全文获取类型
收费全文 | 1975篇 |
免费 | 84篇 |
国内免费 | 17篇 |
专业分类
化学 | 1385篇 |
晶体学 | 17篇 |
力学 | 44篇 |
数学 | 356篇 |
物理学 | 274篇 |
出版年
2023年 | 18篇 |
2022年 | 9篇 |
2021年 | 18篇 |
2020年 | 34篇 |
2019年 | 33篇 |
2018年 | 32篇 |
2017年 | 31篇 |
2016年 | 62篇 |
2015年 | 58篇 |
2014年 | 52篇 |
2013年 | 120篇 |
2012年 | 135篇 |
2011年 | 128篇 |
2010年 | 67篇 |
2009年 | 79篇 |
2008年 | 128篇 |
2007年 | 148篇 |
2006年 | 143篇 |
2005年 | 104篇 |
2004年 | 94篇 |
2003年 | 72篇 |
2002年 | 85篇 |
2001年 | 46篇 |
2000年 | 49篇 |
1999年 | 28篇 |
1998年 | 23篇 |
1997年 | 24篇 |
1996年 | 33篇 |
1995年 | 19篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 16篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 11篇 |
1988年 | 10篇 |
1987年 | 8篇 |
1986年 | 3篇 |
1985年 | 17篇 |
1984年 | 9篇 |
1982年 | 5篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1971年 | 5篇 |
1962年 | 3篇 |
排序方式: 共有2076条查询结果,搜索用时 0 毫秒
51.
52.
Jim Ho 《Analytica chimica acta》2002,457(1):125-148
Biological aerosol detection in real time is an urgent civilian and military requirement. Such detection capability will be useful in environmental monitoring, for example, in gathering information in perceived hazardous areas such as housing developments downwind of sewage treatment plants. To be truly functional, the instrument has to operate continuously, 24 h a day and 7 days a week with minimal maintenance and few false alarms. A novel concept is proposed. The system employs a rapid front-end warning/alarming mechanism based on optical technologies that provides useful information for protection decision makers. This is connected to a sample collector that feeds a slower back-end liquid chemistry system that provides analytical results to the medical personnel to assist in prophylaxis and therapy decisions. Experience gained from measuring fluorescence signals of single bacterial spores under flow cytometry (FCM) using UV excitation at 340-360 nm, was applied to concept testing of a prototype instrument, built to do the same for aerosols. This machine was capable of resolving particle size as well as fluorescence intensity of each particle under laboratory and field conditions; it was called the fluorescent aerodynamic particle sizer (FLAPS). This paper describes practical aspects of measuring biological aerosols when the results must be compared to reference samplers that provide culturable or “live” data. Treatment of particle size and fluorescence information is discussed with respect to FLAPS and reference data fidelity. Along with an objective method to evaluate FLAPS data correlation to reference data, an approach for determining limit of detection in the field is discussed. In addressing the back-end detector chemistry, we have prioritized a number of important biological characteristics that must be given to a clinician to help in prophylaxis and therapy decisions. A series of biochemical measurements are proposed to define the threat of a sample and different solutions are given to implement these tests. We predict that the future for biological detection looks promising for fluorescence in situ hybridization (FISH) techniques in identifying microorganisms. A conceptual instrument based on merging FCM and microchip-based analysis is described. 相似文献
53.
Valle-Algarra FM Medina A Gimeno-Adelantado JV Llorens A Jiménez M Mateo R 《Talanta》2005,66(1):194-201
Various solid-phase extraction (SPE) procedures for clean-up, two perfluoroacylation reagents (pentafluoropropionic anhydride (PFPA) and heptafluorobutyric anhydride (HFBA)) and two chromatographic columns (HP-1701 and HP-5) have been assessed comparatively to achieve the determination of type B trichothecenes (deoxynivalenol (DON), nivalenol (NIV), 3- and 15-acetyldeoxynivalenol (3- and 15-ADON)) in wheat grain by gas chromatography (GC)-electron-capture detection (ECD). Spiked wheat samples were extracted with acetonitrile-water (84:16, v/v). Tested SPE procedures were MycoSep 225 column, Florisil and different cartridges prepared in the laboratory with mixtures of various sorbents like alumina, Celite 545, C18, silica and charcoal. We propose MycoSep 225 column, and cartridges made with alumina-charcoal-silica and alumina-charcoal-C18 silica mixtures as clean-up procedures on the basis of recovery values (89.6, 87.3 and 86.1% for deoxynivalenol, respectively, at 1.0 mg/kg spiking level). The two last procedures are less expensive. Pentafluoropropionic anhydride was more stable against moisture and less expensive, while recoveries were similar to those obtained with heptafluorobutyric anhydride. HP-1701 column can separate 3- and 15-acetyldeoxynivalenol derivatives while HP-5 cannot, although this last column provided lower bleed and better sensitivity. 相似文献
54.
A method for simultaneous analysis of eight azolic fungicides: cyproconazole, diniconazole, tetraconazole, thiabendazole, flusilazole, triadimenol, triadimefon, carbendazim and the degradation product 2-aminobenzimidazole in wine samples is described. The compounds are isolated from the samples and concentrated by solid-phase extraction on polymeric cartridges. The determination is carried out by liquid chromatography with mass spectrometric detection in positive ionization and selected ion monitoring modes. The influence of parameters such as the mobile phase composition, column temperature, corona current and fragmentor voltage is studied and the proposed method is validated. Recoveries of the nine compounds added to wine samples range from 83 to 109%, with relative standard deviations below 10%. The quantitation limits are between 9 and 31 microg/L. Real wine samples are analyzed by the proposed method, also. 相似文献
55.
