全文获取类型
收费全文 | 604篇 |
免费 | 31篇 |
专业分类
化学 | 382篇 |
晶体学 | 8篇 |
力学 | 10篇 |
数学 | 39篇 |
物理学 | 196篇 |
出版年
2023年 | 7篇 |
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 22篇 |
2019年 | 14篇 |
2018年 | 17篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 21篇 |
2013年 | 35篇 |
2012年 | 34篇 |
2011年 | 40篇 |
2010年 | 21篇 |
2009年 | 24篇 |
2008年 | 25篇 |
2007年 | 30篇 |
2006年 | 24篇 |
2005年 | 28篇 |
2004年 | 17篇 |
2003年 | 30篇 |
2002年 | 21篇 |
2001年 | 9篇 |
2000年 | 13篇 |
1998年 | 8篇 |
1997年 | 6篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 10篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 6篇 |
1973年 | 2篇 |
1970年 | 4篇 |
1968年 | 3篇 |
1959年 | 2篇 |
排序方式: 共有635条查询结果,搜索用时 0 毫秒
101.
ortho‐Directing Chromium Arene Complexes as Efficient Mediators for Enantiospecific C(sp2)–C(sp3) Cross‐Coupling Reactions 下载免费PDF全文
Dr. Raphael Bigler Prof. Dr. Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2018,57(4):1082-1086
A new strategy for the coupling of a broad scope of electronically diverse aromatics to boronic esters is reported. The coupling sequence, which relies on the directed ortho‐lithiation of chromium arene complexes followed by boronate formation and oxidation, occurs with complete ortho‐selectivity and enantiospecificity to give the coupling products in excellent yields and with high functional group tolerance. An intermediate chromium arene boronate complex was characterized by X‐ray, NMR, and IR experiments to elucidate the reaction mechanism. 相似文献
102.
P. Hari C. Cheney G. Luepke S. Singh N. Tolk J. S. Sanghera I. D. Aggarwal 《Journal of Non》2000,270(1-3):265-268
In this study we report first measurements of wavelength-selective infrared-induced materials modification of bulk As2S3 and As2Se3. These materials are currently being considered as candidate materials for infrared optical fiber transmission in the range of 1–10 μm. Our study is aimed at modifying oxygen, hydrogen and carbon impurities bound to chalcogenide constituent elements in the materials to reduce absorption. Tunable infrared radiation from the W.M. Keck Free Electron Laser (FEL) at Vanderbilt was used to excite specific vibrational modes, S–O–H and CHx modes in bulk As2S3 and Se–H, CHx and S–H2 modes in bulk As2Se3. Changes in vibrational mode amplitudes are monitored by measuring the intensity of the Fourier transform infrared (FTIR) spectra before and after irradiation at appropriate wavelengths. By tuning wavelengths to hydrogen vibrational modes, we find evidence that hydrogen is released and/or redistributed athermally. In particular, following irradiation at specific resonant wavelengths, vibrational mode amplitudes as monitored by FTIR associated with CHx are significantly reduced in bulk As2S3 and As2Se3 samples. In As2S3, the changes in CHx modes are reversed by heat treatment at 115°C for 35 min in nitrogen atmosphere. 相似文献
103.
Dr. Jingjing Wu Dr. Chao Shu Zhihang Li Dr. Adam Noble Prof. Dr. Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2023,62(38):e202309684
Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable reactions for the synthesis of structurally diverse alkyl halides. However, many reported protocols rely on stoichiometric strong oxidants or highly electrophilic halogenating agents. Herein, we describe visible-light photoredox-catalyzed decarboxylative halogenation reactions of N-hydroxyphthalimide-activated carboxylic acids that avoid stoichiometric oxidants and use inexpensive inorganic halide salts as the halogenating agents. Bromination with lithium bromide proceeds under simple, transition-metal-free conditions using an organic photoredox catalyst and no other additives, whereas dual photoredox-copper catalysis is required for chlorination with lithium chloride. The mild conditions display excellent functional-group tolerance, which is demonstrated through the transformation of a diverse range of structurally complex carboxylic acid containing natural products into the corresponding alkyl bromides and chlorides. In addition, we show the generality of the dual photoredox-copper-catalyzed decarboxylative functionalization with inorganic salts by extension to thiocyanation with potassium thiocyanide, which was applied to the synthesis of complex alkyl thiocyanates. 相似文献
104.
