全文获取类型
收费全文 | 2523篇 |
免费 | 310篇 |
国内免费 | 157篇 |
专业分类
化学 | 1892篇 |
晶体学 | 33篇 |
力学 | 113篇 |
综合类 | 4篇 |
数学 | 250篇 |
物理学 | 698篇 |
出版年
2024年 | 5篇 |
2023年 | 95篇 |
2022年 | 114篇 |
2021年 | 128篇 |
2020年 | 163篇 |
2019年 | 173篇 |
2018年 | 161篇 |
2017年 | 111篇 |
2016年 | 173篇 |
2015年 | 166篇 |
2014年 | 188篇 |
2013年 | 236篇 |
2012年 | 274篇 |
2011年 | 253篇 |
2010年 | 166篇 |
2009年 | 129篇 |
2008年 | 133篇 |
2007年 | 115篇 |
2006年 | 68篇 |
2005年 | 41篇 |
2004年 | 25篇 |
2003年 | 11篇 |
2002年 | 20篇 |
2001年 | 5篇 |
2000年 | 14篇 |
1999年 | 1篇 |
1998年 | 6篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1993年 | 3篇 |
1991年 | 1篇 |
1990年 | 6篇 |
1986年 | 1篇 |
1985年 | 2篇 |
排序方式: 共有2990条查询结果,搜索用时 78 毫秒
131.
Multi‐Colored Fibers by Self‐Assembly of DNA,Histone Proteins,and Cationic Conjugated Polymers 下载免费PDF全文
Fengyan Wang Zhang Liu Bing Wang Dr. Liheng Feng Prof. Libing Liu Prof. Fengting Lv Prof. Yilin Wang Prof. Shu Wang 《Angewandte Chemie (International ed. in English)》2014,53(2):424-428
The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color‐encoded IPC fibers were also obtained based on the co‐assembly of DNA, histone proteins, and blue‐, green‐, or red‐ (RGB‐) emissive CCPs by tuning the fluorescence resonance energy‐transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP‐coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi‐colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering. 相似文献
132.
Peng Lv Zhong-min Wang Ying Peng Wen-ping Liu Muhammad-Sadeeq Balogun Huai-ying Zhou 《Journal of Solid State Electrochemistry》2014,18(9):2563-2572
The effect of Cu content on structure, hydrogen storage, and electrochemical properties of LaNi4.1-x Co0.6Mn0.3Cu x alloys has been investigated. For sample, A, B, C, and D are used to represent alloys (x?=?0, 0.15, 0.3, and 0.45), respectively. The results indicate that the four alloys are all single-phase alloy with LaNi5 phase of CaCu5 hexagonal structure, the hydrogen storage capacities of the alloy are about 1.49 wt% (A), 1.48 wt% (B), 1.43 wt% (C), and 1.25 wt% (D) at 303 K. With the increase of Cu content (x) from A to D, hydrogen desorption plateau pressure and pressure hysteresis decrease. Alloy electrode A shows better activation property and higher capacity (334.44 mAh/g). The addition of Cu improves the cyclic stability of the alloy electrodes when x?=?0?~?0.45. However, their self-discharge properties and high-rate dischargeability (HRD) decrease with the increase of x. Further, electrochemical kinetics and electrochemical impedance spectroscopy (EIS) analysis show that the reaction of alloy electrode is controlled by charge transfer step, and the adding of Cu benefits the electrode properties in alkaline solution. 相似文献
133.
采用电化学聚合技术,在掺杂的导电聚吡咯薄膜修饰过的铅笔芯电极上,吸附葡萄糖氧化酶制备葡萄糖生物传感器。首先在含有0.1 mol/L吡咯和0.01 mol/L HCl的溶液中,于0.7 V恒电位下吡咯单体氧化聚合,在铅笔芯电极表面形成聚吡咯薄膜;然后将葡萄糖氧化酶吸附在修饰过的电极上制备出葡萄糖氧化酶-聚吡咯-铅笔芯电极电流型生物传感器。实验考察了吡咯聚合时间、聚合温度、葡萄糖氧化酶吸附量、检测电压以及干扰物对传感器性能的影响。实验结果表明,在优化条件下,传感器的灵敏度为17.78μA/mmol/L,线性范围0.8 mmol/L,线性相关度R=0.9918,响应时间小于16 s,检测下限为18.75μmol/L,有较强的抗干扰能力。 相似文献
134.
