全文获取类型
收费全文 | 96336篇 |
免费 | 3599篇 |
国内免费 | 2667篇 |
专业分类
化学 | 37145篇 |
晶体学 | 946篇 |
力学 | 7743篇 |
综合类 | 119篇 |
数学 | 34405篇 |
物理学 | 22244篇 |
出版年
2024年 | 86篇 |
2023年 | 428篇 |
2022年 | 644篇 |
2021年 | 705篇 |
2020年 | 849篇 |
2019年 | 773篇 |
2018年 | 10958篇 |
2017年 | 10740篇 |
2016年 | 6936篇 |
2015年 | 1789篇 |
2014年 | 1375篇 |
2013年 | 1756篇 |
2012年 | 5394篇 |
2011年 | 12096篇 |
2010年 | 6769篇 |
2009年 | 7049篇 |
2008年 | 7738篇 |
2007年 | 9745篇 |
2006年 | 1174篇 |
2005年 | 2156篇 |
2004年 | 2199篇 |
2003年 | 2544篇 |
2002年 | 1675篇 |
2001年 | 783篇 |
2000年 | 722篇 |
1999年 | 578篇 |
1998年 | 530篇 |
1997年 | 453篇 |
1996年 | 524篇 |
1995年 | 405篇 |
1994年 | 306篇 |
1993年 | 255篇 |
1992年 | 218篇 |
1991年 | 220篇 |
1990年 | 172篇 |
1989年 | 152篇 |
1988年 | 112篇 |
1987年 | 113篇 |
1986年 | 128篇 |
1985年 | 93篇 |
1984年 | 74篇 |
1983年 | 62篇 |
1982年 | 56篇 |
1981年 | 49篇 |
1980年 | 50篇 |
1979年 | 45篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Pekka Juusola Pentti Minkkinen Lasse Leino Jarmo K. Laihia 《Monatshefte für Chemie / Chemical Monthly》2007,138(10):951-965
Summary. (E)- and (Z)-Urocanic acids are endogenous chemicals in the normal mammalian skin. The first and the second thermodynamic dissociation
constants (pK
a1 and pK
a2) of urocanic acid isomers were determined using UV spectrophotometry in aqueous solutions. The values with standard deviation
(pK
a1 = 3.43 ± 0.12 and pK
a2 = 5.80 ± 0.04) and (pK
a1 = 2.7 ± 0.3 and pK
a2 = 6.65 ± 0.04) were obtained to (E)- and (Z)-urocanic acids, respectively. The second dissociations were studied also by potentiometric titration in aqueous sodium chloride
solutions up to the isotonic salt concentration (0.154 mol dm−3), and the second thermodynamic dissociation constants as well as activity parameters for both isomers were determined at
temperature 25°C and for (E)-urocanic acid also at 37°C. The obtained pK
a2 values were close to those found by UV spectrophotometry. The equations for the calculation of the second stoichiometric
dissociation constants of urocanic acid isomers on molality and molarity scale in aqueous sodium chloride solutions were derived.
The obtained pK
a1 and pK
a2 values for (Z)-urocanic acid appear to be essentially lower than some previously reported values in literature.
An erratum to this article is available at . 相似文献
992.
The molar conductivities (Λ) of solutions of n-tetrabutylammonium tetraphenylborate (NBu4BPh4) in 3-pentanone have been measured in the temperature range from 283.15 to 329.15 K. The conductance data have been analyzed
using the Lee-Wheaton conductivity equation with the distance parameter (a) set at Bjerrum’s pairing distance, and the limiting molar conductivities (Λo) and the association equilibrium constants (K
A) have been derived. The limiting ion conductivities (λ_±o) have been evaluated according to the method of Krumgalz. The λ+
o values have been compared with λ+
o values calculated from the empirical equation of Gill. The thermodynamic functions, Gibbs energy (Δ G
A
o), enthalpy (Δ H
A
o) and entropy (Δ S
A
o) for the process of ion-pair formation as well as the activation energy of the ionic movement (ΔH
∗) have been evaluated. The obtained results are discussed in terms of ion-ion and ion-solvent interactions. 相似文献
993.
