffraction, as well as photoluminescence (PL) and Fourier-transformed infrared spectroscopy was used to study in detail structural and optical properties of the metamorphic QW structures. Optimization of the growth conditions (the substrate temperature, the As4/III ratio) and elastic strain profiles governed by variation of an inverse step in the In content profile between the MBL and the InAlAs virtual substrate results in decrease in the TD density (down to 3?×?107 cm?2), increase of the thickness of the low-TD-density near-surface MBL region to 250–300?nm, the extremely low surface roughness with the RMS value of 1.6–2.4?nm, measured by AFM, as well as rather high 3.5?μm-PL intensity at temperatures up to 300?K in such structures. The obtained results indicate that the metamorphic InSb/In(Ga,Al)As QW heterostructures of proper design, grown under the optimum MBE conditions, are very promising for fabricating the efficient mid-IR emitters on a GaAs platform. 相似文献
16.
Meng Zang Chaocheng Zhao Yongqiang Wang Shuiquan Chen 《Journal of Saudi Chemical Society》2019,23(6):645-654
Along with the rapid development of industry, VOCs gradually move into the spotlight, and now become a kind of harmful environmental pollutants that cannot be overlooked. This paper introduces the hazards of VOCs and the common catalytic combustion catalysts, noble metal catalysts and non-noble metal catalysts, for the elimination of VOCs. Perovskite catalysts, as one of the non-noble catalysts, play an important role in the field of catalytic combustion in recent years. According to the classification of elements doping in perovskites, the research achievements in the past five years were analyzed and reviewed. In addition, this paper also analyzes and elaborates the reaction kinetics and QSAR/QSPR models for the introduction of structural properties and reaction mechanisms. 相似文献
17.
Sadra Mahmoudi Bahram Hashemi Shahraki 《Journal of Dispersion Science and Technology》2019,40(1):33-42
This paper concerns with developing of parameters which influence terminal velocities of air and CO2 bubbles in distilled water and kerosene pools. The objective of this study is to validate and correct the formulas that were developed by previous investigators for prediction of terminal velocities. The investigation revealed that the terminal velocity of a single rigid spherical bubble in Newtonian fluids can be developed by balancing of mechanical forces acting on the bubble. However, for large bubbles, because of deforming of the bubble which is a result of interfacial tension, the effect of surface tension should be considered in the terminal velocity prediction formula. By using PSO algorithm and plotting experimental data of terminal velocity against the size of gas bubbles, the suitable equation for each of systems was chosen. Results showed that Jamialahmadi model is more practical for terminal velocity prediction. Jamialahmadi model requires a modification to be utilized for air-kerosene, CO2-kerosene, air- distilled water and CO2-distilled water systems. The developed PSO algorithm model is accurate for prediction of experimental data with an average R2 value of 0.9722. 相似文献
18.
X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copolymerization and oxime "Click" postfunctionalization was developed towards X-ray opaque polylactide copolymers.A functionalized cyclic carbonate was first synthesized and used as comonomer of polylactide copolymers,which were subjected to postfunctionalization of oxime "Click" reaction towards iodinated polylactide copolymers.The chemical structure and physical properties of the target products were traced and confirmed.In vitro cytotoxicity evaluation with 3T3-Swiss albino by Alamar blue demonstrated a low cytotoxicity.The X-ray radiopacity was analyzed by Micro-CT and quantified by Hounsfield Units value,which could be tailorable by the feedstock.It is a promising X-ray visible implantable biomaterial in biomedical applications. 相似文献
19.
Tomas Do Roman Guran Rea Jarosova Petra Ondrackova Zbysek Sladek Martin Faldyna Vojtech Adam Ondrej Zitka 《Molecules (Basel, Switzerland)》2020,25(23)
Respiratory infections are a real threat for humans, and therefore the pig model is of interest for studies. As one of a case for studies, Actinobacillus pleuropneumoniae (APP) caused infections and still worries many pig breeders around the world. To better understand the influence of pathogenic effect of APP on a respiratory system—lungs and tracheobronchial lymph nodes (TBLN), we aimed to employ matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF MSI). In this study, six pigs were intranasally infected by APP and two were used as non-infected control, and 48 cryosections have been obtained. MALDI-TOF MSI and immunohistochemistry (IHC) were used to study spatial distribution of infectious markers, especially interleukins, in cryosections of porcine tissues of lungs (necrotic area, marginal zone) and tracheobronchial lymph nodes (TBLN) from pigs infected by APP. CD163, interleukin 1β (IL-1β) and a protegrin-4 precursor were successfully detected based on their tryptic fragments. CD163 and IL-1β were confirmed also by IHC. The protegrin-4 precursor was identified by MALDI-TOF/TOF directly on the tissue cryosections. CD163, IL-1β and protegrin-4 precursor were all significantly (p < 0.001) more expressed in necrotic areas of lungs infected by APP than in marginal zone, TBLN and in control lungs. 相似文献
20.
Florio M. Ciaglia Fabio Di Cosmo Alberto Ibort Giuseppe Marmo 《Entropy (Basel, Switzerland)》2020,22(11)
The evolution of states of the composition of classical and quantum systems in the groupoid formalism for physical theories introduced recently is discussed. It is shown that the notion of a classical system, in the sense of Birkhoff and von Neumann, is equivalent, in the case of systems with a countable number of outputs, to a totally disconnected groupoid with Abelian von Neumann algebra. The impossibility of evolving a separable state of a composite system made up of a classical and a quantum one into an entangled state by means of a unitary evolution is proven in accordance with Raggio’s theorem, which is extended to include a new family of separable states corresponding to the composition of a system with a totally disconnected space of outcomes and a quantum one. 相似文献