An Ylide Transformation of Rhodium(I) Carbene: Enantioselective Three‐Component Reaction through Trapping of Rhodium(I)‐Associated Ammonium Ylides by β‐Nitroacrylates 下载免费PDF全文
Xiaochu Ma Dr. Jun Jiang Siying Lv Wenfeng Yao Yang Yang Dr. Shunying Liu Dr. Fei Xia Prof. Dr. Wenhao Hu 《Angewandte Chemie (International ed. in English)》2014,53(48):13136-13139
The chiral RhI–diene‐catalyzed asymmetric three‐component reaction of aryldiazoacetates, aromatic amines, and β‐nitroacrylates was achieved to obtain γ‐nitro‐α‐amino‐succinates in good yields and with high diastereo‐ and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of RhI‐associated ammonium ylides by nitroacrylates. This new transformation represents the first example of RhI‐carbene‐induced ylide transformation. 相似文献
135.
Screening and analysis of metabolites in rat urine after oral administration of Apocynum venetum L. extracts using HPLC–TOF‐MS 下载免费PDF全文
Liang Zhao Lei Lv Hai Zhang Guang guo‐Tan Yifeng Chai Guoqing Zhang 《Journal of separation science》2014,37(5):515-526
HPLC with diode array detection and ESI‐TOF‐MS was used for the study of the constituents in Apocynum venetum L. extracts and the metabolites in rat urine after oral administration of A. venetum L. extracts. A formula database of the known constituents in A. venetum L. was established, and 21 constituents were rapidly identified by accurately matching their molecular masses with the formulae of the compounds in the database. Furthermore, 34 metabolites were detected and elucidated in the rat urine. The scientific and plausible biotransformation pathways of the flavonoid components in A. venetum L. were also proposed together with the presentation of clues for potential mechanisms of bioactivity. This specific and sensitive HPLC–ESI‐TOF‐MS method can be used to identify the chemical components in the extracts of A. venetum L. and their metabolites in rat urine. This method can also be used to reveal the possible metabolic mechanisms of action of the extract components in vivo. 相似文献
136.
Linyan Yang Liangliang Xin Wen Gu Shengyun Liao Peiyao Du Jinlei Tian Yanping Zhang Rui Lv Xiaohua Wei Xin Liu Daizheng Liao 《中国化学》2014,32(3):227-232
A new coordination polymer, [Co2(L)2(4,4′‐bipy)]n·3nH2O ( 1 ) based on 5‐(3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazol‐4‐yl)isophthalic acid (H2 L ) and 4,4′‐bipyridine (4,4′‐bipy) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR, and elemental analysis. Temperature‐dependent magnetic susceptibility and thermal degradation for 1 were also studied. The asymmetric unit of compound 1 consists of two crystallographically independent Co(II) ion, two L 2? ligand, one 4,4′‐bipy ligand, and three lattice water molecules. The 2D triangle networks were linked by the bridging 4,4′‐bipy ligand to give rise to a 2‐fold interpenetrated 3D architecture. The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II) cations and three L 2? ligands. So we can define Co(II) ions as 4‐connected nodes and the L 2? ligands as 3‐connected nodes. Thus, the 3D structure can be described as a 2‐fold parallel interpenetrated ins InS 3,4‐conn topology. 相似文献
137.
