全文获取类型
收费全文 | 1696篇 |
免费 | 315篇 |
国内免费 | 163篇 |
专业分类
化学 | 1098篇 |
晶体学 | 13篇 |
力学 | 88篇 |
综合类 | 30篇 |
数学 | 223篇 |
物理学 | 722篇 |
出版年
2024年 | 2篇 |
2023年 | 33篇 |
2022年 | 28篇 |
2021年 | 43篇 |
2020年 | 76篇 |
2019年 | 73篇 |
2018年 | 62篇 |
2017年 | 42篇 |
2016年 | 79篇 |
2015年 | 70篇 |
2014年 | 86篇 |
2013年 | 111篇 |
2012年 | 141篇 |
2011年 | 151篇 |
2010年 | 90篇 |
2009年 | 94篇 |
2008年 | 85篇 |
2007年 | 94篇 |
2006年 | 100篇 |
2005年 | 79篇 |
2004年 | 77篇 |
2003年 | 48篇 |
2002年 | 46篇 |
2001年 | 30篇 |
2000年 | 26篇 |
1999年 | 46篇 |
1998年 | 40篇 |
1997年 | 25篇 |
1996年 | 36篇 |
1995年 | 31篇 |
1994年 | 29篇 |
1993年 | 27篇 |
1992年 | 24篇 |
1991年 | 24篇 |
1990年 | 19篇 |
1989年 | 25篇 |
1988年 | 22篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1976年 | 4篇 |
1973年 | 4篇 |
1930年 | 1篇 |
排序方式: 共有2174条查询结果,搜索用时 31 毫秒
1.
Transport in Porous Media - Membrane filtration of feed containing multiple species of particles is a common process in the industrial setting. In this work, we propose a model for filtration of a... 相似文献
2.
The aim of this work was to further investigate the anticancer potential of Juglans mandshurica Maxim, including the separation of active constituents and their anti-proliferative effects with underlying mechanism of action. Five alkaloids (1–5) were isolated from the bark of J. mandshurica. Among them, 1 showed the highest cytotoxic activities against Hep3B and HepG2 cells with an IC50 values of 61.80 and 56.24 μM, respectively. Therefore, the cellular mechanism involved 1 was subsequently studied. Our results showed that 1 markedly caused apoptosis and autophagy, but without cell cycle arrest in HepG2 cells. Interestingly, only autophagic cell death was induced in 1-treated Hep3B cells. It is concluded that the isolated alkaloids exerted a certain anti-hepatoma potential, and our results may provide a basis for the further investigation of the alkaloids extracted from J. mandshurica. 相似文献
3.
Rational Design of an Ultrasensitive and Highly Selective Chemodosimeter by a Dual Quenching Mechanism for Cysteine Based on a Facile Michael‐Transcyclization Cascade Reaction 下载免费PDF全文
Xiangmin Li Yongjun Zheng Hongjuan Tong Rui Qian Dr. Lin Zhou Prof. Dr. Guixia Liu Prof. Dr. Yun Tang Prof. Dr. Hao Li Prof. Dr. Kaiyan Lou Prof. Dr. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9247-9256
Differentiation of biologically important thiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) is still a challenging task. Herein, we present a novel fluorescent chemodosimeter capable of selectively detecting Cys over other biothiols including Hcy and GSH and other amino acids by a facile thiol‐Michael addition/transcyclization rearrangement cascade click process. The unique transcyclization step is critical for the selectivity as a result of the kinetically favorable formation of a six‐membered ring with the Cys Michael adduct. Moreover, the probe adopts a distinctive dual quenching mechanism—photoinduced electron transfer (PET) and photoinduced intramolecular charge transfer (ICT) to deliver a drastic turn‐on fluorescence response only at the Cys‐selective transcylization step. The judicious selection of strong electron‐withdrawing naphthalimide fluorophore with maleimide group enhances the electrophilicity and thus reactivity for the cascade process leading to fast detection and ultrasensitivity with a detection limit of 2.0 nm (S/N=3). The probe has demonstrated its practical utility potential in Cys imaging in live cells. 相似文献
4.
Guo Min Lou Deng-Ji Shao Lin-Jiao Li Yin-Fei Liang Ying-Zhong Yang Xiao-Yan 《Chemistry of Natural Compounds》2022,58(4):656-658
Chemistry of Natural Compounds - A new chamigrane sesquiterpene, antroalbol F (1), along with one known compound, acaciicolinol C (2), were isolated from cultures of the fungus Antrodiella... 相似文献
5.
Megan L. Qualls Dr. Jinchao Lou Dillon P. McBee Prof. Joshua A. Baccile Prof. Michael D. Best 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(45):e202201164
Liposomes are effective therapeutic delivery nanocarriers due to their ability to encapsulate and enhance the pharmacokinetic properties of a wide range of therapeutics. Two primary areas in which improvement is needed for liposomal drug delivery is to enhance the ability to infiltrate cells and to facilitate derivatization of the liposome surface. Herein, we report a liposome platform incorporating a cyclic disulfide lipid (CDL) for the dual purpose of enhancing cell entry and functionalizing the liposome membrane through thiol-disulfide exchange. In order to accomplish this, CDL-1 and CDL-2 , composed of lipoic acid (LA) or asparagusic acid (AA) appended to a lipid scaffold, were designed and synthesized. A fluorescence-based microplate immobilization assay was implemented to show that these compounds enable convenient membrane decoration through reaction with thiol-functionalized small molecules. Additionally, fluorescence microscopy experiments indicated dramatic enhancements in cellular delivery when CDLs were incorporated within liposomes. These results demonstrate that multifunctional CDLs serve as an exciting liposome system for surface decoration and enhanced cellular delivery. 相似文献
6.
