全文获取类型
收费全文 | 1541篇 |
免费 | 109篇 |
国内免费 | 2篇 |
专业分类
化学 | 1229篇 |
晶体学 | 3篇 |
力学 | 32篇 |
综合类 | 1篇 |
数学 | 194篇 |
物理学 | 193篇 |
出版年
2023年 | 28篇 |
2022年 | 25篇 |
2021年 | 31篇 |
2020年 | 51篇 |
2019年 | 34篇 |
2018年 | 22篇 |
2017年 | 17篇 |
2016年 | 80篇 |
2015年 | 75篇 |
2014年 | 69篇 |
2013年 | 75篇 |
2012年 | 101篇 |
2011年 | 102篇 |
2010年 | 73篇 |
2009年 | 54篇 |
2008年 | 99篇 |
2007年 | 103篇 |
2006年 | 97篇 |
2005年 | 89篇 |
2004年 | 78篇 |
2003年 | 57篇 |
2002年 | 34篇 |
2001年 | 27篇 |
2000年 | 16篇 |
1999年 | 21篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 10篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 11篇 |
1983年 | 8篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1975年 | 5篇 |
1916年 | 3篇 |
排序方式: 共有1652条查询结果,搜索用时 31 毫秒
991.
Katherine Valderrama Leonardo Castellanos Sven Zea 《Journal of separation science》2010,33(15):2316-2321
The sponge Discodermia dissoluta is the source of the potent antimitotic compound (+)‐discodermolide. The relatively abundant and shallow populations of this sponge in Santa Marta, Colombia, allow for studies to evaluate the natural and biotechnological supply options of (+)‐discodermolide. In this work, an RP‐HPLC‐UV methodology for the quantification of (+)‐discodermolide from sponge samples was tested and validated. Our protocol for extracting this compound from the sponge included lyophilization, exhaustive methanol extraction, partitioning using water and dichloromethane, purification of the organic fraction in RP‐18 cartridges and then finally retrieving the (+)‐discodermolide in the methanol–water (80:20 v/v) fraction. This fraction was injected into an HPLC system with an Xterra RP‐18 column and a detection wavelength of 235 nm. The calibration curve was linear, making it possible to calculate the LODs and quantification in these experiments. The intra‐day and inter‐day precision showed relative standard deviations lower than 5%. The accuracy, determined as the percentage recovery, was 99.4%. Nine samples of the sponge from the Bahamas, Bonaire, Curaçao and Santa Marta had concentrations of (+)‐discodermolide ranging from 5.3 to 29.3 μg/g?1 of wet sponge. This methodology is quick and simple, allowing for the quantification in sponges from natural environments, in situ cultures or dissociated cells. 相似文献
992.
Andreas Thomas Simon Beuck Jens Christian Eickhoff Sven Guddat Oliver Krug Matthias Kamber Wilhelm Schänzer Mario Thevis 《Analytical and bioanalytical chemistry》2010,396(8):2899-2908
Influencing the endurance in elite sports is one of the key points in modern sports science. Recently, a new class of prohibited
substances reached in the focus of doping control laboratories and their misuse was classified as gene doping. The adenosine
monophosphate activated protein kinase activator 5-amino-4-imidazolecarboxyamide ribonucleoside (AICAR) was found to significantly
enhance the endurance even in sedentary mice after treatment. Due to endogenous production of AICAR in healthy humans, considerable
amounts were present in the circulation and, thus, were excreted into urine. Considering these facts, the present study was
initiated to fix reference values of renally cleared AICAR in elite athletes. Therefore a quantitative analytical method by
means of isotope-dilution liquid chromatography (analytical column: C6-phenyl) coupled to tandem mass spectrometry, after
a sample preparation consisting of a gentle dilution of native urine, was developed. Doping control samples of 499 athletes
were analysed, and AICAR concentrations in urine were determined. The mean AICAR value for all samples was 2,186 ng/mL with
a standard deviation of 1,655 ng/mL. Concentrations were found to differ depending on gender, type of sport and type of sample
collection (in competition/out of competition). The method was fully validated for quantitative purposes considering the parameters
linearity, inter- (12%, 7% and 10%) and intraday precision (14%, 9% and 12%) at low, mid and high concentration, robustness,
accuracy (approx. 100%), limit of quantification (100 ng/mL), stability and ion suppression effects, employing an in-house
synthesised 13C5-labelled AICAR as internal standard. 相似文献
993.
