全文获取类型
收费全文 | 2165篇 |
免费 | 107篇 |
国内免费 | 15篇 |
专业分类
化学 | 1673篇 |
晶体学 | 13篇 |
力学 | 34篇 |
综合类 | 16篇 |
数学 | 226篇 |
物理学 | 325篇 |
出版年
2023年 | 19篇 |
2022年 | 13篇 |
2021年 | 39篇 |
2020年 | 44篇 |
2019年 | 53篇 |
2018年 | 38篇 |
2017年 | 30篇 |
2016年 | 56篇 |
2015年 | 51篇 |
2014年 | 57篇 |
2013年 | 115篇 |
2012年 | 148篇 |
2011年 | 150篇 |
2010年 | 81篇 |
2009年 | 96篇 |
2008年 | 159篇 |
2007年 | 134篇 |
2006年 | 129篇 |
2005年 | 136篇 |
2004年 | 119篇 |
2003年 | 87篇 |
2002年 | 93篇 |
2001年 | 26篇 |
2000年 | 30篇 |
1999年 | 24篇 |
1998年 | 24篇 |
1997年 | 22篇 |
1996年 | 24篇 |
1995年 | 14篇 |
1994年 | 18篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 11篇 |
1990年 | 21篇 |
1989年 | 13篇 |
1988年 | 13篇 |
1987年 | 14篇 |
1986年 | 6篇 |
1985年 | 21篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 15篇 |
1981年 | 18篇 |
1980年 | 17篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 10篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 7篇 |
排序方式: 共有2287条查询结果,搜索用时 15 毫秒
121.
Quantum tunneling effects play an important role in a variety of chemical reactions considerably affecting the reaction rates via opening the classically forbidden paths and emerging as highly efficient or selective processes. However, in the case of electrochemical reactions, quantum tunneling effects are less investigated due to complicated nature of chemical interactions at the electrified interfaces. In this review, we summarize the experimental/theoretical concept of electrochemical quantum proton tunneling (EQPT), which is a key element in microscopic electrode processes. First, we review the experimental observations of EQPT, and next, we discuss possible theoretical pictures of the process. This review shows that a combination of a wide spectrum of scientific efforts is required to understand microscopic mechanism of EQPT including development of the precise electrochemistry-oriented experimental techniques and methodologies, formulation of the appropriate theoretical models for specific systems, and performance of the advanced computational simulations. 相似文献
122.
Doaa H. M. Alsaadi Aedla Raju Ken Kusakari Faruk Karahan Nazim Sekeroglu Takashi Watanabe 《Molecules (Basel, Switzerland)》2020,25(23)
The growth and quality of licorice depend on various environmental factors, including the local climate and soil properties; therefore, its cultivation is often unsuccessful. The current study investigated the key factors that affect the contents of bioactive compounds of Glycyrrhiza glabra L. root and estimated suitable growth zones from collection sites in the Hatay region of Turkey. The contents of three bioactive compounds (glycyrrhizic acid, glabridin, and liquiritin), soil factors (pH, soil bearing capacity, and moisture content), and geographical information (slope, aspect, curvature, elevation, and hillshade) were measured. Meteorological data (temperature and precipitation) were also obtained. An analysis of variance (ANOVA) and multivariate analysis of variance (MANOVA) were performed on the data. The soil bearing capacity, moisture content, slope, aspect, curvature, and elevation of the study area showed statistically significant effects on the glycyrrhizic acid and liquiritin contents. A habitat suitability zone map was generated using a GIS-based frequency ratio (FR) model with spatial correlations to the soil, topographical, and meteorological data. The final map categorized the study area into four zones: very high (15.14%), high (31.50%), moderate (40.25%), and low suitability (13.11%). High suitability zones are recommended for further investigation and future cultivation of G. glabra. 相似文献
123.
Hiroshi Takikawa Arata Nishii Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Keiichi Hirano Masanobu Uchiyama Ken Ohmori Keisuke Suzuki 《Angewandte Chemie (International ed. in English)》2020,59(30):12440-12444
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
124.
Hiroshi Fujimoto Ken Sakata Kenichi Fukui 《International journal of quantum chemistry》1996,60(1):401-408
Electron delocalization between the reagent and reactant molecules is the principal driving force of chemical reactions. It brings about the formation of new bonds and the cleavage of old bonds. By taking the aromatic substitution reaction as an example, we have shown the orbitals participating in electron delocalization. The interacting orbitals obtained are localized around the reaction sites, showing the chemical bonds that should be generated and broken transiently along the reaction path. By projecting a reference orbital function that has been chosen to specify the bond being formed on to the MOs of the reactant molecules, the reactive orbitals that are very similar to the interacting orbital have been obtained. The local potential of the reaction site for electron donation estimated for substituted benzene molecules by using these projected orbitals shows a fair correlation with the experimental scale of the electron-donating and -withdrawing strength of substituent groups. The reactivity is shown to be governed by local electronegativity and local chemical hardness and also by the localizability of interaction on the reaction site. © 1996 John Wiley & Sons, Inc. 相似文献
125.
