全文获取类型
收费全文 | 46914篇 |
免费 | 3113篇 |
国内免费 | 3260篇 |
专业分类
化学 | 18817篇 |
晶体学 | 382篇 |
力学 | 3731篇 |
综合类 | 498篇 |
数学 | 10615篇 |
物理学 | 19244篇 |
出版年
2024年 | 34篇 |
2023年 | 398篇 |
2022年 | 693篇 |
2021年 | 975篇 |
2020年 | 1033篇 |
2019年 | 1070篇 |
2018年 | 955篇 |
2017年 | 1094篇 |
2016年 | 1235篇 |
2015年 | 958篇 |
2014年 | 1548篇 |
2013年 | 2946篇 |
2012年 | 1864篇 |
2011年 | 2052篇 |
2010年 | 1657篇 |
2009年 | 2731篇 |
2008年 | 2981篇 |
2007年 | 3375篇 |
2006年 | 2818篇 |
2005年 | 2221篇 |
2004年 | 1858篇 |
2003年 | 2154篇 |
2002年 | 2563篇 |
2001年 | 1926篇 |
2000年 | 1833篇 |
1999年 | 1443篇 |
1998年 | 1415篇 |
1997年 | 784篇 |
1996年 | 744篇 |
1995年 | 688篇 |
1994年 | 745篇 |
1993年 | 545篇 |
1992年 | 620篇 |
1991年 | 411篇 |
1990年 | 393篇 |
1989年 | 291篇 |
1988年 | 259篇 |
1987年 | 261篇 |
1986年 | 231篇 |
1985年 | 207篇 |
1984年 | 216篇 |
1983年 | 126篇 |
1982年 | 173篇 |
1981年 | 167篇 |
1980年 | 105篇 |
1979年 | 132篇 |
1978年 | 100篇 |
1977年 | 85篇 |
1976年 | 39篇 |
1973年 | 34篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
An identification method to estimate surface shortwave fluxes on temperature and thickness observations of sea ice in CHINARE 2006 下载免费PDF全文
In this paper, a parameter identification method to determine surface shortwave fluxes using temperature and thickness measurements of sea ice in CHINARE 2006 is presented. Adopting a new standard for the calculation of the thermodynamic properties of seawater named TEOS‐10, the surface shortwave fluxes are calculated by the temperature and thickness observations that were measured at Nella Fjord around Zhongshan Station, Antarctica. New simulations for temperature profiles in a different measurement period are performed by three parameterization schemes including the present method, Zillman and Shine. All numerical results are compared with in situ measurements. Results show that better simulations of the surface shortwave radiations and temperature distributions are possible with the identification method than Zillman and Shine. Therefore this method is valid, and the obtained shortwave radiation function can be applied in sea ice modeling. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
92.
Alexandre S. Miranda Paula M. Marcos Jos R. Ascenso M. Paula Robalo Vasco D. B. Bonifcio Mrio N. Berberan-Santos Neal Hickey Silvano Geremia 《Molecules (Basel, Switzerland)》2021,26(6)
Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)- or N-(bromoethyl)phthalimides and K2CO3 in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono- and mainly distal di-substituted derivatives in the cone conformation, in a total of eight compounds. They were isolated by column chromatography, and their conformations and the substitution patterns were established by NMR spectroscopy (1H, 13C, COSY and NOESY experiments). The X-ray structures of four dihomooxacalix[4]arene phthalimide derivatives (2a, 3a, 3b and 5a) are reported, as well as their photophysical properties. The microwave (MW)-assisted alkylations drastically reduced the reaction times (from days to less than 45 min) and produced higher yields of both 1,3-di-substituted phthalimides (3a and 6a) with higher selectivity. Ball milling did not reveal to be a good method for this kind of reaction. 相似文献
93.
