全文获取类型
收费全文 | 5937篇 |
免费 | 624篇 |
国内免费 | 743篇 |
专业分类
化学 | 4927篇 |
晶体学 | 79篇 |
力学 | 28篇 |
综合类 | 35篇 |
数学 | 8篇 |
物理学 | 2227篇 |
出版年
2024年 | 1篇 |
2023年 | 42篇 |
2022年 | 98篇 |
2021年 | 125篇 |
2020年 | 131篇 |
2019年 | 142篇 |
2018年 | 182篇 |
2017年 | 217篇 |
2016年 | 236篇 |
2015年 | 190篇 |
2014年 | 280篇 |
2013年 | 953篇 |
2012年 | 367篇 |
2011年 | 371篇 |
2010年 | 296篇 |
2009年 | 370篇 |
2008年 | 377篇 |
2007年 | 479篇 |
2006年 | 367篇 |
2005年 | 356篇 |
2004年 | 281篇 |
2003年 | 267篇 |
2002年 | 223篇 |
2001年 | 137篇 |
2000年 | 134篇 |
1999年 | 96篇 |
1998年 | 111篇 |
1997年 | 66篇 |
1996年 | 41篇 |
1995年 | 57篇 |
1994年 | 48篇 |
1993年 | 63篇 |
1992年 | 37篇 |
1991年 | 26篇 |
1990年 | 20篇 |
1989年 | 20篇 |
1988年 | 22篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有7304条查询结果,搜索用时 15 毫秒
61.
Stimulated by the recent experimental success in production and characterization of YCN@Cs(6)‐C82, the possibility of encapsulating YCN cluster in the C78 fullerene has been performed using density functional theory. Six isomers of YCN@C78 are considered based on six lowest energy C782? isomers. The results reveal that YCN@D3h(24109)‐C78 and YCN@C2v(24107)‐C78, both of which satisfy the isolated‐pentagon rule, present excellent thermodynamic stability with very small energy differences. Moreover, the large HOMO‐LUMO gaps (1.55 and 1.47 eV for YCN@D3h(24109)‐C78 and YCN@C2v(24107)‐C78, respectively) indicate their high kinetic stabilities. Significantly, in both the structures, the encapsulated YCN cluster is triangular, similar to the cases of YCN@Cs(6)‐C82 and TbCN@C2(5)‐C82. In addition, electronic absorption spectra, infrared spectra, and 13C nuclear magnetic resonance spectra of two stable structures have also been explored to further disclose the molecular structures and properties. © 2015 Wiley Periodicals, Inc. 相似文献
62.
Enantiomeric separation of 1,3‐dimethylamylamine by capillary electrophoresis with indirect UV detection using a dual‐selector system 下载免费PDF全文
The CE method employing an indirect UV detection for the enantioseparation of 1,3‐dimethylamylamine (DMAA), widely used in various preworkout and dietary supplements labeled as a constituent of geranium extract has been developed. The dual‐selector system consisting of negatively charged sulfated α‐CD (1.1% w/v) and sulfated β‐CD (0.2% w/v) in 5 mM phosphate/Tris buffer (pH 3.0) containing the addition of 10 mM benzyltriethylammonium chloride (BTEAC) as the chromophoric additive was used for the enantiomeric separation of DMAA stereoisomers with the LODs in the range of 7.82–9.24 μg/mL. The method was partly validated and applied for the determination of the stereoisomeric composition of DMAA in commercial dietary supplements to verify the potential natural origin of DMAA. 相似文献
63.
64.
Taranjeet Kaur Ravinder Kumar Wanchoo 《International journal of environmental analytical chemistry》2015,95(6):494-507
Photocatalytic degradation of propiconazole, a triazole pesticide, in the presence of titanium dioxide (TiO2) under ultraviolet (UV) illumination was performed in a batch type photocatalytic reactor. A full factorial experimental design technique was used to study the main effects and the interaction effects between operational parameters in the photocatalytic degradation of propiconazole in a batch photo-reactor using the TiO2 aqueous suspension. The effects of catalyst concentration (0.15–0.4 gL?1), initial pH (3–9), initial concentration (5–35 mg L?1) and light conditions were optimised at a reaction time duration of 90 min by keeping area/volume ratio constant at 0.919 cm2 mL?1. Photocatalytic oxidation of propiconazole showed 85% degradation and 76.57% mineralisation under UV light (365 nm/30 Wm?2) at pH 6.5, initial concentration 25 mg L?1 and constant temperature (25 ± 1 °C). The Langmuir–Hinshelwood kinetic model has successfully elucidated the effects of the initial concentration on the degradation of propiconazole and the data obtained are consistent with the available kinetic parameters. The photocatalytic transformation products of propiconazole were identified by using gas chromatography–mass spectrometry (GC/MS). The pathway of degradation obtained from mass spectral analysis shows the breakdown of transformation products into smaller hydrocarbons (m/z 28 and 39). 相似文献
65.