内嵌金属富勒烯的笼外化学修饰 总被引:1,自引:0,他引:1
内嵌金属富勒烯以其独特的结构和新奇的性质吸引了众多科学家的目光,对它们进行笼外化学修饰是最近十年来新兴的研究热点,这对于考察内嵌金属富勒烯的结构及化学物理性质并拓宽其应用范围具有重要意义。本文将内嵌金属富勒烯与各种底物的不同作用分类,以反应类型为线索,详细概括了已发表的内嵌金属富勒烯的各种笼外化学反应,包括各种环化反应、内嵌金属富勒烯与杯芳烃及冠醚的自组装、单键相连的衍生物、水溶性衍生物以及用内嵌金属富勒烯填充碳纳米管等。在对各种化学反应阐述的同时,对内嵌金属富勒烯的可能应用也进行了总结,并提出了自己的看法。 相似文献
994.
Stochastic gradient descent(SGD) is one of the most common optimization algorithms used in pattern recognition and machine learning.This algorithm and its variants are the preferred algorithm while optimizing parameters of deep neural network for their advantages of low storage space requirement and fast computation speed.Previous studies on convergence of these algorithms were based on some traditional assumptions in optimization problems.However,the deep neural network has its unique propertie... 相似文献
995.
以仲胺、氧杂环丁-3-酮和三甲基氰硅烷为原料,无水甲醇为溶剂,无需催化剂,一步反应合成目标化合物3-仲氨基氧杂环丁烷-3-腈衍生物(1a~1d),产物结构经1H NMR、13C NMR和ESI-MS表征。并以异吲哚啉、氧杂环丁-3-酮和三甲基氰硅烷的反应为模型反应,考察影响产物1a收率的主要因素,优化反应条件为:物料摩尔比为n(异吲哚啉)∶n(氧杂环丁-3-酮)∶n(三甲基氰硅烷)=2.0∶1∶2.5;反应溶剂为无水甲醇,在65℃反应6h,在此反应条件下,化合物1a收率78.3%。化合物1a与苯基溴化镁在四氢呋喃中室温反应5h,可得到2-(3-苯基氧杂环丁烷-3-基)异吲哚啉(4)和[3-(异吲哚啉-2-基)氧杂环丁烷-3-基](苯基)甲酮(5),收率分别为40.1%和31.5%。 相似文献
996.
核电结构土-结相互作用分析分区混合计算方法 总被引:3,自引:2,他引:1
土-结构相互作用分析是核电结构进行抗震设计和安全评估的重要环节.在核电结构的土-结相互作用分析中,阻尼和非线性是影响结构反应的重要因素.若采用频域分析,可以方便考虑阻尼,但需通过等效线性化来考虑非线性,不适合于强震作用下的土体非线性.若采用时域分析的逐步积分方法,适合于考虑非线性,但材料阻尼一般采用瑞利阻尼模型,除了紧靠指定阻尼比的少数几个振型外,其他振型的反应将受到瑞利阻尼模型所确定的大阻尼所抑制,造成地震反应与真实情形有较大差异.若采用时域分析的模态叠加法,可合理计入阻尼效应,但模态叠加法不能考虑非线性.因此,如何合理考虑阻尼和非线性是核电结构土-结相互作用分析需要关注的问题.基于此,本文提出一种模态叠加和时步积分结合的土-结相互作用分区算法.其中,出于安全性考虑,地震作用下核电主体结构一般不允许进入非线性,因此结构可采用模态叠加方法,以便合理考虑结构阻尼;土体和基础采用显式时步积分法,可考虑土体非线性;通过人工边界条件考虑无限域的影响(辐射阻尼).通过简单算例对该方法进行了验证,并用于CAP1400核电结构的土-结相互作用分析中,对比分析了采用模态阻尼和瑞利阻尼时核电结构和场地反... 相似文献
997.
Qiqin Cai Dingrong Yi Fumin Zou Zhaoyi Zhou Nan Li Feng Guo 《Entropy (Basel, Switzerland)》2022,24(9)
To scientifically and effectively evaluate the service capacity of expressway service areas (ESAs) and improve the management level of ESAs, we propose a method for the recognition of vehicles entering ESAs (VeESAs) and estimation of vehicle dwell times using electronic toll collection (ETC) data. First, the ETC data and their advantages are described in detail, and then the cleaning rules are designed according to the characteristics of the ETC data. Second, we established feature engineering according to the characteristics of VeESA and proposed the XGBoost-based VeESA recognition (VR-XGBoost) model. Studied the driving rules in depth, we constructed a kinematics-based vehicle dwell time estimation (K-VDTE) model. The field validation in Part A/B of Yangli ESA using real ETC transaction data demonstrates that the effectiveness of our proposal outperforms the current state-of-the-art. Specifically, in Part A and Part B, the recognition accuracies of VR-XGBoost are 95.9% and 97.4%, respectively, the mean absolute errors (MAEs) of dwell time are 52 and 14 s, respectively, and the root mean square errors (RMSEs) are 69 and 22 s, respectively. In addition, the confidence level of controlling the MAE of dwell time within 2 min is more than 97%. This work can effectively recognize the VeESA and accurately estimate the dwell time, which can provide a reference idea and theoretical basis for the service capacity evaluation and layout optimization of the ESA. 相似文献
998.
