全文获取类型
收费全文 | 2240篇 |
免费 | 96篇 |
国内免费 | 31篇 |
专业分类
化学 | 1254篇 |
晶体学 | 7篇 |
力学 | 84篇 |
数学 | 707篇 |
物理学 | 315篇 |
出版年
2023年 | 23篇 |
2022年 | 51篇 |
2021年 | 94篇 |
2020年 | 94篇 |
2019年 | 101篇 |
2018年 | 103篇 |
2017年 | 89篇 |
2016年 | 118篇 |
2015年 | 69篇 |
2014年 | 93篇 |
2013年 | 176篇 |
2012年 | 134篇 |
2011年 | 137篇 |
2010年 | 110篇 |
2009年 | 75篇 |
2008年 | 128篇 |
2007年 | 103篇 |
2006年 | 65篇 |
2005年 | 65篇 |
2004年 | 55篇 |
2003年 | 39篇 |
2002年 | 46篇 |
2001年 | 13篇 |
2000年 | 16篇 |
1999年 | 16篇 |
1998年 | 16篇 |
1997年 | 17篇 |
1996年 | 17篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 9篇 |
1990年 | 9篇 |
1989年 | 15篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 21篇 |
1984年 | 13篇 |
1982年 | 14篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 14篇 |
1978年 | 15篇 |
1977年 | 19篇 |
1976年 | 16篇 |
1975年 | 18篇 |
1974年 | 9篇 |
1973年 | 12篇 |
排序方式: 共有2367条查询结果,搜索用时 390 毫秒
101.
Than Ha An Quoc Pham Thien Huu Nguyen Duyen Ky Vo Pham Thuong Hoai Khacef Ahmed 《Plasma Chemistry and Plasma Processing》2022,42(1):73-89
Plasma Chemistry and Plasma Processing - Non-thermal plasma is widely considered as an effective technology for applications in agriculture. Particularly, numerous reports studies have highlighted... 相似文献
102.
Dr. Thi Minh Thi Le Dr. Thibaud Brégent Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201514
Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH3CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism. 相似文献
103.
Tien Song Hiep Pham Shinichi Hasegawa Peter Mahon Katia Guérin Marc Dubois Aimin Yu 《Electroanalysis》2022,34(3):435-444
Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future. 相似文献
104.
Maximilian Knies Dr. Matthias F. Groh Tobias Pietsch Mai Lê Anh Prof. Dr. Michael Ruck 《ChemistryOpen》2021,10(2):110-116
Bi2S3 was dissolved in the presence of either AuCl/PtCl2 or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl3 (BMIm=1-n-butyl-3-methylimidazolium; x=4–4.3) through annealing the mixtures at 180 or 200 °C. Upon cooling to room temperature, orange, air-sensitive crystals of [BMIm](Bi4S4)[AlCl4]5 ( 1 ) or Ag(Bi7S8)[S(AlCl3)3]2[AlCl4]2 ( 2 ) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl2, suggesting an essential role of the metal cations. X-ray diffraction on single-crystals of 1 revealed a monoclinic crystal structure that contains (Bi4S4)4+ heterocubanes and [AlCl4]− tetrahedra as well as [BMIm]+ cations. The intercalation of the ionic liquid was confirmed via solid state NMR spectroscopy, revealing unusual coupling behavior. The crystal structure of 2 consists of (Bi7S8)5+ spiro-dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K. 相似文献
105.
Clayton A. Whitmore Mariam I. Boules William J. Behof Justin R. Haynes Dmitry Koktysh Adam J. Rosenberg Mohammed N. Tantawy Wellington Pham 《Molecules (Basel, Switzerland)》2021,26(8)
Promethazine, an antihistamine drug used in the clinical treatment of nausea, has been demonstrated the ability to bind Abeta in a transgenic mouse model of Alzheimer’s disease. However, so far, all of the studies were performed in vitro using extracted tissues. In this work, we report the design and synthesis of a novel [11C]promethazine PET radioligand for future in vivo studies. The [11C]promethazine was isolated by RP-HPLC with radiochemical purity >95% and molar activity of 48 TBq/mmol. The specificity of the probe was demonstrated using human hippocampal tissues via autoradiography. 相似文献
106.
