全文获取类型
收费全文 | 1274篇 |
免费 | 119篇 |
国内免费 | 92篇 |
专业分类
化学 | 990篇 |
晶体学 | 14篇 |
力学 | 42篇 |
综合类 | 3篇 |
数学 | 170篇 |
物理学 | 266篇 |
出版年
2024年 | 2篇 |
2023年 | 22篇 |
2022年 | 19篇 |
2021年 | 32篇 |
2020年 | 37篇 |
2019年 | 50篇 |
2018年 | 37篇 |
2017年 | 32篇 |
2016年 | 51篇 |
2015年 | 51篇 |
2014年 | 46篇 |
2013年 | 67篇 |
2012年 | 102篇 |
2011年 | 87篇 |
2010年 | 70篇 |
2009年 | 55篇 |
2008年 | 73篇 |
2007年 | 61篇 |
2006年 | 65篇 |
2005年 | 66篇 |
2004年 | 53篇 |
2003年 | 41篇 |
2002年 | 61篇 |
2001年 | 59篇 |
2000年 | 41篇 |
1999年 | 33篇 |
1998年 | 14篇 |
1997年 | 22篇 |
1996年 | 26篇 |
1995年 | 16篇 |
1994年 | 13篇 |
1993年 | 6篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 1篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1485条查询结果,搜索用时 31 毫秒
71.
Development of a solid‐phase microextraction fiber by the chemical binding of graphene oxide on a silver‐coated stainless‐steel wire with an ionic liquid as the crosslinking agent 下载免费PDF全文
Min Sun Juanjuan Feng Yanan Bu Huimin Duan Xiaojiao Wang Chuannan Luo 《Journal of separation science》2014,37(24):3691-3698
Graphene oxide was bonded onto a silver‐coated stainless‐steel wire using an ionic liquid as the crosslinking agent by a layer‐by‐layer strategy. The novel solid‐phase microextraction fiber was characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and Raman microscopy. A multilayer graphene oxide layer was closely coated onto the supporting substrate. The thickness of the coating was about 4 μm. Coupled with gas chromatography, the fiber was evaluated using five polycyclic aromatic hydrocarbons (fluorene, anthracene, fluoranthene, 1,2‐benzophenanthrene, and benzo(a)pyrene) as model analytes in direct‐immersion mode. The main conditions (extraction time, extraction temperature, ionic strength, and desorption time) were optimized by a factor‐by‐factor optimization. The as‐established method exhibited a wide linearity range (0.5–200 μg/L) and low limits of determination (0.05–0.10 μg/L). It was applied to analyze environmental water samples of rain and river water. Three kinds of the model analytes were quantified and the recoveries of samples spiked at 10 μg/L were in the range of 92.3–120 and 93.8–115%, respectively. The obtained results indicated the fiber was efficient for solid‐phase microextraction analysis. 相似文献
72.
Guang-Xin Yang Hui-Sheng Zhuang Han-Yu Chen Xian-Yin Ping Dan Bu 《Analytical and bioanalytical chemistry》2014,406(6):1693-1700
A functionalized gold-nanoparticle bio-barcode assay, based on real-time immuno-PCR (IPCR), was designed for the determination of 3,4,3',4'-tetrachlorobiphenyl (PCB77). 15 nm gold nanoparticles were synthesized, and modified with thiol-capped DNA and goat anti-rabbit IgG. The nanoparticle probes were used to replace antibody–DNA conjugate in the IPCR, and were fixed on the PCR tube wall via the immune reaction. Real-time PCR was performed to quantify the DNA signal directly. Under optimized conditions, the new method was used to detect PCB77 with a linearity range from 5 pg L?1 to 10 ng L?1, and the limit of detection (LOD) was 1.72 pg L?1. Real samples of Larimichthys polyactis, collected from the East China Sea, were analyzed. Recovery was from 82 % to 112 %, and the coefficient of variation (CV) was acceptable. The results were compared with GC–ECD, revealing that the method would be acceptable for providing rapid, semi-quantitative, and reliable test results for making environmental decisions. FIGURE
? 相似文献
73.
基于透明质酸构筑的药物递送载体及其应用 总被引:1,自引:0,他引:1
传统纳米药物控释载体主要通过细胞胞吞作用实现药物递送,其主要过程为被动靶向机制,因此会影响纳米载体在肿瘤组织的富集和治疗效果。近年来生物大分子透明质酸因其优异的水溶性、生物相容性、可降解性和肿瘤靶向性备受科研工作者青睐,已被广泛用于药物控释载体的构筑中,并成为靶向肿瘤治疗纳米载体领域的研究热点。本文根据透明质酸基纳米载体治疗机制的不同,从透明质酸基纳米载体在化疗、光热治疗、光动力治疗以及联合治疗的应用方面对其性能进行了总结和评述,并在此基础上展望了未来透明质酸基纳米治疗载体的研究方向和发展趋势。 相似文献
74.
