全文获取类型
收费全文 | 17029篇 |
免费 | 2703篇 |
国内免费 | 1924篇 |
专业分类
化学 | 12366篇 |
晶体学 | 191篇 |
力学 | 1178篇 |
综合类 | 142篇 |
数学 | 2049篇 |
物理学 | 5730篇 |
出版年
2024年 | 38篇 |
2023年 | 323篇 |
2022年 | 360篇 |
2021年 | 513篇 |
2020年 | 625篇 |
2019年 | 650篇 |
2018年 | 509篇 |
2017年 | 534篇 |
2016年 | 741篇 |
2015年 | 741篇 |
2014年 | 924篇 |
2013年 | 1138篇 |
2012年 | 1520篇 |
2011年 | 1552篇 |
2010年 | 1060篇 |
2009年 | 941篇 |
2008年 | 1091篇 |
2007年 | 980篇 |
2006年 | 976篇 |
2005年 | 793篇 |
2004年 | 601篇 |
2003年 | 545篇 |
2002年 | 546篇 |
2001年 | 460篇 |
2000年 | 345篇 |
1999年 | 364篇 |
1998年 | 289篇 |
1997年 | 268篇 |
1996年 | 299篇 |
1995年 | 236篇 |
1994年 | 207篇 |
1993年 | 161篇 |
1992年 | 170篇 |
1991年 | 179篇 |
1990年 | 130篇 |
1989年 | 124篇 |
1988年 | 81篇 |
1987年 | 71篇 |
1986年 | 81篇 |
1985年 | 60篇 |
1984年 | 54篇 |
1983年 | 46篇 |
1982年 | 32篇 |
1981年 | 31篇 |
1980年 | 29篇 |
1978年 | 24篇 |
1977年 | 25篇 |
1976年 | 23篇 |
1974年 | 20篇 |
1973年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
P. Müller‐Buschbaum J. Perlich M. M. Abul Kashem L. Schulz S. V. Roth Y. J. Cheng J. S. Gutmann 《固体物理学:研究快报》2007,1(3):119-121
Nanostructures formed in a titanium dioxide (TiO2)–poly(styrene)‐block‐poly(ethyleneoxide) nanocomposite film on top of fluor‐doped tin oxide (FTO) layers are investigated. The combinatorial approach is based on probing a wedge‐shaped FTO‐gradient with grazing incidence small angle X‐ray scattering (GISAXS) in combination with a moderate micro‐focus X‐ray beam. The characteristic lateral length is given by adjacent nanowire‐shaped TiO2 regions. It decreases from 200 nm on the thick FTO layer to 90 nm on the bare glass surface.
992.
A cesium 6S(1/2) --> 8S(1/2) two-photon-transition (TPT)-stabilized 822.5 nm diode laser is reported for the first time to our knowledge. Allan deviation of 4.4 x 10(-13) (60 s) was achieved, and the possible systematic errors were evaluated as smaller than 2 kHz. We demonstrate that the cesium TPT-stabilized diode laser could be a reliable frequency reference at 822.5 nm wavelength. 相似文献
993.
Fan X Medved M Karczmar GS Yang C Foxley S Arkani S Recant W Zamora MA Abe H Newstead GM 《Magnetic resonance imaging》2007,25(5):593-603
The purpose of this study was to test whether an empirical mathematical model (EMM) of dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) can distinguish between benign and malignant breast lesions. A modified clinical protocol was used to improve the sampling of contrast medium uptake and washout. T(1)-weighted DCE magnetic resonance images were acquired at 1.5 T for 22 patients before and after injection of Gd-DTPA. Contrast medium concentration as a function of time was calculated over a small region of interest containing the most rapidly enhancing pixels. Then the curves were fitted with the EMM, which accurately described contrast agent uptake and washout. Results demonstrate that benign lesions had uptake (P<2.0 x 10(-5)) and washout (P<.01) rates of contrast agent significantly slower than those of malignant lesions. In addition, secondary diagnostic parameters, such as time to peak of enhancement, enhancement slope at the peak and curvature at the peak of enhancement, were derived mathematically from the EMM and expressed in terms of primary parameters. These diagnostic parameters also effectively differentiated benign from malignant lesions (P<.03). Conventional analysis of contrast medium dynamics, using a subjective classification of contrast medium kinetics in lesions as "washout," "plateau" or "persistent" (sensitivity=83%, specificity=50% and diagnostic accuracy=72%), was less effective than the EMM (sensitivity=100%, specificity=83% and diagnostic accuracy=94%) for the separation of benign and malignant lesions. In summary, the present research suggests that the EMM is a promising alternative method for evaluating DCE-MRI data with improved diagnostic accuracy. 相似文献
994.
