全文获取类型
收费全文 | 1444篇 |
免费 | 43篇 |
国内免费 | 8篇 |
专业分类
化学 | 848篇 |
晶体学 | 9篇 |
力学 | 63篇 |
数学 | 86篇 |
物理学 | 489篇 |
出版年
2023年 | 26篇 |
2022年 | 32篇 |
2021年 | 51篇 |
2020年 | 51篇 |
2019年 | 44篇 |
2018年 | 39篇 |
2017年 | 40篇 |
2016年 | 51篇 |
2015年 | 39篇 |
2014年 | 54篇 |
2013年 | 119篇 |
2012年 | 99篇 |
2011年 | 126篇 |
2010年 | 55篇 |
2009年 | 46篇 |
2008年 | 73篇 |
2007年 | 70篇 |
2006年 | 69篇 |
2005年 | 53篇 |
2004年 | 38篇 |
2003年 | 33篇 |
2002年 | 29篇 |
2001年 | 17篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 9篇 |
1992年 | 14篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有1495条查询结果,搜索用时 314 毫秒
91.
Shiwani Berry Shamsher S. Bari Pooja Yadav Ankita Garg Sadhika Khullar Sanjay K. Mandal 《合成通讯》2020,50(19):2969-2980
Abstract An efficient protocol for the stereoselective synthesis of pyrazolo[5,1-b]thiazole-3-carboxylate tethered β-lactam conjugates 8a–j from novel pyrazolo [5,1-b]thiazole-3-carboxylate substituted Schiff’s bases 6a–f is reported here. The reaction between various ketene precursors and novel Schiff’s bases 6a–f afforded exclusive formation of trans-β-lactams 8a–j. The substrate scope of this approach was investigated extensively by varying different groups (R, Z). All the novel compounds were characterized using various spectroscopic techniques, such as FT-IR, 1H NMR, 13C NMR, elemental analysis, 13C NMR (DEPT-135), and mass spectrometry in representative cases. Single crystal X-ray crystallographic study of trans-ethyl 7-(1-(4-methoxyphenyl)-4-oxo-3-phenoxyazetidin-2-yl)-6-methyl-2-(methylthio)pyrazolo[5,1-b]thiazole-3-carboxylate 8a has confirmed the molecular structure and the stereochemical outcome. To the best of our knowledge, the synthesis of such types of Schiff’s bases and β-lactam conjugates has not been reported so far. 相似文献
92.
Rene F. Roller Ankita Malik Maria A. Carillo Monika Garg Antonella Rella Marie‐Kristin Raulf Bernd Lepenies Peter H. Seeberger Daniel Varn Silva 《Angewandte Chemie (International ed. in English)》2020,59(29):12035-12040
Glypiation is a common posttranslational modification of eukaryotic proteins involving the attachment of a glycosylphosphatidylinositol (GPI) glycolipid. GPIs contain a conserved phosphoglycan that is modified in a cell‐ and tissue‐specific manner. GPI complexity suggests roles in biological processes and effects on the attached protein, but the difficulties to get homogeneous material have hindered studies. We disclose a one‐pot intein‐mediated ligation (OPL) to obtain GPI‐anchored proteins. The strategy enables the glypiation of folded and denatured proteins with a natural linkage to the glycolipid. Using the strategy, glypiated eGFP, Thy1, and the Plasmodium berghei protein MSP119 were prepared. Glypiation did not alter the structure of eGFP and MSP119 proteins in solution, but it induced a strong pro‐inflammatory response in vitro. The strategy provides access to glypiated proteins to elucidate the activity of this modification and for use as vaccine candidates against parasitic infections. 相似文献
93.
