全文获取类型
收费全文 | 10076篇 |
免费 | 1351篇 |
国内免费 | 1384篇 |
专业分类
化学 | 9750篇 |
晶体学 | 80篇 |
力学 | 24篇 |
综合类 | 90篇 |
数学 | 5篇 |
物理学 | 2862篇 |
出版年
2024年 | 8篇 |
2023年 | 98篇 |
2022年 | 226篇 |
2021年 | 358篇 |
2020年 | 404篇 |
2019年 | 455篇 |
2018年 | 340篇 |
2017年 | 382篇 |
2016年 | 539篇 |
2015年 | 509篇 |
2014年 | 539篇 |
2013年 | 960篇 |
2012年 | 808篇 |
2011年 | 615篇 |
2010年 | 599篇 |
2009年 | 669篇 |
2008年 | 633篇 |
2007年 | 689篇 |
2006年 | 632篇 |
2005年 | 546篇 |
2004年 | 468篇 |
2003年 | 389篇 |
2002年 | 279篇 |
2001年 | 189篇 |
2000年 | 198篇 |
1999年 | 151篇 |
1998年 | 154篇 |
1997年 | 151篇 |
1996年 | 116篇 |
1995年 | 148篇 |
1994年 | 114篇 |
1993年 | 103篇 |
1992年 | 79篇 |
1991年 | 67篇 |
1990年 | 43篇 |
1989年 | 31篇 |
1988年 | 29篇 |
1987年 | 36篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
91.
本文建立了一种快速灵敏检测水中硫离子的新方法。该方法利用聚胸腺嘧啶单链DNA保护的铜纳米簇为荧光探针。以聚胸腺嘧啶单链DNA为模板制备了具有荧光性质的铜纳米簇,当加入S2-后,铜纳米簇荧光显著猝灭。铜纳米簇荧光猝灭量与S2-浓度在0.125~8μmol/L范围内有良好的线性,检测限为22nmol/L。该方法对S2-有较好的选择性,实际样品检测结果显示回收率良好,说明该方法可以用于实际水样中S2-的检测。由于聚胸腺嘧啶单链DNA为模板制备的铜纳米簇制备过程简单快速,可在5min内完成,使得检测时间大大缩短。 相似文献
92.
Haiqiao Wang Shasha Song Prof. Dr. Jingcheng Hao Prof. Dr. Aixin Song 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(34):12194-12201
The gelation behavior of lithocholate (LC?) with different metal ions in water was investigated. The microstructures of hydrogels were determined to be three‐dimensional (3D) networks of fibrous aggregates. The formation of fibrils was speculated to be mainly driven by the coordination between carboxylate of LC? and metal ions, accompanied by the assistance of noncovalent interactions such as electrostatic and hydrophobic interactions. The hydrogels, which can maintain the mechanical strength at higher temperature, exhibit thermal stability. Their gelation capability was enhanced with the increase in acidity. The hydrogels of LC? and Cu2+ mixtures served as the precursors for producing network nanostructures of CuS nanoparticles. These new CuS networks exhibit high fluorescence quenching ability and can act as an effective fluorescent sensing platform for ssDNA detection. 相似文献
93.
Postfunctionalization of BN‐Embedded Polycyclic Aromatic Compounds for Fine‐Tuning of Their Molecular Properties 下载免费PDF全文
Dr. Xiao‐Ye Wang Dong‐Chu Yang Fang‐Dong Zhuang Jia‐Jie Liu Dr. Jie‐Yu Wang Prof. Jian Pei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(24):8867-8873
New BN‐embedded, thiophene‐fused, polycyclic aromatic compounds with planar geometry were designed and synthesized. The molecules showed excellent stability and chemical robustness. Postfunctionalization on this skeleton was demonstrated with a series of electrophilic bromination, palladium‐catalyzed cross‐coupling, and Knoevenagel condensation reactions. The π skeleton remained intact during these late‐stage transformations. The optical and electronic properties have been well tuned through incorporation of electron‐rich and ‐deficient groups on the backbone. This work shows the great advantage of the postfunctionalization strategy on BN‐containing polycyclic aromatic compounds for fast diversification and materials screening. 相似文献
94.
Dr. Thomas Schwarze Janine Riemer Dr. Sascha Eidner Prof. Hans‐Jürgen Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11306-11310
A highly K+‐selective two‐photon fluorescent probe for the in vitro monitoring of physiological K+ levels in the range of 1–100 mM is reported. The two‐photon excited fluorescence (TPEF) probe shows a fluorescence enhancement (FE) by a factor of about three in the presence of 160 mM K+, independently of one‐photon (OP, 430 nm) or two‐photon (TP, 860 nm) excitation and comparable K+‐induced FEs in the presence of competitive Na+ ions. The estimated dissociation constant (Kd) values in Na+‐free solutions (KdOP=(28±5) mM and KdTP=(36±6) mM ) and in combined K+/Na+ solutions (KdOP=(38±8) mM and KdTP=(46±25) mM ) reflecting the high K+/Na+ selectivity of the fluorescent probe. The TP absorption cross‐section (σ2PA) of the TPEF probe+160 mM K+ is 26 GM at 860 nm. Therefore, the TPEF probe is a suitable tool for the in vitro determination of K+. 相似文献
95.