Jungang Wang Jiajia Li Jinhuan Liu Binbin Hua Xiaofen Wang Yucai Lv Yanzhuan Cao Zongjun Cui 《Applied biochemistry and biotechnology》2014,173(2):510-521
Clostridium straminisolvens (CSK1) is a novel cellulolytic bacterium isolated from a cellulose-degrading bacterial community MC1. In this study, the influence of the following cell disruption and elution methods on CSK1cellulase release was investigated: (1) freezing–thawing, (2) ultrasonication, (3) elution, (4) freezing–thawing following elution, (5) ultrasonication following elution, and lastly (6) high-pressure homogenization following elution. The activity of the cellulases CMCase, β-glucosidase, Avicelase, FPase, and xylanase in crude extracts increased 81.5, 23.8, 87.7, 46.3, and 51.7 %, respectively, with an observed optimal treatment method for each cellulase type. The release of protein from CSK1 cells increased following either cell disruption or elution and was highest at 88.3 % in the homogenization high pressure following elution treatment. A newly observed protein was present following cell elution. The performance of cell elution as determined by real time-PCR indicated that the first time cell elution removed more than 90 % of the CSK1 cells from the substrate. These findings demonstrate that cell disruption and elution are effective methods for inducing cellulase release, and elution is the key step for CSK1. To our knowledge, this study presents the first evidence of optimal treatments for induction of cellulase release of Clostridium straminisolvens. This information will be of great value for use in subsequent efforts to better understand the cellulase characteristics of CSK1 and cellulose degradation mechanisms of the MC1 community. 相似文献
138.
Preparation of novel magnetic fluorescent microspheres from copperas and fluorescence enhancement with zinc ions 总被引:1,自引:0,他引:1
The aim of this study is to develop a new method for the preparation of Fe3O4@SiO2–An NPs from copperas. The core–shell structures of the nanoparticles and chemical composition have been confirmed by TEM, XRD and FTIR techniques. Fluorescence Enhancement of Fe3O4@SiO2–An NPs with zinc ions was investigated by fluorescence emission spectra. The results indicated that the Fe3O4 NPs with a high purity (Total Fe 72.16 %) were obtained from copperas by chemical co-precipitation method and have a uniform spherical morphology with an average diameter of about 10 nm. The Fe3O4 NPs coated with silica nanoparticles were prepared, and an attempt had been made that the Fe3O4@SiO2 NPs were modified by 3-aminopropyltriethoxysilane and 9-anthranone successively. The recommended mole ratio of ethanol to water and the content of ammonia water added were 4:1 and 25 wt% respectively, which have an obviously effect on the combination of the final well-ordered MNPs with the amino functionalities and reactant components. The functionalized Fe3O4@SiO2–An NPs have a fluorescence property and this fluorescence effect can be enhanced with the Zn2+ ions attachment. Meanwhile, the saturated magnetization of Fe3O4@SiO2–An NPs was 37.8 emug?1 at 25 °C and this fluorescent material exhibited excellent magnetic properties. A new way was therefore provided for the comprehensive utilization of the unmarketable copperas. Moreover, the functionalized Fe3O4@SiO2–An NPs have a big potential in environmental decontamination, medical technology and biological science. 相似文献
139.
Houfu Lv Dr. Tianfu Liu Dr. Xiaomin Zhang Dr. Yuefeng Song Hiroaki Matsumoto Prof. Dr. Na Ta Chaobin Zeng Prof. Dr. Guoxiong Wang Prof. Dr. Xinhe Bao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16102-16107
In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal–oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4Sr0.6Co0.2Fe0.7Mo0.1O3−δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal–oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts. 相似文献
140.
Xiangyu Ma Yuyuan Bai Yongbo Song Qinzhen Li Ying Lv Hui Zhang Prof. Haizhu Yu Prof. Manzhou Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17387-17391
Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size-evolution principles. Reported here is the largest known FCC-based (FCC=face centered cubic) silver nanocluster, [Ag100(SC6H33,4F2)48(PPh3)8]−: the first all-octahedral symmetric nesting Ag nanocluster with a four-layered Ag6@Ag38@Ag48S24@Ag8S24P8 structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC-based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC-based Russian nesting doll model constitutes a new platform for the study of the size-evolution principles of Ag NCs. 相似文献