Martin Kellert Jan-Simon Jeshua Friedrichs Nadine Anke Ullrich Alexander Feinhals Jonas Tepper Peter Lnnecke Evamarie Hey-Hawkins 《Molecules (Basel, Switzerland)》2021,26(7)
The development of novel, tumor-selective and boron-rich compounds as potential agents for use in boron neutron capture therapy (BNCT) represents a very important field in cancer treatment by radiation therapy. Here, we report the design and synthesis of two promising compounds that combine meta-carborane, a water-soluble monosaccharide and a linking unit, namely glycine or ethylenediamine, for facile coupling with various tumor-selective biomolecules bearing a free amino or carboxylic acid group. In this work, coupling experiments with two selected biomolecules, a coumarin derivative and folic acid, were included. The task of every component in this approach was carefully chosen: the carborane moiety supplies ten boron atoms, which is a tenfold increase in boron content compared to the l-boronophenylalanine (l-BPA) presently used in BNCT; the sugar moiety compensates for the hydrophobic character of the carborane; the linking unit, depending on the chosen biomolecule, acts as the connection between the tumor-selective component and the boron-rich moiety; and the respective tumor-selective biomolecule provides the necessary selectivity. This approach makes it possible to develop a modular and feasible strategy for the synthesis of readily obtainable boron-rich agents with optimized properties for potential applications in BNCT. 相似文献
94.
利用热丝化学气相沉积法(HFCVD)在碳化硅基底上制备金刚石薄膜,采用场发射扫描电子显微镜、拉曼光谱仪、原子力显微镜研究了在不同甲烷浓度条件下制备的金刚石薄膜表面形貌及物相组成,在干摩擦条件下通过往复式摩擦磨损实验测试并计算了已制备金刚石薄膜的摩擦系数和磨损率,结合物相分析及摩擦磨损实验结果分析了甲烷浓度的改变对金刚石薄膜摩擦磨损性能的影响。结果表明,由于甲烷气体含量的升高,金刚石薄膜结晶质量下降,薄膜由微米晶向纳米晶转变。摩擦磨损实验结果显示:3%甲烷浓度条件下制备的金刚石薄膜耐磨性较好,磨损率为2.2×10-7 mm3/mN;5%甲烷浓度条件下制备的金刚石薄膜摩擦系数最低(0.032),磨损率为5.7×10-7 mm3/mN,制备的金刚石薄膜的耐磨损性能相比于碳化硅基底(磨损率为9.89×10-5 mm3/mN)提升了两个数量级,显著提高了碳化硅基底的耐磨性。 相似文献
95.
Yuwei Wang Jia-Jun Yan Shengnan Hu Prof. David James Young Prof. Hong-Xi Li Prof. Zhi-Gang Ren 《化学:亚洲杂志》2021,16(18):2681-2686
A photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water. 相似文献
96.
For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R2 = 0.98) compared to LH (R2 = 0.97) and Eley-Rideal (R2 = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives. 相似文献
97.
Dr. Anton A. Anisimov Dr. Fedor V. Drozdov Yulia S. Vysochinskaya Ekaterina O. Minyaylo Prof. Alexander S. Peregudov Prof. Fedor M. Dolgushin Dr. Olga I. Shchegolikhina Prof. Aziz M. Muzafarov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11404-11407
This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70–80 %) and were fully characterized by 1H, 13C, 29Si, 11B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane, was also confirmed by single-crystal XRD. 相似文献
98.
Alberto Fernández-Alarcón Dr. José Manuel Guevara-Vela José Luis Casals-Sainz Dr. Aurora Costales Dr. Evelio Francisco Dr. Ángel Martín Pendás Dr. Tomás Rocha Rinza 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17035-17045
The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H2O)2. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built. 相似文献
99.
Minghao Xie Zhiheng Lyu Ruhui Chen Prof. Dr. Younan Xia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15636-15642
Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil-phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac)2 in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac)2 and OAc leads to the formation of a PtII–oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of PtII precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals. 相似文献
100.
Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor
Dengchao Zheng Hao Wen Xun Sun Xin Guan Jie Zhang Wenli Tian Hao Feng Dr. Hongjing Wang Prof. Yadong Yao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17149-17155
In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm−2 (specific capacity C: 1178 C g−1) at 2 mA cm−2 in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg−1 at 143.8 Wkg−1 power density with a capacitance retention of 83.6 % after 5000 cycles. 相似文献