全文获取类型
收费全文 | 860篇 |
免费 | 44篇 |
国内免费 | 10篇 |
专业分类
化学 | 621篇 |
晶体学 | 5篇 |
力学 | 25篇 |
数学 | 138篇 |
物理学 | 125篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 19篇 |
2020年 | 13篇 |
2019年 | 35篇 |
2018年 | 14篇 |
2017年 | 8篇 |
2016年 | 27篇 |
2015年 | 35篇 |
2014年 | 37篇 |
2013年 | 60篇 |
2012年 | 71篇 |
2011年 | 59篇 |
2010年 | 34篇 |
2009年 | 38篇 |
2008年 | 60篇 |
2007年 | 54篇 |
2006年 | 45篇 |
2005年 | 36篇 |
2004年 | 39篇 |
2003年 | 38篇 |
2002年 | 29篇 |
2001年 | 9篇 |
2000年 | 3篇 |
1999年 | 13篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1991年 | 4篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1971年 | 3篇 |
1970年 | 3篇 |
1968年 | 2篇 |
1966年 | 4篇 |
排序方式: 共有914条查询结果,搜索用时 0 毫秒
21.
Dr. Michael Peter Mercer Sam Affleck Dr. Edgardo Maximiliano Gavilán-Arriazu Dr. Alana Aragón Zülke Dr. Philip A. Maughan Shivam Trivedi Prof. Maximilian Fichtner Dr. Anji Reddy Munnangi Prof. Ezequiel P. M. Leiva Prof. Harry Ernst Hoster 《Chemphyschem》2022,23(5):e202100748
Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge. 相似文献
22.
Rukmanikrishnan Balasubramanian Ramalingam Srinivasan Kim Sam Soo Lee Jaewoong 《Cellulose (London, England)》2021,28(9):5577-5590
Cellulose - Sustainable food packaging films were developed using a combination of k-Carrageenan (k-C), hydroxyl ethyl cellulose (HEC), silicon dioxide (SiO2), and silver (Ag) nanoparticles. The... 相似文献
23.
Back Cover: Quantum Mechanics/Molecular Mechanics Study on the Oxygen Binding and Substrate Hydroxylation Step in AlkB Repair Enzymes (Chem. Eur. J. 2/2014) 下载免费PDF全文
24.
Dramatic Influence of an Anionic Donor on the Oxygen‐Atom Transfer Reactivity of a MnV–Oxo Complex 下载免费PDF全文
Heather M. Neu Dr. Matthew G. Quesne Tzuhsiung Yang Dr. Katharine A. Prokop‐Prigge Prof. Kyle M. Lancaster James Donohoe Prof. Serena DeBeer Dr. Sam P. de Visser Prof. David P. Goldberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14584-14588
Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2‐electron oxygen‐atom‐transfer (OAT) chemistry. The 6‐coordinate [MnV(O)(TBP8Cz)(CN)]? was generated from addition of Bu4N+CN? to the 5‐coordinate MnV(O) precursor. The cyanide‐ligated complex was characterized for the first time by Mn K‐edge X‐ray absorption spectroscopy (XAS) and gives Mn?O=1.53 Å, Mn?CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN? complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e?‐reduced MnIII(CN)? complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000‐fold versus the same reaction for the parent 5‐coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol?1, ΔS≠=?10 cal mol?1 K?1. Computational studies fully support the structures, spin states, and relative reactivity of the 5‐ and 6‐coordinate MnV(O) complexes. 相似文献
25.
Water disinfection activity of cellulose filters treated with polycarboxylic acid and aromatic amine
A cellulose filter for water disinfection was developed using a polycarboxylic acid and an aromatic amine via a simple process with water as a solvent. 1,2,3,4-Butanetetracarboxylic acid/m-phenylenediamine solution was applied to cellulose filters using a pad–dry–curing process. The surfaces of treated cellulose filters were examined by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The liquid permeabilities of treated cellulose filters were determined by capillary flow porometry, and their water disinfection efficacies were measured by non-pressure-driven filtration. Chlorinated cellulose filters disinfected Escherichia coli- and Staphylococcus aureus-containing solutions to a much higher degree than observed for nonchlorinated cellulose filters. 相似文献
26.
Kyle M. Lambert Joshua B. Cox Lin Liu Amy C. Jackson Sam Yruegas Kenneth B. Wiberg John L. Wood 《Angewandte Chemie (International ed. in English)》2020,59(24):9757-9766
The development of a concise total synthesis of (±)‐phyllantidine ( 1 ), a member of the securinega family of alkaloids containing an unusual oxazabicyclo[3.3.1]nonane core, is described. The synthesis employs a unique synthetic strategy featuring the ring expansion of a substituted cyclopentanone to a cyclic hydroxamic acid as a key step that allows facile installation of the embedded nitrogen‐oxygen (N?O) bond. The optimization of this sequence to effect the desired regiochemical outcome and its mechanistic underpinnings were assessed both computationally and experimentally. This synthetic approach also features an early‐stage diastereoselective aldol reaction to assemble the substituted cyclopentanone, a mild reduction of an amide intermediate without N?O bond cleavage, and the rapid assembly of the butenolide found in ( 1 ) via use of the Bestmann ylide. 相似文献
27.