Martin Krtký Katarína Svr
kov Quynh Anh Vu rka tpnkov Jarmila Vinov 《Molecules (Basel, Switzerland)》2021,26(4)
Based on the broad spectrum of biological activity of hydrazide–hydrazones, trifluoromethyl compounds, and clinical usage of cholinesterase inhibitors, we investigated hydrazones obtained from 4-(trifluoromethyl)benzohydrazide and various benzaldehydes or aliphatic ketones as potential inhibitors of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). They were evaluated using Ellman’s spectrophotometric method. The hydrazide–hydrazones produced a dual inhibition of both cholinesterase enzymes with IC50 values of 46.8–137.7 µM and 19.1–881.1 µM for AChE and BuChE, respectively. The majority of the compounds were stronger inhibitors of AChE; four of them (2-bromobenzaldehyde, 3-(trifluoromethyl)benzaldehyde, cyclohexanone, and camphor-based 2o, 2p, 3c, and 3d, respectively) produced a balanced inhibition of the enzymes and only 2-chloro/trifluoromethyl benzylidene derivatives 2d and 2q were found to be more potent inhibitors of BuChE. 4-(Trifluoromethyl)-N’-[4-(trifluoromethyl)benzylidene]benzohydrazide 2l produced the strongest inhibition of AChE via mixed-type inhibition determined experimentally. Structure–activity relationships were identified. The compounds fit physicochemical space for targeting central nervous systems with no apparent cytotoxicity for eukaryotic cell line together. The study provides new insights into this CF3-hydrazide–hydrazone scaffold. 相似文献
107.
Cadars S Sein J Duma L Lesage A Pham TN Baltisberger JH Brown SP Emsley L 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(1):24-34
The robustness of the refocused INADEQUATE MAS NMR pulse sequence for probing through-bond connectivities has been demonstrated in a large range of solid-state applications. This pulse sequence nevertheless suffers from artifacts when applied to multispin systems, e.g. uniformly labeled (13)C solids, which distort the lineshapes and can potentially result in misleading correlation peaks. In this paper, we present a detailed account that combines product-operator analysis, numerical simulations and experiments of the behavior of a three-spin system during the refocused INADEQUATE pulse sequence. The origin of undesired anti-phase contributions to the spectral lineshapes are described, and we show that they do not interfere with the observation of long-range correlations (e.g. two-bond (13)C-(13)C correlations). The suppression of undesired contributions to the refocused INADEQUATE spectra is shown to require the removal of zero-quantum coherences within a z-filter. A method is proposed to eliminate zero-quantum coherences through dephasing by heteronuclear dipolar couplings, which leads to pure in-phase spectra. 相似文献
108.
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
109.
Cellulose - The paper is a review on the extraction processes of cellulosic fibers from flax and hemp. The two lignocellulosic crops have a long history of use by humans for extraction of the bast... 相似文献
110.
Aromatic Homologation by Non‐Chelate‐Assisted RhIII‐Catalyzed CH Functionalization of Arenes with Alkynes 下载免费PDF全文
Manh V. Pham Prof. Dr. Nicolai Cramer 《Angewandte Chemie (International ed. in English)》2014,53(13):3484-3487
Larger condensed arenes are of interest owing to their electro‐ and photochemical properties. An efficient synthesis is the catalyzed aromatic annulation of a smaller arene with two alkyne molecules. Besides difunctionalized starting materials, directed C? H functionalization can be used for such aromatic homologation. However, thus far the requirement of either pre‐functionalized substrates or suitable directing groups were limiting this approach. Herein, we describe a rhodium(III)‐catalyzed method allowing the use of completely unbiased arenes and internal alkynes. The reaction works best with copper(II) 2‐ethylhexanoate and decabromodiphenyl ether as the oxidant combination. This aromatic annulation tolerates a variety of functional groups and delivers homologated condensed arenes. Aside from simple benzenes, naphthalenes and higher condensed arenes provide access to highly substituted and highly soluble acenes structures having important electronic and photophysical properties. 相似文献