全文获取类型
收费全文 | 755篇 |
免费 | 40篇 |
国内免费 | 1篇 |
专业分类
化学 | 404篇 |
晶体学 | 8篇 |
力学 | 10篇 |
数学 | 41篇 |
物理学 | 198篇 |
无线电 | 135篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 12篇 |
2020年 | 27篇 |
2019年 | 19篇 |
2018年 | 22篇 |
2017年 | 4篇 |
2016年 | 25篇 |
2015年 | 14篇 |
2014年 | 23篇 |
2013年 | 43篇 |
2012年 | 40篇 |
2011年 | 40篇 |
2010年 | 24篇 |
2009年 | 26篇 |
2008年 | 33篇 |
2007年 | 33篇 |
2006年 | 28篇 |
2005年 | 32篇 |
2004年 | 20篇 |
2003年 | 33篇 |
2002年 | 21篇 |
2001年 | 11篇 |
2000年 | 14篇 |
1998年 | 12篇 |
1997年 | 8篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 15篇 |
1981年 | 13篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1978年 | 7篇 |
1977年 | 12篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1970年 | 4篇 |
排序方式: 共有796条查询结果,搜索用时 0 毫秒
131.
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
132.
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
133.
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
134.
Sanjeev Kumar Vaishali Singh Saroj Aggarwal Uttam Kumar Mandal R.K. Kotnala 《Journal of magnetism and magnetic materials》2012
CoxZnyFe3−x−yO4 ferrite (x=1 to 0; y=0 to1) nanocrystals have been synthesized by reverse microemulsion method. The nanocrystals are then comprehensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission transmission electron microscopy (FETEM), and magnetic properties were measured by using Vibrating sample magnetometer. X-ray analysis showed that all the crystals were cubic spinel. The lattice constant increased with the increase in Zn substitution. FETEM reveals that particle size varies in the range from 3 to 6 nm. As the concentration of Zn increases the magnetic behavior varies from ferromagnetic at y=0 and 0.2 to superparamagnetic to paramagnetic at y=1. The Curie temperature decreases with increasing concentration of Zn. 相似文献
135.
We classify the smallest two fold blocking sets with respect to the (n−k)-spaces in PG(n, 2). We show that they either consist of two disjoint k-dimensional subspaces or are equal to a (k + 1)-dimensional space minus one point. 相似文献
136.
The quantification of biofilm mechanical properties can serve as a basis for understanding biofilm resilience and for developing biofilm control strategies. One aspect of tensile testing that is likely to be important for a viscoelastic material such as bacterial biofilm, but unfortunately is often overlooked (i.e., not controlled or reported), is the strain rate used during testing. Thus, we performed tensile testing on intact S. epidermidis biofilms using the microcantilever method at 12 strain rate values ranging over approximately 3 orders of magnitude (0.013-9.07 s(-1)). Ultimate or cohesive strength, elastic modulus, and toughness increased with increasing strain rate and approached a plateau at approximately 1.3 s(-1). Failure strain, on the other hand, did not exhibit any trend with strain rate. Given that the mean values of some parameters increased by as much as 1 order of magnitude over the strain rate range used in this work, we suggest that the strain rate during tensile testing should be carefully controlled and reported to facilitate comparisons among different studies. Furthermore, the quantitative expressions developed in this work that relate mechanical property values with strain rate may be useful for modeling the deformation of bacterial biofilms under applied loads. 相似文献
137.
138.
Aggarwal VK Ball LT Carobene S Connelly RL Hesse MJ Partridge BM Roth P Thomas SP Webster MP 《Chemical communications (Cambridge, England)》2012,48(74):9230-9232
The expedient enantioselective synthesis of 5 bisabolane sesquiterpenes has been achieved using a common, one-pot lithiation-borylation reaction of secondary benzylic carbamates and either protodeboronation or oxidation to give the natural products in fewer than 5 steps, with high yield and >94?:?6 er. 相似文献
139.
Catherine J. Fletcher Daniel J. Blair Katherine M.P. Wheelhouse Varinder K. Aggarwal 《Tetrahedron》2012,68(37):7598-7604
A concise, highly enantioselective synthesis of sesquiterpene natural products (?)-debromoaplysin and (?)-aplysin has been completed. The key steps included lithiation–borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps. 相似文献
140.
The solandelactones A-H comprise a novel class of oxygenated fatty acids bearing an eight-membered lactone, trans cyclopropane, and a 2-ene-1,4-diol subunit. The relative stereochemistry of the 1,4-diol subunit is anti in solandelactones A, C, E & G, and syn in solandelactones B, D, F & H. Having prepared one member of the solandelactones bearing anti stereochemistry (solandelactone E), we have targeted the syn series and developed methodology for the synthesis of enantioenriched syn-2-ene-1,4-diols. The methodology comprises asymmetric deprotonation of an alkyl 2,4,6-triisopropylbenzoate using sBuLi/sparteine, followed by addition of the α-lithiobenzoate to β-silyl vinyl boronic acid ethylene glycol ester. The boron-ate complex generated undergoes a 1,2-metallate rearrangement furnishing an intermediate allyl boronic ester which is trapped by an aldehyde in the presence of MgBr(2) to furnish anti-β-hydroxy E-allylsilanes in good yields, high diastereoselectivity and high enantioselectivity. These sensitive products were oxidized using mCPBA to the corresponding epoxides and subsequently treated with acid to furnish syn-E-2-ene-1,4-diols (~4:1 d.r.). Application of the methodology to appropriately functionalized aldehyde and ω-alkenyl 2,4,6-triisopropylbenzoate coupling partners, led to a short, highly selective route to solandelactone F (bearing a syn-E-2-ene-1,4-diol). 相似文献