Jrg Kressler Bernd Rudolf Ken Shimomai Toshiaki Ougizawa Takashi Inoue 《Macromolecular rapid communications》1995,16(8):631-636
Pressure, volume, temperature (PVT) measurements reveal that during the intramolecular cyclization reaction of poly(acrylonitrile) (PAN) and poly(styrene-co-acrylonitrile) (SAN) the volume decreases. This volume contraction becomes smaller with increasing styrene content in the random copolymers and should be related to the simultaneous decrease of longer acrylonitrile homo-sequences. The onset temperature of the cyclization reaction is raised with higher styrene contents in the random copolymers. Thus, it can be excluded that the cyclization reaction has a major influence on the discoloration process of SAN samples having relatively small acrylonitrile contents (less than 50 mol-%) during thermal annealing below 300°C. 相似文献
126.
Organic single crystals of 2-methyl-4-nitroaniline (MNA) up to 3 mm in diameter and 20 mm in length have been successfully grown by the Bridgman method using the purified reagent by sublimation. The crystals are transparent and yellow in colour by controlling the growth conditions. In the spectra of yellow coloured crystals no absorption peak is observed until about 450 nm. Also, the crystals of MNA have the two cleavage planes (311 ) and (010). 相似文献
127.
作为一种新型结构材料, 非晶态合金的韧性需要进一步提高. 提高非晶态合金韧性的方法有引入枝晶相、调整其成分改变其泊松比影响其剪切带衍生、裂纹扩展等.本文通过表面机械加工的方法来调控非晶态合金的微观结构及韧性. 我们采用真空电弧熔炼、亚稳态薄板离心浇铸系统制备了Zr52.5Cu17.9Ni14.6Al10Ti5 (原子百分比) (Vit105)非晶合金板,并用表面机械研磨处理方法(surface mechanical attrition treatment, SMAT), 在Vit105板上形成纳米尺度局域类晶体序结构. 基于差示扫描量热分析、纳米压痕实验, 我们发现SMAT处理后的Vit105合金板表面附近弛豫焓更低, 微观结构更加均匀、稳定. 通过显微维氏硬度计测试, 发现SMAT处理后样品的表面附近硬度增大,硬度值分布也更均匀. 通过三点弯断裂实验, 可得到SMAT处理后合金板缺口韧度值从70.7 ± 4.7 MPa·m1/2提高到112.8 ± 3.7 MPa·m1/2. SMAT处理后合金板断裂后, 缺口前端剪切带密度比未处理的更大. Vit105合金板韧性的提高源于SMAT处理对剪切带萌生的促进作用. 该研究表明,表面机械加工可以在非晶态合金中形成局域类晶体有序结构, 影响其结构均匀性, 增大其硬度, 促进剪切带萌生, 提高其韧性. 表面机械加工作为一种新型的改变材料性能的手段, 具有广阔的应用前景. 相似文献
128.
A simple Cu-DNAzyme system is used for signal transduction of a CuO nanoparticle-labeled immunoassay, which makes the immunoassay fast, simple, cost-effective, and sensitive, thus promising for biomedical applications and point-of-care testing. 相似文献
129.
Toshio Nishi Hideyuki Nukaga So Fujinami Ken Nakajima 《高分子科学》2007,(1):35-41
Atomic force microscopy (AFM) has the advantage of obtaining mechanical properties as well as topographic information at the same time. By analyzing force-distance curves measured over two-dimensional area using Hertzian contact mechanics, Young's modulus mapping was obtained with nanometer-scale resolution. Furthermore, the sample deformation by the force exerted was also estimated from the force-distance curve analyses. We could thus reconstruct a real topographic image by incorporating apparent topographic image with deformation image. We applied this method to carbon black reinforced natural rubber to obtain Young's modulus distribution image together with reconstructed real topographic image. Then we were able to recognize three regions; rubber matrix, carbon black (or bound rubber) and intermediate regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first to report on the quantitative evaluation of the interfacial region in real space. 相似文献
130.
Dynamics of ice nucleation on water repellent surfaces 总被引:3,自引:0,他引:3
Alizadeh A Yamada M Li R Shang W Otta S Zhong S Ge L Dhinojwala A Conway KR Bahadur V Vinciquerra AJ Stephens B Blohm ML 《Langmuir : the ACS journal of surfaces and colloids》2012,28(6):3180-3186
Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications. 相似文献