AbstractEffective extraction of phyto-biomolecules insures retaining maximum functionality along with higher recovery. In this study, ultrasound-solvent assisted extraction (USAE) was employed for optimal extraction of phyto-biomolecules from Sesamum indicum (sesame) leaves using the approach of Response Surface Methodology (RSM). The optimized condition of 200?W power, 59% methanol concentration with 1:14?g/mL solid–liquid ratio and 15?min of extraction time yielded 367.39?±?1.85?mg GAE/100?g of total phenolic content, 96.72?±?3.27% of free radical scavenging activity and 81.20?±?2.87% of iron chelating activity respectively. The extract consist of essential phytocomponents like gallic acid, chlorogenic acid, and quercetin with lipid peroxidation activities of >50% over incubation time of 48?h. Also, showed antimicrobial activity against various Gram’s negative and positive food borne pathogens. The results of this study implied the importance of USAE for effective and optimum recovery of phyto-biomolecules from Sesame leaves with retained functional properties. 相似文献
94.
Biswarup Chakraborty Shweta Kalra Rodrigo Beltrn‐Suito Chittaranjan Das Tim Hellmann Prashanth W. Menezes Matthias Driess 《化学:亚洲杂志》2020,15(6):852-859
In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu9S5 has been prepared from a molecular copper(I) precursor, [{(PyHS)2CuI(PyHS)}2](OTf)2 ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu9S5, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu9S5/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO2 and IrO2 electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu9S5/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu9S5 can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu9S5 that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals. 相似文献
95.
96.
Soujan Ghosh Swati Chowdhury Subrata Kundu Sudipta Sasmal Dimitrios Z. Politis Stelios M. Potirakis Masashi Hayakawa Suman Chakraborty Sandip K. Chakrabarti 《Entropy (Basel, Switzerland)》2022,24(1)
We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock. 相似文献
97.
In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH4 and CO2 adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy. 相似文献
98.
This study was conducted in a continuous three-stage system of anaerobic (R1)-anoxic(R2)-aerobic (R3) reactors with synthetic
wastewater containing phenol (1000 mg/L), chemical oxygen demand (COD) (3000 mg/L), CN− (30 mg/L), SCN−(400 mg/L), and NH
4
+
-N (600 mg/L) as principal pollutants and well-acclimated heterogeneous microbial cultures. The final effluent was partially
returned to R2 with a recycle ratio of 1. Anaerobic stage served to detoxify the feed by removing up to 80% of cyanide. Complete
SCN− removal and denitrification could be achieved in the anoxic stage by utilizing phenol as an internal source of carbon. Nitrification
efficiency of 93% was obtained in the aerobic reactor. The results demonstrated that the three-stage system can give the desired
final treated effluent quality (0 mg/L of phenol, 0.2 mg/L of CN−, 210 mg/L of COD, and 20 mg/L of NH
4
+
-N) and that the NO
3
−
-N concentration can be lowered by a higher recycle ratio. 相似文献
99.
Chakraborty T Holm AI Hvelplund P Nielsen SB Poully JC Worm ES Williams ER 《Journal of the American Society for Mass Spectrometry》2006,17(12):1675-1680
Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process. 相似文献
100.
Rabindra N. Roy Lakshmi N. Roy Kathleen A. Allen Casey J. Mehrhoff Isaac B. Henson Jessica M. Stegner Alexis L. Jenkins Ankita A. Shah Stephen D. Rocchio 《Journal of solution chemistry》2012,41(6):1044-1053
In this study, we report the pH values of two buffer solutions without chloride ion and eight buffer solutions with NaCl with an ionic strength I=0.16 mol?kg?1. Electromotive force (emf) techniques have been used to get the cell potentials at 12 temperatures from 5 to 55?°C, including 37?°C. An extended form of the Bates-Guggenheim convention is used in the entire ionic strength range, 0.04 to 0.16?mol?kg?1. The residual liquid junction potentials (??E j ) of the buffer solutions of MOBS have been estimated from previous measurements with a flowing junction cell. These values of ??E j have been used for correction in order to ascertain the operational pH values of four buffer solutions of MOBS at 25 and 37?°C. These solutions are recommended as pH standards for physiological application in the pH range 7.4 to 7.7. 相似文献