Laily Rahmawati Sang Hee Park Dong Seon Kim Hwa Pyoung Lee Nur Aziz Chae Young Lee Seung A Kim Seok Gu Jang Dong Sam Kim Jae Youl Cho 《Molecules (Basel, Switzerland)》2022,27(1)
Prasiola japonica possesses several biological activities. However, reports on the anti-inflammatory activities and molecular mechanisms of its different solvent fractions remain limited. In this study, we investigated the potential anti-inflammatory activities of P. japonica ethanol extract (Pj-EE) and four solvent fractions of Pj-EE made with hexane (Pj-EE-HF), chloroform (Pj-EE-CF), butanol (Pj-EE-BF), or water (Pj-EE-WF) in both in vitro (LPS-induced macrophage-like RAW264.7 cells) and in vivo (carrageenan-induced acute paw edema mouse models) experiments. The most active solvent fraction was selected for further analysis. Various in vitro and in vivo assessments, including nitric oxide (NO), cytokines, luciferase assays, real-time polymerase chain reactions, and immunoblotting analyses were performed to evaluate the underlying mechanisms. In addition, the phytochemical constituents were characterized by Liquid chromatography-tandem mass spectrometry. In in vitro studies, the highest inhibition of NO production was observed in Pj-EE-CF. Further examination revealed that Pj-EE-CF decreased the expression of inflammation-related cytokines in LPS-induced RAW264.7 cells and suppressed subsequent AP-1-luciferase activity by inhibition of phosphorylation events in the AP-1 signaling pathway. Pj-EE-CF treatment also demonstrated the strongest reduction in thickness and volume of carrageenan-induced paw edema, while Pj-EE-BF showed the lowest activity. Furthermore, Pj-EE-CF also reduced gene expression and cytokines production in tissue lysates of carrageenan-induced paw edema. These findings support and validate the evidence that Pj-EE, and especially Pj-EE-CF, could be a good natural source for an anti-inflammatory agent that targets the AP1 pathway. 相似文献
28.
Kristian K. Müller-Nedebock Shaul M. Aharoni Sam F. Edwards 《Macromolecular Symposia》1995,98(1):701-717
Networks of rigid molecules do not fit into the paradigm of classical theories of rubber elasticity. Some experimental properties of rigid polyamide networks are summarised, and the basis for a theoretical understanding of such systems is discussed and elaborated in terms of the properties such as the existence of several conformational states and twist of such network elements. 相似文献
29.
The charge structure and interaction mechanism on In-doped sulphur spinel FeInxCr2−xS4 are studied. The temperature dependence of magnetization μB, measured from 60 K to room temperature, suggests that FeInxCr2−xS4 (x=0.1, 0.3) are ferrimagnetic. The Néel temperature is decreased with increasing non-magnetic In substitution as consequence of reduction of superexchange interaction for increased lattice parameter. FeInxCr2−xS4 is investigated by Mössbauer spectra from 4.2 K to room temperature. The asymmetric line broadening is observed for the sample FeInxCr2−xS4 and considered to be dynamic Jahn–Teller relaxation. The charge state of Fe ions is ferrous in character. 相似文献
30.
Our objective was to investigate whether hemorrhage control can be achieved faster when high-intensity focused ultrasound (HIFU) is applied in the presence of ultrasound contrast agents (UCA) as compared to HIFU only application. Incisions (3 cm long and 0.5 cm deep) were produced in the livers of anesthetized rabbits. UCA Optison (0.18 ml/kg) was injected into the mesenteric vein. A HIFU applicator (5.5 MHz, 6800 W/cm2 in situ) was scanned at a rate of 1–2 mm/s in one direction over the incision (with multiple passes if needed), until hemostasis was achieved. Hemostasis times were 59 ± 23 s (n = 21) in the presence of Optison and 70 ± 23 s (n = 29) without Optison. The presence of Optison produced on average 37% reduction in hemostasis times normalized to initial bleeding rates (p < 0.05), as well as 60% faster formation of the coagulum seal over the incision (p < 0.05). Gross and histological observations showed similar appearance of HIFU lesions produced in the presence of Optison and HIFU lesions produced without Optison. Our results suggest potential utility of UCA for increasing efficiency of HIFU-induced hemostasis of solid organ injuries. 相似文献