Indachlorins: Nonplanar Indanone‐Annulated Chlorin Analogues with Panchromatic Absorption Spectra between 300 and 900 nm 下载免费PDF全文
Dr. Lalith P. Samankumara Dr. Sarina J. Dorazio Dr. Joshua Akhigbe Ruoshi Li Dr. Arunpatcha Nimthong‐Roldán Dr. Matthias Zeller Prof. Dr. Christian Brückner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11118-11128
Indaphyrins, pyrrole‐modified porphyrins containing a cleaved pyrrole β,β′‐bond and two annulated indanone moieties, possess unusually broadened and redshifted UV/Vis spectra because of their π‐expanded chromophores. The parent free base indaphyrin has been crystallographically characterized, highlighting its strongly ruffled conformation incorporating a helimeric twist. It was shown to be susceptible to regiospecific derivatizations at the opposite side of the ring‐cleaved pyrrole (dihydroxylation, followed by functional group transformations of the resulting diol functionality), generating indaphyrin‐based chlorin analogues, indachlorins, that incorporate a dihydroxypyrroline, pyrrolindione, oxazolone, or a morpholine moiety. Structural modifications resulted in further broadening and hyper‐ and bathochromic shifts of the optical spectra, some of which possess a nearly panchromatic absorption between 300 to well above 900 nm. The extents to which these modifications affect their solid‐state conformations were analyzed. 相似文献
66.
Fast Photoresponse and Long Lifetime UV Photodetectors and Field Emitters Based on ZnO/Ultrananocrystalline Diamond Films 下载免费PDF全文
Adhimoorthy Saravanan Prof. Dr. Bohr‐Ran Huang Jun‐Cheng Lin Gerd Keiser Prof. Dr. I‐Nan Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):16017-16026
We have designed photodetectors and UV field emitters based on a combination of ZnO nanowires/nanorods (ZNRs) and bilayer diamond films in a metal–semiconductor–metal (MSM) structure. The ZNRs were fabricated on different diamond films and systematic investigations showed an ultra‐high photoconductive response from ZNRs prepared on ultrananocrystalline diamond (UNCD) operating at a lower voltage of 2 V. We found that the ZNRs/UNCD photodetector (PD) has improved field emission properties and a reduced turn‐on field of 2.9 V μm?1 with the highest electron field emission (EFE) by simply illuminating the sample with ultraviolet (UV) light. The photoresponse (Iphoto/Idark) behavior of the ZNRs/UNCD PD exhibits a much higher photoresponse (912) than bare ZNRs (229), ZNRs/nanocrystalline diamond (NCD; 518), and ZNRs/microcrystalline diamond (MCD; 325) under illumination at λ=365 nm. A photodetector with UNCD films offers superior stability and a longer lifetime compared with carbon materials and bare ZNRs. The lifetime stability of the ZNRs/UNCD‐based device is about 410 min, which is markedly superior to devices that use bare ZNRs (92 min). The ZNRs/UNCD PD possesses excellent photoresponse properties with improved lifetime and stability; in addition, ZNRs/UNCD‐based UV emitters have great potential for applications such as cathodes in flat‐panel displays and microplasma display devices. 相似文献
67.
以4-氯-1-丁醇,N-甲基咪唑和苯甲酸钠为原料,用微波法制得碱性离子液体{[OHBMIM]Ph COO(AIL)},其结构经FT-IR表征;以苯甲醛和苯乙酮为原料,AIL为催化剂,经微波促进的缩合反应合成了查尔酮(1),其结构经1H NMR和FT-IR确证。考察了AIL用量、微波功率、物料比和反应时间对1产率的影响。合成1的最佳反应条件为:AIL 1 mmol,苯甲醛5 mmol,n(苯甲醛)∶n(苯乙酮)=1.1,于微波功率140 W反应5 min,产率95.8%。AIL具有较好的循环使用性,循环使用6次,1产率没有明显降低。 相似文献
68.