以钨酸(H2WO4)为钨前驱体,十二烷胺(DDA)为模板剂,利用模板剂的结构导向功能,合成了比表面积为57.3 m2·g-1的介孔三氧化钨(DDA-WO3),是未用DDA制备的非介孔WO3(H2WO4-WO3)的2.35倍。X射线衍射(XRD)结果表明,400 ℃下煅烧的DDA-WO3是具有单斜晶型结晶孔壁的无序介孔结构。此外,400~550 ℃下煅烧的DDA-WO3的结晶度均高于同条件的H2WO4-WO3。400 ℃下的DDA-WO3/FTO(掺氟氧化锡)在1.0 V的Ag/AgCl偏压作用下,可以产生0.18 mA·cm-2的饱和光电流,是H2WO4-WO3/FTO(0.06 mA·cm-2)的3倍。增强的光电化学(PEC)活性主要因为DDA-WO3/FTO的大表面积降低了低结晶度对PEC性能的不利影响,成为影响PEC活性的主要因素。500 ℃煅烧导致了DDA-WO3/FTO介孔结构的坍塌,但高的结晶度仍然保持其优越的PEC催化活性。 相似文献
7.
Huadong Yuan Prof. Jianwei Nai Dr. Yongjin Fang Gongxun Lu Prof. Xinyong Tao Prof. Xiong Wen Lou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):15973-15977
The growth of Li dendrites hinders the practical application of lithium metal anodes (LMAs). In this work, a hollow nanostructure, based on hierarchical MoS2 coated hollow carbon particles preloaded with sulfur (C@MoS2/S), was designed to modify the LMA. The C@MoS2 hollow nanostructures serve as a good scaffold for repeated Li plating/stripping. More importantly, the encapsulated sulfur could gradually release lithium polysulfides during the Li plating/stripping, acting as an effective additive to promote the formation of a mosaic solid electrolyte interphase layer embedded with crystalline hybrid lithium-based components. These two factors together effectively suppress the growth of Li dendrites. The as-modified LMA shows a high Coulombic efficiency of 98 % over 500 cycles at the current density of 1 mA cm−2. When matched with a LiFePO4 cathode, the assembled full cell displays a highly improved cycle life of 300 cycles, implying the feasibility of the proposed LMA. 相似文献
8.
Dr. Xue Feng Lu Prof. Bao Yu Xia Prof. Shuang-Quan Zang Prof. Xiong Wen Lou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4662-4678
In view of the clean and sustainable energy, metal–organic frameworks (MOFs) based materials, including pristine MOFs, MOF composites, and their derivatives are emerging as unique electrocatalysts for oxygen reduction reaction (ORR). Thanks to their tunable compositions and diverse structures, efficient MOF-based materials provide new opportunities to accelerate the sluggish ORR at the cathode in fuel cells and metal–air batteries. This Minireview first provides some introduction of ORR and MOFs, followed by the classification of MOF-based electrocatalysts towards ORR. Recent breakthroughs in engineering MOF-based ORR electrocatalysts are highlighted with an emphasis on synthesis strategy, component, morphology, structure, electrocatalytic performance, and reaction mechanism. Finally, some current challenges and future perspectives for MOF-based ORR electrocatalysts are also discussed. 相似文献
9.
Mathias B. Danielsen Dr. Chenguang Lou Jolanta Lisowiec-Wachnicka Prof. Anna Pasternak Per T. Jørgensen Prof. Jesper Wengel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1368-1379
Off-target effects remain a significant challenge in the therapeutic use of gapmer antisense oligonucleotides (AONs). Over the years various modifications have been synthesized and incorporated into AONs, however, precise control of RNase H-induced cleavage and target sequence selectivity has yet to be realized. Herein, the synthesis of the uracil and cytosine derivatives of a novel class of 2′-deoxy-2′-fluoro-3′-C-hydroxymethyl-β-d -lyxo-configured nucleotides has been accomplished and the target molecules have been incorporated into AONs. Experiments on exonuclease degradation showed improved nucleolytic stability relative to the unmodified control. Upon the introduction of one or two of the novel 2′-fluoro-3′-C-hydroxymethyl nucleotides as modifications in the gap region of a gapmer AON was associated with efficient RNase H-mediated cleavage of the RNA strand of the corresponding AON:RNA duplex. Notably, a tailored single cleavage event could be engineered depending on the positioning of a single modification. The effect of single mismatched base pairs was scanned along the full gap region demonstrating that the modification enables a remarkable specificity of RNase H cleavage. A cell-based model system was used to demonstrate the potential of gapmer AONs containing the novel modification to mediate gene silencing. 相似文献
10.
Zemin Sun Mengwei Yuan Kefan Shi Yuhui Liu Di Wang Dr. Caiyun Nan Dr. Huifeng Li Prof. Genban Sun Prof. Xiaojing Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7244-7249
NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni2+ to the surroundings of Li+, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm−2, which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO2. Reasonable intercalation adjustment effectively activates laminated Ni2+ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials. 相似文献