Phosphate selective electrodes have been produced based upon rubbery membranes containing heterocylic macrocycles as sensors covalently bound to a cross-linked polystyrene-block–polybutadiene-block–polystyrene (SBS) polymer. The membranes were robust and the best HPO42−-selective membrane fabricated was composed of 7.1% (m/m) dicumyl peroxide, 28.3% (m/m) 2-nitrophenyloctylether, 9.8% (m/m) 3-(10-undecenyl)-1,5,8-triazacyclodecane-2,4-dione, 31.0% (m/m) SBS and 23.8% (m/m) PoleStar™ 200R (clay-based filler). The characteristics of this electrode were a linear Nernstian range of 3.9×10−3 to 1×10−6 mol dm−3 HPO42− with a limit of detection of 1.0×10−6 mol dm−3 HPO42−, a slope of −29.7±0.9 mV per activity decade and a pH range from 6 to 8. Selectivity coefficients for phosphate against various interfering anions (chloride, sulfate and nitrate) were determined. Response times were 2 min or under, stability of response and electrode lifetime in continuous use were also very satisfactory. The response behavior of HPO42−-ISEs based upon mobile and bound ionophores was comparable and suggests that mobility of the ionophore is not necessary to obtain a working ISE and that covalent binding of ionophores can be used to produce ISEs of increased stability and robustness. 相似文献
56.
Maria Luisa Moyá Antonio Barrios Maria del Mar Graciani Rafael Jiménez Ernestina Muñoz Francisco Sánchez John Burgess 《Transition Metal Chemistry》1991,16(2):165-168
Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4-bipy)]3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (kL/s–1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G
exp
with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of G
calc
versus G
exp
are linear with slopes of near unity. 相似文献
57.
Jim Agler 《Integral Equations and Operator Theory》1982,5(1):608-631
We develop techniques which allow one to describe in simple terms the set of operators on Hilbert space of the form M* () |M, where M is multiplication by z on a Hilbert space of analytic functions satisfying certain technical assumptions, M* () is the direct sum of a countably infinite number of copies of M*, andM is invariant for M* (). One of the main ingredients in our technique is the Arveson Extension Theorem and this paper illustrates the great power and tractability of that theorem in a concrete setting.Research partially supported by NSF grant MCS 81-02518 相似文献
58.
Jiménez JC Chavarría B López-Macià A Royo M Giralt E Albericio F 《Organic letters》2003,5(12):2115-2118
[reaction: see text] A solid-phase method for the synthesis of tentoxin has been developed. Two key steps-dehydration and N-alkylation-are carried out while the peptide is anchored to the resin. The method, which has been validated by the preparation of a library of tentoxin analogues, should be applicable to the generation of further libraries that have the tentoxin scaffold structure, as well as other structures containing N-alkylated didehydroamino acids. 相似文献
59.
Francisco Ros Pilar Jiménez María Victoria Roux 《Monatshefte für Chemie / Chemical Monthly》2007,28(4):941-949
The cohesion potential energy of the crystal of one enantiomer of ethyl 3-cyano-3-(3,4-dimethyloxyphenyl)-2,2,4-trimethylpentanoate,
−47.7 ± 0.1 kJ mol−1 (0–90°C), was found out from the heat of sublimation (123.2 ± 5.1 kJ mol−1, 78.6°C) and the kinetic energies for the gas phase and the crystal. It was found that the entropy function of Debye’s theory of solids mathematically agreed with the vibrational entropy of the gas (variationally obtained), allowing to disclose
the vibrational energy using the Debye energy function (E
vib 835.0 kJ mol−1 (78.6°C), E
0 included). E
kin for the crystal (771.1 kJ mol−1 (78.6°C)) was obtained by Debye’s theory with the experimental heat capacity. The cohesion energy represented a moderate part of the sublimation energy.
The cohesion energy of the racemic crystal, −44.2 kJ mol−1, was obtained by the heat of formation of the crystal in the solid state (3.0 kJ mol−1, 83.3°C) and E
kin for the crystal (by Debye’s theory). The decrease in cohesion on formation of the crystal accounted for the energy of formation. The change in potential
energy on liquefaction of the racemate from the gas state was disclosed obtaining added-up E
vib + rot for the liquid in the way as to E
vib for the gas, the Debye entropy function being increasedly suited for the liquid (E
vib + rot 763.4 kJ mol−1 (115.4°C)). Positive ΔE
pot, 13.0 kJ mol−1, arised from the increase in electronic energy (Δ
l
νmean − 154.3 cm−1, by the dielectric nature of the liquid), added to the cohesion energy. 相似文献
60.
Pericàs MA Puigjaner C Riera A Vidal-Ferran A Gómez M Jiménez F Muller G Rocamora M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4164-4178
New families of enantiopure bis(oxazolines) with 4,5-trans (5 a-g) or 4,5-cis (6 c) stereochemistry at the individual rings have been prepared in high yield. Their eta(3)-allyl palladium complexes (8 a-g, 9 c and 10) have been used as catalytic precursors in allylic alkylation reactions with excellent enantioselectivities (up to 96 %) for the trans oxazoline derivatives, while Pd/6 c system was inactive. NMR studies on palladium eta(3)-1,3-diphenylallyl intermediates (11 a, c and e) showed the presence of syn/syn- and syn/anti-allyl isomers in solution; this resembles the first example of eta(3)-eta(1)-eta(3) isomerism in Pd allylic complexes containing bis(oxazolines) derived from malonic acid. 相似文献