Synthesis of polyamidoamine dendrimer (PAMAM/CuS/AA) nanocomposite and its application in the removal of Isma acid fast yellow G Dye 下载免费PDF全文
The adsorption of Isma acid fast yellow G dye was studied using polyamidoamine (PAMAM)/Copper sulfide (CuS)/AA nanocomposite containing different amounts of CuS by batch technique. PAMAM dendrimer/CuS/AA nanocomposites were synthesized via gamma irradiation cross‐linking method with the aid of sonication. The nanocomposites were characterized by Fourier‐transform infrared, X‐ray diffraction, transmission electron microscope, energy dispersive spectroscopy X‐ray, thermal gravimetric analysis, ultraviolet‐visible, and fluorescence spectroscopy. The size of the CuS nanoparticles was formed in the range of 12–19 nm. The adsorption capacity of the nanocomposites was evaluated as a function of initial dye concentration, pH, adsorbent dosage, and time. It was verified that the adsorption rate fits a pseudo‐second‐order kinetics for initial Isma acid fast yellow G dye concentrations. Results indicated that the adsorption of Isma acid fast yellow G dye fitted well to the Langmuir model. Our results demonstrate that the PAMAM dendrimer/CuS/AA nanocomposite is very promising for removing organic dyes from wastewater. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
69.
Direct Conversion of Bulk Metals to Size‐Tailored,Monodisperse Spherical Non‐Coinage‐Metal Nanocrystals 下载免费PDF全文
Rui‐Chun Luo Chao Li Prof. Xi‐Wen Du Prof. Jing Yang 《Angewandte Chemie (International ed. in English)》2015,54(16):4787-4791
Monodisperse non‐noble metal nanocrystals (NCs) that are highly uniform in shapes and particle size are much desired in various advanced applications, and are commonly prepared by either thermal decomposition or reduction, where reactive organometallic precursors or/and strong reducing agents are mandatory; however, these are usually toxic, costly, or suffer a lack of availability. Bulk Group 12 metals can now be converted into ligand‐protected, highly crystalline, monodisperse spherical metal NCs with precisely controlled sizes without using any precursors and reducers. The method is based on low‐power NIR‐laser‐induced size‐selective layer‐by‐layer surface vaporization. The monodisperse Cd NCs show pronounced deep‐UV (DUV) localized surface plasmon resonance making them highly competitive DUV‐plasmonic materials. This approach will promote appreciably the emergence of a wide range of monodisperse technically important non‐coinage metal NCs with compelling functionalities. 相似文献
70.
For self-interstitial atom (SIA) clusters in various concentrated alloys, one-dimensional (1D) migration is induced by electron irradiation around 300 K. But at elevated temperatures, the 1D migration frequency decreases to less than one-tenth of that around 300 K in iron-based bcc alloys. In this study, we examined mechanisms of 1D migration at elevated temperatures using in situ observation of SUS316L and its model alloys with high-voltage electron microscopy. First, for elevated temperatures, we examined the effects of annealing and short-term electron irradiation of SIA clusters on their subsequent 1D migration. In annealed SUS316L, 1D migration was suppressed and then recovered by prolonged irradiation at 300 K. In high-purity model alloy Fe-18Cr-13Ni, annealing or irradiation had no effect. Addition of carbon or oxygen to the model alloy suppressed 1D migration after annealing. Manganese and silicon did not suppress 1D migration after annealing but after short-term electron irradiation. The suppression was attributable to the pinning of SIA clusters by segregated solute elements, and the recovery was to the dissolution of the segregation by interatomic mixing under electron irradiation. Next, we examined 1D migration of SIA clusters in SUS316L under continuous electron irradiation at elevated temperatures. The 1D migration frequency at 673 K was proportional to the irradiation intensity. It was as high as half of that at 300 K. We proposed that 1D migration is controlled by the competition of two effects: induction of 1D migration by interatomic mixing and suppression by solute segregation. 相似文献