Yanli Li Peiran Zhao Dr. Teng Gong Han Wang Dr. Xingwu Jiang Hui Cheng Dr. Yanyan Liu Dr. Yelin Wu Prof. Wenbo Bu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22726-22732
Redox homeostasis is one of the main reasons for reactive oxygen species (ROS) tolerance in hypoxic tumors, limiting ROS-mediated tumor therapy. Proposed herein is a redox dyshomeostasis (RDH) strategy based on a nanoplatform, FeCysPW@ZIF-82@CAT Dz, to disrupt redox homeostasis, and its application to improve ROS-mediated hypoxic tumor therapy. Once endocytosed by tumor cells, the catalase DNAzyme (CAT Dz) loaded zeolitic imidazole framework-82 (ZIF-82@CAT Dz) shell can be degraded into Zn2+ as cofactors for CAT Dz mediated CAT silencing and electrophilic ligands for glutathione (GSH) depletion under hypoxia, both of which lead to intracellular RDH and H2O2 accumulation. These “disordered” cells show reduced resistance to ROS and are effectively killed by ferrous cysteine-phosphotungstate (FeCysPW) induced chemodynamic therapy (CDT). In vitro and in vivo data demonstrate that the pH/hypoxia/H2O2 triple stimuli responsive nanocomposite can efficiently kill hypoxic tumors. Overall, the RDH strategy provides a new way of thinking about ROS-mediated treatment of hypoxic tumors. 相似文献
75.
Songhao Guo Yongsheng Zhao Kejun Bu Yongping Fu Hui Luo Mengting Chen Matthew P. Hautzinger Yingqi Wang Prof. Song Jin Prof. Wenge Yang Prof. Xujie Lü 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(40):17686-17692
A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)2(GA)Pb2I7 (HA=n-hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non-luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above-band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two-fold higher PL emission compared with the pristine (HA)2(GA)Pb2I7. 相似文献
76.
冠状病毒是一类广泛存在且对人及家畜具有严重危害的病原体,其中于2003年全球爆发的严重急性呼吸综合征病毒(SARS-CoV)以及2012年被发现并传播的中东呼吸综合征病毒(MERS-CoV)给人们的生命健康以及全球经济造成了严重威胁以及重大损失,特别是2019年末爆发的新型冠状病毒(SARS-CoV-2),截至目前为止已经造成了几百万的感染病例以及几十万人的死亡。可以看出,冠状病毒具有较高的传播性以及较高的致死率,时刻威胁着人们的健康安全,但是针对冠状病毒的感染目前还没有批准上市的有效药物,也没有用于预防的疫苗。本文围绕目前关于冠状病毒的潜在成药性靶点,详细介绍了针对这些靶点的具有代表性的抑制剂的结构设计及其化学合成方法,以期为目前抗冠状病毒药物的研发提供一些参考。 相似文献
77.
The tittle compounds have directly been synthesized by one-step reaction of two different aldehydes in the presence of ammonia in good to excellent yields. 相似文献
78.
Lukáš Bučinský Stanislav Biskupič Dylan Jayatilaka 《Theoretical chemistry accounts》2011,129(2):181-197
The 2nd order Douglas-Kroll-Hess (DKH2) and the Infinite Order Two Component (IOTC) radial distributions of electron density
of canonical Hartree-Fock (HF) orbitals of radon atom are presented. Furthermore, the total electron density is revisited.
The picture change error (PCE) correction is investigated by analytical means. The point charge model of nucleus and the Gaussian
nucleus model are employed. The basis set is extrapolated by means of including tight s and also p Gaussians within the original triple zeta basis set. It is found that the DKH1 PCE corrected DKH2 total electron and s orbital contact densities are negative for the point charge model of nucleus if tight enough s Gaussians are included in the basis set. It is shown that this failure is caused due to the missing terms of the second order
Douglas-Kroll transformation for the DKH2 electron density. PCE is found the most striking in the DKH2/IOTC electron density
of s orbitals close to the nucleus. The radial distributions of the 2-component p
1/2 orbital densities are considerably affected by PCE at the nucleus as well. Furthermore, the PCE corrected DKH2/IOTC scalar
p orbital densities have a non-zero value of electron density at nucleus and can be considered as an spin-orbit (SO) average
of the p
1/2 and p
3/2 orbitals. The d and f orbitals are affected by PCE in the vicinity of the nucleus only little. The PCE corrected DKH2 and IOTC radial distributions
of orbital densities are nodeless, which is completely in agreement with the radial distribution of the analytic or numeric
DCH orbital densities. 相似文献
79.
Laibin Zhang Huifang Li Jilai Li Xiaohua Chen Yuxiang Bu 《Journal of computational chemistry》2010,31(4):825-836
A comprehensive theoretical study of electronic transitions of naphtho‐homologated base analogs, namely, yy‐T , yy‐C , yy‐A , and yy‐G , was performed. The nature of the low‐lying excited states is discussed, and the results are compared with those from experiment and also with those of y‐bases. Geometrical characteristics of the lowest excited singlet ππ* and nπ* states were explored using the CIS method, and the effects of methanol solution and paring with their complementary natural bases on the relevant absorption and emission spectra of these modified bases were examined. The calculated excitation and emission energies agree well with the measured data, where experimental results are available. In methanol solution, the fluorescence from yy‐A and yy‐G would be expected to occur around 539 and 562 nm, respectively, suggesting that yy‐A is a green‐colored fluorophore, whereas yy‐G is a yellow‐colored fluorophore. The methanol solution was found to red‐shift both the absorption and emission maxima of yy‐A , yy‐T , and yy‐C , but blue‐shift those for yy‐G . Generally, though base pairing has no significant effects on the absorption and fluorescence maxima of yy‐A , yy‐C , and yy‐T , it blue‐shifts those for yy‐G . © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 相似文献
80.