Two-dimensional ultrasound Doppler velocimeter for velocity field measurements of liquid metal flows
Sven Franke Andreas Fischer Lars Büttner Jürgen Czarske Dirk Räbiger Sven Eckert 《PAMM》2011,11(1):649-650
We present a novel fluid flow measurement system based on the pulsed-wave ultrasound Doppler velocimetry being able to determine two-dimensional velocity fields. It applies for the measurement of unsteady liquid metal flows driven by electromagnetic forces concerning the research field of magnetohydrodynamics. The application of advanced processing techniques enable high data acquisition rates and concurrently a high spatial resolution facilitating to resolve transient liquid metal flow structures which could not been acquired so far. An experimental setup utilizing liquid metal in a cubic vessel exposed to a stationary rotating magnetic field was used to validate the reliability of the measurement system. The swirling fluid motion in its horizontal section could be resolved into a velocity field grid of 24 × 24 vectors while achieving frame rates of about 30 fps. Results from a further study driving liquid metal in a cylindrical vessel by a pulsed rotating magnetic field are presented. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
994.
Sven Tobisch Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(11):3441-3458
The present computational mechanistic study explores comprehensively the organoactinide‐mediated intramolecular hydroamination/cyclisation (IHC) of aminodienes by employing a reliable DFT method. All the steps of a plausible catalytic reaction course have been scrutinised for the IHC of (4E,6)‐heptadienylamine 1 t by [(CGC)Th(NMe2)2] precatalyst 2 (CGC=[Me2Si(η5‐Me4C5)(tBuN)]2?). For each of the relevant elementary steps the most accessible pathway has been identified from a multitude of mechanistic possibilities. The operative mechanism involves rapid substrate association/dissociation equilibria for the 3 t ‐S resting state and also for azacyclic intermediates 4 a , 4 s , easily accessible and reversible exocyclic ring closure, supposedly facile isomerisation of the azacycle’s butenyl tether prior to turnover‐limiting protonolysis. The following aspects are in support of this scenario: 1) the derived rate law is consistent with the experimentally obtained empirical rate law; 2) the accessed barrier for turnover‐limiting protonolysis does agree remarkably well with observed performance data; 3) the ring‐tether double‐bond selectivity is consistently elucidated, which led to predict the product distribution correctly. This study provides a computationally substantiated rationale for observed activity and selectivity data. Steric demands at the CGC framework appear to be an efficient means for modulating both performance and ring‐tether double‐bond selectivity. The careful comparison of (CGC)4f‐element and (CGC)5f‐element catalysts revealed that aminodiene IHC mediated by organoactinides and organolanthanides proceeds through a similar mechanistic scenario. However, cyclisation and protonolysis steps, in particular, feature a markedly different reactivity pattern for the two catalyst classes, owing to enhanced bond covalency of early actinides when compared to lanthanides. 相似文献
995.
996.
Kshitij Sanjay Shinde Philipp Michael Michael Rössle Sven Thiele Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2020,58(20):2864-2874
The incorporation of functional groups into unsaturated polyolefine-polymers often represent a challenging task. Based on the known cyclopropanation of double bonds with diazoesters in the presence of metal-catalysts of low molecular weight compounds, we in this article develop an approach to decorate the polymer backbone of poly(diene)s with ester as well as carboxylic groups via cyclopropanation. Therefore, predominantly cis-1,4-poly(isoprene)s are converted with ethyl or tert-butyl diazoacetate using copper(I) N-heterocyclic carbene (NHC) catalysts, while focusing on the technically relevant cyclohexane as solvent. The application of commercially available NHC-Cu(I) catalysts results in modification degrees of 4–5%, while an increased solvent polarity, like dichloromethane, results in up to 17% modification. The resulting esters were further converted to the corresponding free carboxylic groups by deprotection using trifluoroacetic acid. Thus, an introduction of functional groups along the polymer backbone with a wide variety of application, like ionic interaction or hydrogen bonding motifs, was successfully demonstrated. Its potential for upscaling makes this approach feasible for an application in large-scale production processes, such as for manufacturing of modified synthetic rubbers. 相似文献
997.
Xuelin Fan Swen Zerebecki Ran Du René Hübner Galina Marzum Guocan Jiang Yue Hu Stephan Barcikowki Sven Reichenberger Alexander Eychmüller 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5755-5760
Noble metal aerogels (NMAs) are an emerging class of porous materials. Embracing nano-sized highly-active noble metals and porous structures, they display unprecedented performance in diverse electrocatalytic processes. However, various impurities, particularly organic ligands, are often involved in the synthesis and remain in the corresponding products, hindering the investigation of the intrinsic electrocatalytic properties of NMAs. Here, starting from laser-generated inorganic-salt-stabilized metal nanoparticles, various impurity-free NMAs (Au, Pd, and Au-Pd aerogels) were fabricated. In this light, we demonstrate not only the intrinsic electrocatalytic properties of NMAs, but also the prominent roles played by ligands in tuning electrocatalysis through modulating the electron density of catalysts. These findings may offer a new dimension to engineer and optimize the electrocatalytic performance for various NMAs and beyond. 相似文献
998.