Kai‐Hsuan Hsieh Chih‐Ying Hsu I‐Ju Hung Chih‐Ling Yeh Yau‐Hung Chen Chien‐Chung Cheng 《中国化学会会志》2021,68(1):34-38
Liposomes composed of cell‐penetrating peptide derivatives increased transport across the cell membrane. Conjugating rhodamine to a cell‐penetrating peptide increased the toxicity of rhodamine in E. coli and zebrafish embryos. A similar total protein inhibition pattern with different intensities, indicating that the interaction pathways of the rho‐KTTKS‐CONH2 monomer and liposomes were the same. It suggests that the rho‐KTTKS‐CONH2 liposomes showed higher toxicity because better transport across the cell membrane increased the effective concentration inside cells. The staining of zebrafish embryos using rho‐KTTKS‐CONH2 liposomes showed a longer retention time, suggesting that it can penetrate deeper tissues or organs in zebrafish. 相似文献
995.
Chromatographia - In this study, a poly(glycidyl methacrylate) nanoparticle (PGMA NP)-coated column system with two antibiotics as selector was constructed for enantioseparation. The PGMA NP... 相似文献
996.
Hui Xie Yanyan Niu Ying Deng Hui Cheng Chengxiang Ruan Guangjiu Li Wei Sun 《中国化学会会志》2021,68(1):114-120
In this paper, an electrochemical aptamer sensor was proposed for the highly sensitive detection of mercury ion (Hg2+). Carbon nanofiber (CNF) was prepared by electrospinning and high‐temperature carbonization, which was used for the loading of platinum nanoparticles (PtNPs) by the hydrothermal method. The Pt@CNF nanocomposite was modified on the surface of carbon ionic liquid electrode (CILE) to obtain Pt@CNF/CILE, which was further decorated by gold nanoparticles (AuNPs) through electrodeposition to get Au/Pt@CNF/CILE. Self‐assembling of the thiol‐based aptamer was further realized by the formation of Au‐S bond to get an electrochemical aptamer sensor (Aptamer/Au/Pt@CNF/CILE). Due to the specific binding of aptamer probe to Hg2+ with the formation of T‐Hg2+‐T structure, a highly sensitive quantitative detection of Hg2+ could be achieved by recording the changes of current signal after reacting with Hg2+ within the concentration range from 1.0 × 10?15 mol/L to 1.0 × 10?6 mol/L and the detection limit of 3.33 × 10?16 mol/L (3σ). Real water samples were successfully analyzed by this method. 相似文献
997.
Rui-Jia Chen Jun-Jie Wang Li Han Yu-Cheng Gu Zhi-Ping Xu Jia-Gao Cheng Xu-Sheng Shao Xiao-Yong Xu Zhong Li 《Journal of heterocyclic chemistry》2021,58(7):1429-1436
A series of diamide derivatives containing α-amino acids were designed and synthesized. These compounds were evaluated for their insecticidal activities against Plutella xylostella, Mythimna separate, Myzus persicae, and Tetranychus cinnabarinus. Most of the title compounds containing an l -phenylglycine skeleton were endowed with good activities at the concentration of 500 mg·L−1. Compounds ( R)-A6 showed a potential value for further optimization as an insecticidal lead with the LC50 value of 86.8 mg·L−1. 相似文献
998.
Bumhee Lim Yangyang Cheng Takehiro Kato Anh-Tuan Pham Eliott Le Du Abhaya Kumar Mishra Elija Grinhagena Dimitri Moreau Naomi Sakai Jerome Waser Stefan Matile 《Helvetica chimica acta》2021,104(8):e2100085
Thiol-mediated uptake is emerging as method of choice to penetrate cells. This study focuses on irreversible covalent inhibitors of thiol-mediated uptake. High-content high-throughput screening of the so far largest collection of hypervalent iodine reagents affords inhibitors that are more than 250 times more active than Ellman’s reagent and rival the best dynamic covalent inhibitors. Comparison with other irreversible reagents reveals that inhibition within one series follows reactivity, whereas inhibition across series deviates from reactivity. These trends support that molecular recognition, besides dynamic covalent exchange, contributes significantly to thiol-mediated uptake. The most powerful inhibitors besides the best hypervalent iodine reagents were Fukuyama’s nosyl protecting group and super-cinnamaldehydes that have been introduced as irreversible activators of the pain receptor TRPA1. Considering that several viruses use different forms of thiol-mediated uptake to enter cells, the identification of new irreversible inhibitors of thiol-mediated uptake is of general interest for the discovery of new antivirals. 相似文献
999.