Lei Yang Xiaoyu Guo Xiaowei Song Deyuan Lu Wenjing Cai Zixiang Xiong 《Entropy (Basel, Switzerland)》2022,24(11)
This paper proposes an improved human-body-segmentation algorithm with attention-based feature fusion and a refined corner-based feature-point design with sub-pixel stereo matching for the anthropometric system. In the human-body-segmentation algorithm, four CBAMs are embedded in the four middle convolution layers of the backbone network (ResNet101) of PSPNet to achieve better feature fusion in space and channels, so as to improve accuracy. The common convolution in the residual blocks of ResNet101 is substituted by group convolution to reduce model parameters and computational cost, thereby optimizing efficiency. For the stereo-matching scheme, a corner-based feature point is designed to obtain the feature-point coordinates at sub-pixel level, so that precision is refined. A regional constraint is applied according to the characteristic of the checkerboard corner points, thereby reducing complexity. Experimental results demonstrated that the anthropometric system with the proposed CBAM-based human-body-segmentation algorithm and corner-based stereo-matching scheme can significantly outperform the state-of-the-art system in accuracy. It can also meet the national standards GB/T 2664-2017, GA 258-2009 and GB/T 2665-2017; and the textile industry standards FZ/T 73029-2019, FZ/T 73017-2014, FZ/T 73059-2017 and FZ/T 73022-2019. 相似文献
999.
1000.
Jifeng Yu Song Li Dianze Chen Dandan Liu Huiqin Guo Chunmei Yang Wei Zhang Li Zhang Gui Zhao Xiaoping Tu Liang Peng Sijin Liu Xing Bai Yongping Song Zhongxing Jiang Ruliang Zhang Wenzhi Tian 《Molecules (Basel, Switzerland)》2022,27(17)
Background: Targeting the CD47/SIRPα signaling pathway represents a novel approach to enhance anti-tumor immunity. However, the crystal structure of the CD47/SIRPα has not been fully studied. This study aims to analyze the structure interface of the complex of CD47 and IMM01, a novel recombinant SIRPα-Fc fusion protein. Methods: IMM01-Fab/CD47 complex was crystalized, and diffraction images were collected. The complex structure was determined by molecular replacement using the program PHASER with the CD47-SIRPαv2 structure (PDB code 2JJT) as a search model. The model was manually built using the COOT program and refined using TLS parameters in REFMAC from the CCP4 program suite. Results: Crystallization and structure determination analysis of the interface of IMM01/CD47 structure demonstrated CD47 surface buried by IMM01. Comparison with the literature structure (PDB ID 2JJT) showed that the interactions of IMM01/CD47 structure are the same. All the hydrogen bonds that appear in the literature structure are also present in the IMM01/CD47 structure. These common hydrogen bonds are stable under different crystal packing styles, suggesting that these hydrogen bonds are important for protein binding. In the structure of human CD47 in complex with human SIRPα, except SER66, the amino acids that form hydrogen bonds are all conserved. Furthermore, comparing with the structure of PDB ID 2JJT, the salt bridge interaction from IMM01/CD47 structure are very similar, except the salt bridge bond between LYS53 in IMM01 and GLU106 in CD47, which only occurs between the B and D chains. However, as the side chain conformation of LYS53 in chain A is slightly different, the salt bridge bond is absent between the A and C chains. At this site between chain A and chain C, there are a salt bridge bond between LYS53 (A) and GLU104 (C) and a salt bridge bond between HIS56 (A) and GLU106 (C) instead. According to the sequence alignment results of SIRPα, SIRPβ and SIRPγ in the literature of PDB ID 2JJT, except ASP100, the amino acids that form common salt bridge bonds are all conserved. Conclusion: Our data demonstrated crystal structure of the IMM01/CD47 complex and provides a structural basis for the structural binding interface and future clinical applications. 相似文献