Jens Bielefeld Sven Doye 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6194-6199
The scientific interest in catalytic hydroaminoalkylation reactions of alkenes has vastly increased over the past decade, but these reactions have struggled to become a viable option for general laboratory or industrial use because of reaction times of several days. The titanium-based catalytic system introduced in this work not only reduces the reaction time by several orders of magnitude, into the range of minutes, but the catalyst is also demonstrated to be easily available from common starting materials, at a cost of approximately 1 € per millimole of catalyst. We were also able to formally perform C−H activation of methylamine and achieve coupling to a broad variety of alkenes, through silyl protection of the amine and simple deprotection by water. 相似文献
999.
Christoph J. Dürr Andreas Kaiser Sven Brandau Axel K. T. Habicht Michael Klimpel Christopher Barner‐Kowollik 《Journal of polymer science. Part A, Polymer chemistry》2012,50(1):174-180
The synthesis of acrylonitrile‐butadiene rubbers (NBRs) via trithiocarbonate‐mediated reversible addition fragmentation chain transfer (RAFT) polymerization of acrylonitrile (ACN) and 1,3‐butadiene (BD) in solution under azeotropic conditions (38/62) was investigated for a broad range of common solvents: N,N‐dimethylacetamide (DMAc), chlorobenzene, 1,4‐dioxane, tert‐butanol, isobutyronitrile, toluene, trimethylacetonitrile, dimethyl carbonate, acetonitrile, methyl acetate, acetone, and tert‐butyl methyl ether. The gravimetrically determined conversions for the free radical polymerizations of ACN/BD after 22 h at 100 °C were in the range of 15% for methyl acetate to 35% for DMAc. The origin of the differences in conversion is attributed to the unequal decomposition behavior of the employed azo initiator 2,2′‐azobis(N‐butyl‐2‐methylpropionamide) ( 1 ) in the solvents under investigation, as determined by ultraviolet–visible (UV–vis) spectroscopy. Relative decomposition of 1 in solution (0.1 mol L?1) at 100 °C was calculated from the UV–vis spectra for selected solvents. 90% of 1 in DMAc was decomposed after 22 h, 83% in tert‐butanol, 57% in 1,4‐dioxane, 53% in isobutyronitrile, 45% in chlorobenzene, and 21% in toluene. The evolution of molecular weight with conversion using the initiator 1 was in accordance with the theoretically expected values, regardless of the solvent studied. Moreover, the RAFT‐mediated copolymerization of ACN/BD in DMAc with azo initiators 1 , 1‐[(1‐cyano‐1‐methylethyl)azo]formamide ( 2 ) and 1,1′‐azobis(cyclohexanecarbonitrile) ( 3 ) was investigated. A strong deviation from the linear evolution of molecular weight due to a fast decomposition of these initiators – congruent with high primary radical delivery rates – at the selected temperature was observed when using 2 and 3 . The deviation was not observed when using 1 . © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
1000.
Sinke H. Osong Christina Dahlström Sven Forsberg Britta Andres Per Engstrand Sven Norgren Ann-Christine Engström 《Cellulose (London, England)》2016,23(4):2487-2500
Though research into nanofibrillated cellulose (NFC) has recently increased, few studies have considered co-utilising NFC and nanographite (NG) in composite films, and, it has, however been a challenge to use high-yield pulp fibres (mechanical pulps) to produce this nanofibrillar material. It is worth noting that there is a significant difference between chemical pulp fibres and high-yield pulp fibres, as the former is composed mainly of cellulose and has a yield of approximately 50 % while the latter is consist of cellulose, hemicellulose and lignin, and has a yield of approximately 90 %. NFC was produced by combining TEMPO (2,2,6,6-tetramethypiperidine-1-oxyl)-mediated oxidation with the mechanical shearing of chemi-thermomechanical pulp (CTMP) and sulphite pulp (SP); the NG was produced by mechanically exfoliating graphite. The different NaClO dosages in the TEMPO system differently oxidised the fibres, altering their fibrillation efficiency. NFC–NG films were produced by casting in a Petri dish. We examine the effect of NG on the sheet-resistance and mechanical properties of NFC films. Addition of 10 wt% NG to 90 wt% NFC of sample CC2 (5 mmol NaClO CTMP-NFC homogenised for 60 min) improved the sheet resistance, i.e. from that of an insulating pure NFC film to 180 Ω/sq. Further addition of 20 (CC3) and 25 wt% (CC4) of NG to 80 and 75 wt% respectively, lowered the sheet resistance to 17 and 9 Ω/sq, respectively. For the mechanical properties, we found that adding 10 wt% NG to 90 wt% NFC of sample HH2 (5 mmol NaClO SP-NFC homogenised for 60 min) improved the tensile index by 28 %, tensile stiffness index by 20 %, and peak load by 28 %. The film’s surface morphology was visualised using scanning electron microscopy, revealing the fibrillated structure of NFC and NG. This methodology yields NFC–NG films that are mechanically stable, bendable, and flexible. 相似文献