柔性电子作为新兴的研究热点, 涉及材料、 化学、 物理等多个基础学科的交叉, 以及在生物医用、 可穿戴设备及人工智能等多个领域的应用. 柔性电子设备的制造加工过程中会用到弹性基底、 导电层、 功能层等多种性质各异的材料, 其互相之间的整合受到它们表面性质和界面结合力的限制; 器件的功能、 可靠性、 对环境的敏感性等也受到了器件表界面性质的影响; 因此, 对材料和器件表界面的处理在柔性电子学中具有重要作用. 本文对柔性电子学中常用的表界面化学过程分为3大类进行介绍: 表面电化学过程, 基于特定化合物反应产生的电流制备电化学传感器, 利用电流/电压控制表面负载化合物; 表面修饰, 通过表面改性提高材料的加工性能, 共价修饰分子层或其它材料赋予器件特殊功能性质或保护层; 不同材料之间的界面连接, 通过共价连接或化学反应辅助的物理交联实现不同材料的结合, 提高柔性器件的稳定性, 实现柔性设备的整合. 对各应用进行总结和举例后, 讨论了存在的问题, 并对未来的发展方向及前景进行了展望. 相似文献
1000.
DNA酶中的G-四链体-血红素(G4-hemin)DNA酶结构具有较高的设计性和化学稳定性,因此格外受研究者关注.G-平面作为辅酶因子hemin的结合位点,不仅提供大π平面与hemin结合,而且其平面上的G碱基还可以充当近端配位基团与hemin进行配位.因此,研究G-平面完整性在G4-DNA酶体系中的作用具有重要意义.本文设计了一系列含有空位的G4(G-vacancy,GV)及G-三链体,通过“鸟嘌呤类似物插入”策略实现G-平面完整性以及DNA酶催化活性的恢复.结果表明,末端G-平面完整性是G4-DNA酶具有催化活性的必要条件,且其能够充当近端配位基团与末端碱基协同激活G4-DNA酶.考虑到hemin会选择性地结合于G4的3’-端平面,本文以含有3’-端空位的G4以及G-三链体为模型进行DNA酶的构建.结果表明,相较于末端完整的G4-hemin DNA酶,末端不完整的G4结构所形成的DNA酶催化活性很低.为了进一步验证该平面完整性的重要性,本文提出了“鸟嘌呤衍生物插入”策略,即将鸟嘌呤衍生物(无环鸟苷和鸟苷)插入G-空位以恢复G-平面的完整性.通过圆二色光谱和紫外熔解实验,发现末端平面完整性的缺失会使圆二色特征峰信号和G4结构热稳定性下降,而鸟嘌呤碱基类似物的加入则可以使特征峰信号以及热稳定性得到一定程度的恢复,表明鸟嘌呤碱基类似物的加入确实使G-平面完整性得到恢复.与此同时,随着鸟嘌呤碱基类似物浓度的增加,G4-hemin DNA酶活性逐渐增强,最终恢复至与完整G4一样的活性.在以G-三链体为模型的实验中,本文通过另一条富G序列与G-三链体进行结合,形成复合的(3+1)型G4结构,最终实现了DNA酶活性的恢复.同时,在3’-G-平面末端增加了激活碱基(dA或dTC),结果表明,即使G-平面不完整,末端碱基依旧能够激活DNA酶,但酶活性整体弱于完整G4时的活性.同样,“鸟嘌呤衍生物插入”策略可以使酶活性得到恢复.本文系列实验充分说明了末端碱基可与G-平面形成协同作用,与hemin的铁中心共同形成六配位关系,加速催化中间体生成,进而增强催化活性.有趣的是,通过设计Holliday junction结构研究发现,“鸟嘌呤衍生物插入”策略仅适用于平行G4结构.G-空位的存在不仅降低了G4结构的稳定性,而且降低了其与hemin间的亲和力,二者均是造成G4-DNA酶催化能力下降的主要因素.总之,本文证明了3’-端G-平面的完整性是G4-DNA酶实现其催化能力必不可少的因素,对理解末端G-平面在G4-DNA酶中的作用具有重要的参考意义. 相似文献