Dr. Trapti Aggarwal Kenshiro Hada Yusuke Murata Dr. Yuji Sumii Kazuhiro Tanagawa Kiyoteru Niina Soichiro Mori Dr. Jorge Escorihuela Prof. Dr. Norio Shibata 《Angewandte Chemie (International ed. in English)》2023,62(33):e202307090
Alkyne hydroamination is an effective approach for the production of enamines and enamine-containing N-heterocycles. However, stereoselectivity control is a considerable challenge in this reaction because of the electronic repulsion between an incoming nitrogen lone pair and the alkyne π-system. Herein, we propose a methodology involving β-regio- and Z-selective alkyne hydroamination by using tetrafluoro-λ6-sulfanyl (SF4) alkynes under superbasic, naked anion conditions. The reaction is compatible with a wide variety of N-heterocycles, including indoles, carbazoles, pyrazoles, and imidazoles, and selectively furnishes SF4-linked Z-vinyl enamines with β-regioselectively. Moreover, the method can be extended to the β- and Z-controlled, base-mediated alkyne hydrophenoxylation with phenols to provide SF4-linked Z-vinyl ethers in high yields. As the SF4 unit has attracted attention as a bioisostere for alkynes, p-benzenes, bicyclo[1.1.1]pentyl (BCP) groups, and cubanes in medicinal chemistry, this chemistry represents an effective approach to creating novel drug candidates incorporating SF4-containing molecules. 相似文献
105.
N.L. Misra Sangita Dhara V.C. Adya S.V. Godbole K.D. Singh Mudher S.K. Aggarwal 《Spectrochimica Acta Part B: Atomic Spectroscopy》2008
Applicability of Total Reflection X-ray Fluorescence (TXRF) spectrometry for the determination of trace metals at concentration of µg/g level in thorium oxide was studied. The TXRF spectrometer was calibrated using a multielement standard solution and the method was validated by analyzing another multielement standard solution. Sample preparation conditions were optimized for the TXRF determinations of trace metals in thorium oxide. The elements K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Ba and Pb present in thorium oxide standards were determined after dissolving them in HNO3/HF mixture and separating the bulk matrix, thorium, by solvent extraction using tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) as extractants. A comparison of TXRF determined concentrations of trace elements Ca, V, Cr, Mn, Fe, Ni and Cu with the certified values shows that TXRF determined concentrations have an RSD of 20% (1 s for n = 4) and are within an agreement of 20% of the certified values in most of the cases. 相似文献
106.
Giant Hysteretic Sorption of CO2: In Situ Crystallographic Visualization of Guest Binding within a Breathing Framework at 298 K 下载免费PDF全文
Dr. Prem Lama Dr. Himanshu Aggarwal Charl X. Bezuidenhout Prof. Leonard J. Barbour 《Angewandte Chemie (International ed. in English)》2016,55(42):13271-13275
A dynamic ZnII‐MOF has been shown to exhibit extreme breathing behavior under gas pressure. The very narrow pore form of the activated framework opens up in the presence of carbon dioxide, thus making it a suitable material for CO2 capture. Sorption of CO2 at 298 K and relatively high pressure clearly shows a two‐step isotherm with giant hysteresis for the second step. In‐situ single‐crystal diffraction analysis was carried out under CO2 gas pressure at 298 K using an environmental gas cell in order to visualize the interaction between CO2 and the host framework. The results are well supported by pressure‐gradient differential scanning calorimetry (P‐DSC) and variable‐pressure powder X‐ray analysis. Theoretical calculations have been carried out in order to further back up the crystallographic data. 相似文献
107.