Supramolecular Fluorescent Nanoparticles Constructed via Multiple Non‐Covalent Interactions for the Detection of Hydrogen Peroxide in Cancer Cells 下载免费PDF全文
Xuan Wei Ruijiao Dong Dali Wang Tianyu Zhao Yongsheng Gao Patrick Duffy Prof. Xinyuan Zhu Dr. Wenxin Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11427-11434
Overabundance of hydrogen peroxide originating from environmental stress and/or genetic mutation can lead to pathological conditions. Thus, the highly sensitive detection of H2O2 is important. Herein, supramolecular fluorescent nanoparticles self‐assembled from fluorescein isothiocyanate modified β‐cyclodextrin (FITC‐β‐CD)/rhodamine B modified ferrocene (Fc‐RB) amphiphile were prepared through host–guest interaction between FITC‐β‐CD host and Fc‐RB guest for H2O2 detection in cancer cells. The self‐assembled nanoparticles based on a combination of multiple non‐covalent interactions in aqueous medium showed high sensitivity to H2O2 while maintaining stability under physiological condition. Owing to the fluorescence resonance energy transfer (FRET) effect, addition of H2O2 led to obvious fluorescence change of nanoparticles from red (RB) to green (FITC) in fluorescent experiments. In vitro study showed the fluorescent nanoparticles could be efficiently internalized by cancer cells and then disrupted by endogenous H2O2, accompanying with FRET from “on” to “off”. These supramolecular fluorescent nanoparticles constructed via multiple non‐covalent interactions are expected to have potential applications in diagnosis and imaging of diseases caused by oxidative stresses. 相似文献
96.
New approach for producing fluorescent gold nanoparticles: Poly(ethylene oxide) homopolymers as reductants in the micelles of amphiphilic fluorosilicone‐containing block copolymers 下载免费PDF全文
Jiawen Zhang Lingmin Yi Kai Xu Jing Li Dongzhi Lai 《Journal of polymer science. Part A, Polymer chemistry》2015,53(20):2320-2325
97.
Dr. Graeme J. Stasiuk Dr. Florencia Minuzzi Dr. Myra Sae‐Heng Charlotte Rivas Dr. Hans‐Paul Juretschke Dr. Lorenzo Piemonti Dr. Peter R. Allegrini Dr. Didier Laurent Andrew R. Duckworth Prof. Andrew Beeby Prof. Guy A. Rutter Prof. Nicholas J. Long 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5023-5033
Despite the contribution of changes in pancreatic β‐cell mass to the development of all forms of diabetes mellitus, few robust approaches currently exist to monitor these changes prospectively in vivo. Although magnetic‐resonance imaging (MRI) provides a potentially useful technique, targeting MRI‐active probes to the β cell has proved challenging. Zinc ions are highly concentrated in the secretory granule, but they are relatively less abundant in the exocrine pancreas and in other tissues. We have therefore developed functional dual‐modal probes based on transition‐metal chelates capable of binding zinc. The first of these, Gd ?1 , binds ZnII directly by means of an amidoquinoline moiety (AQA), thus causing a large ratiometric Stokes shift in the fluorescence from λem=410 to 500 nm with an increase in relaxivity from r1=4.2 up to 4.9 mM ?1 s?1. The probe is efficiently accumulated into secretory granules in β‐cell‐derived lines and isolated islets, but more poorly by non‐endocrine cells, and leads to a reduction in T1 in human islets. In vivo murine studies of Gd ?1 have shown accumulation of the probe in the pancreas with increased signal intensity over 140 minutes. 相似文献
98.
Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs 下载免费PDF全文
Dr. D. Suresh Dr. Clara S. B. Gomes Patrícia S. Lopes Dr. Cláudia A. Figueira Bruno Ferreira Prof. Pedro T. Gomes Dr. Roberto E. Di Paolo Prof. António L. Maçanita Prof. M. Teresa Duarte Dr. Ana Charas Prof. Jorge Morgado Diogo Vila‐Viçosa Prof. Maria José Calhorda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9133-9149
New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC4H3‐C(H)?N)2‐C6H4 ( 2 ), 1,3‐(HNC4H3‐C(H)?N)2‐C6H4 ( 3 ), 1,4‐(HNC4H3‐C(H)?N)2‐C6H4 ( 4 ), 4,4′‐(HNC4H3‐C(H)?N)2‐(C6H4‐C6H4) ( 5 ), 1,5‐(HNC4H3C‐(H)?N)2‐C10H6 ( 6 ), 2,6‐(HNC4H3C‐(H)?N)2‐C10H6 ( 7 ), 2,6‐(HNC4H3C‐(H)?N)2‐C14H8 ( 8 )) and star‐shaped (1,3,5‐(HNC4H3‐C(H)?N‐1,4‐C6H4)3‐C6H3 ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph2B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 10 ), Ph2B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 11 ), Ph2B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh2 ( 12 ), Ph2B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 13 ), Ph2B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 14 ), Ph2B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh2 ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh2)3 ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C6H5)3. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m?2, for single layer devices, increasing to 4400 cd m?2 when a hole‐transporting layer is used. 相似文献
99.
Vanessa C. Lussini Dr. James P. Blinco Dr. Kathryn E. Fairfull‐Smith Prof. Steven E. Bottle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18258-18268
Novel profluorescent mono‐ and bis‐isoindoline nitroxides linked to napthalimide and perylene diimide structural cores are described. These nitroxide‐fluorophore probes display strongly suppressed fluorescence in comparison to their corresponding non‐radical diamagnetic methoxyamine derivatives. The perylene‐based probe possessing two isoindoline systems tethered through ethynyl linkages was shown to be the most photostable in solution, demonstrating significantly enhanced longevity over the 9,10‐bis(phenylethynyl)anthracene fluorophore used in previous profluorescent nitroxide probes. 相似文献
100.
Back Cover: Switch‐On Fluorescence of a Perylene‐Dye‐Functionalized Metal–Organic Framework through Postsynthetic Modification (Chem. Eur. J. 30/2015) 下载免费PDF全文