Sanz D Claramunt RM Saini A Kumar V Aggarwal R Singh SP Alkorta I Elguero J 《Magnetic resonance in chemistry : MRC》2007,45(6):513-517
Multinuclear magnetic resonance spectroscopy together with GIAO-DFT calculations allowed establishment of the structure of the products obtained by condensation of 3(5)-amino-4-phenyl-1H-pyrazole and beta-dicarbonyl compounds bearing a trifluoromethyl group. They are 3-phenyl-5-(R)-7-trifluoromethylpyrazolo[1,5-a]pyrimidines. 相似文献
108.
Dipti Yadav Shreya Basuroy Rakesh Kumar Kanak Aggarwal Neelam Srivastava 《Macromolecular Symposia》2024,413(1):2300068
Polymer-in-salt-electrolytes (PISEs) are an important class of electrolytes as they carry the promise of faster and single ion transport. Unfortunately, due to unavailability of a suitable polymer host PISE has still not reached to commercial level. In the present work, using a novel synthesis protocol developed by the group, glutaraldehyde crosslinked wheat starch has been successfully modified with sodium iodide (NaI) to synthesize a flexible PISE membrane with desired electrochemical properties. Present paper reports the effect of crosslinker and exposure to high humidity ambience on electrochemical and morphological properties. It has been established that on exposure to higher humidity atmosphere starch-based PISEs stabilize at lower resistance value, but with higher ion relaxation time, which indicates that effect of high humidity treatment is more on salt dissociation instead of assisting the ion transport. The studied materials have conductivity ≈0.01 S cm−1 range with ESW >2.5 V, ensuring its usability in electrochemical devices. The developed synthesis protocol does not require any complicated synthesis route and/or sophisticated instrument hence the overall process is economical also, adding up to its potentiality for energy device fabrication. 相似文献
109.
A new dithioligand [N′-(2-methoxybenzoyl)hydrazinecarbodithioate] ethyl ester (H2mbhce, 1) formed complexes [M(Hmbhce)2]n {M = Mn(II), Cd(II)} which have been characterized with the help of elemental analyses, magnetic susceptibility measurements, IR, UV–Vis, 1H and 13C NMR and mass spectrometry. [Mn(Hmbhce)2]n (2) crystallized in monoclinic system with space group P21/n. In the polymeric structure of 2, the ligand acts as an uninegative tridentate N(1), O(1), S(3) donor and forms a five membered chelate ring with N(1), C(2) and O(1). The intermediate bond lengths (between single and double bond distances) O(1)–C(2) = 1.241(3), N(2)–C(2) = 1.325(3), N(1)–N(2) = 1.393(2), N(1)–C(8) = 1.311(3) ? and C(8)–S(3) = 1.704(2) Å suggest considerable delocalization of charge which develops slightly aromatic character in the chelate ring. 相似文献
110.
Gabriela Smeureanu Dr. Amit Aggarwal Clifford E. Soll Dr. Julius Arijeloye Erik Malave Charles Michael Drain Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12133-12140
The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20‐tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinato iron(III), ([FeIII(tppf20)]) and H2O2 is typical of the latter: the epoxide is 99 % of the product and turnover numbers are about 350. 1 – 4 Herein, we report that dynamic organic nanoparticles (ONPs) of [FeIII(tppf20)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O2 to yield only 2‐cyclohexene‐1‐one and 2‐cyclohexene‐1‐ol with approximately 10‐fold greater turnover numbers compared to the non‐aggregated metalloporphyrin in acetonitrile/methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89 % water and O2 is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced, thus causing a significant decrease in catalytic turnovers. The allylic products suggest a different oxidative mechanism compared to that of the solvated metalloporphyrins. These results illustrate the unique properties of some ONPs relative to the component molecules or those attached to supports. 相似文献