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81.
The kinetics of the reaction between organocobaloximes, RCo(DH)2H2O, and iodine have been investigated. They reveal the participation of an RCo(DH)2H2O · I2 intermediate which undergoes intramolecular transalkylation and acts as an electrophile towards a second organocobaloxime molecule. The trend in reactivity as the R group is varied is discussed. 相似文献
82.
Hamelin O Pécaut J Fontecave M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(10):2548-2554
Recently, we observed that the enantiopure Lambda form of the tributylammonium salt of the chiral anion tris[tetrachlorobenzene-1,2-bis(olato)]phosphate, also named Trisphat, was able to induce an efficient resolution of a Delta,Lambda racemic mixture of cis-[Ru(dmp)2(NCCH3)2](PF6)2 (dmp=2,9-dimethyl-1,10-phenanthroline) due to the spontaneous and selective precipitation of the heterochiral pair [Delta-Ru(dmp)2(CH3CN)2][Lambda-Trisphat]2. We report here that the combination of such a stereoselective precipitation process and irradiation results in the quantitative conversion of the initial [Ru(dmp)2(NCCH3)2]2+ racemate into only one of the two enantiomers. This is the first example in inorganic chemistry of an asymmetric transformation that leads to a chiral complex with no chiral ligand. Finally, three new racemic ruthenium bis(diimine) complexes, namely [Ru(dmp)2(NCCH3)Py](PF6)2 (Py=pyridine), [Ru(dmp)2(1,3-diaminopropane)](PF6)2, and [Ru(dmp)2(ethylenediamine)](PF6)2 were synthesized. For all of them, crystallization-induced asymmetric transformation proved to be an efficient way of obtaining the corresponding optically active chiral-at-metal complexes in high yields and with excellent stereoselectivities. 相似文献
83.
A novel oligothiophene derivative containing the triphenylamine moiety with high glass transition temperature (Tg; 135 °C), 5,5′‐{bis[4‐di(4‐thiophenyl)amino]phenyl}‐2,2′‐bithiophene (TTPA‐dimer) was synthesized by the dimerization of tris[4‐(2‐thienyl)phenyl]amine (TTPA) with a palladium catalysis. Some types of electroluminescent (EL) devices that use the amorphous material for a hole‐ and an electron‐transporting with an emitting layer were fabricated. These devices emitted a bright green‐yellowish light (λemi; around 510 nm) with a small full width at half maximum (FWHM) rather than that of Alq3. The single layer EL device showed a maximum luminance of 221 cd/m2 at 8 V (0.06 lm/W at 100 cd/m2). On the other hand, the double layer (TTPA‐dimer/Alq3) EL device that used Alq3 as the electron transport material was increased up to 10830 cd/m2 at 12 V (0.89 lm/W at 300 cd/m2) and with a lower turn‐on voltage (3.2 V at 0.1 cd/m2) than other types of EL devices. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
84.
在B3LYP/6-311 G(2df,p)的水平上,对反应X- CH3SCl(X=F,Cl,Br,I)进行了理论研究.计算结果表明:X-(X=Cl,Br,I)与CH3SCl作用时,实际发生的是在硫原子上而不是在碳原子上的亲核取代反应,而且属于加成-消去机理.但是F-与CH3SCl作用则容易发生脱质子反应. 相似文献
85.
Molecular mechanics calculations on cycloheptadiene indicate that the molecule has a structure which undergoes a wide pseudorotational motion between two C1 forms, and a C1 form, and this structure is in equilibrium with the C2 form. It is shown that this equilibrium mixture is consistent with all of the available experimental data. 相似文献
86.
Othman A. Farghaly 《Microchemical Journal》2003,75(2):119-131
Tap water samples (Assiut city, lie in the middle north of upper Egypt, approx. 370 km from Cairo, January-March, 2002) were taken from the eight sampling sites of different locations at Assiut city. The samples are analyzed to determine the total content of cadmium, copper, lead and zinc by differential pulse anodic stripping voltammetry (DPASV) while nickel and cobalt are determined by a new simple differential pulse adsorptive stripping voltammetry (DPAdSV), using dimethylglyoxime (DMG) as the complexing agent. This method uses sodium sulfite as the supporting electrolyte, which facilitates the removal of oxygen interference without the traditional necessity of purging with inert gas. The effect of various parameters was studied using DPASV (for Cd, Pb, Cu and Zn) and AdSV (for Ni and Co) methods. Subsequently, under the so found experimental conditions, the stability of calibration curves and the detection limits (μg/l) have been determined. The data achieved (for all metals utility) are comparable to those measured by the graphite furnace atomic absorption spectrophotometric (GF-AAS) method. The effects of the interferences between these metal ions have been investigated. Moreover, the effect of storage was discussed and the obtained results were compared favorably with standard official methods. Statistical analysis of the database exhibits applicability and the accuracy of the techniques. The results obtained from the two techniques (Voltammetry and GF-AAS) are in very good agreements in the most tap water samples. 相似文献
87.
Studies of the preparation of 1,8-dihydroazocines and transannular cyclization of hydroazocines to produce functionalized pyrrolizidines are described. Results are presented which demonstrate that unsymmetrically substituted acetylenes bearing at least one electron withdrawing groups undergo efficient cycloaddition to 1 - β - styryl - 1,2 - dihydropyridine producing in a regio-selective fashion 3,4 - disubstituted - 1,8 - dihydroazocines. The dihydroazocines generated in this manner can be converted to 1 - formyl - Δ4,5 - epoxyazocines which undergo interesting rearrangement reactions to form pyrrolizidines when subjected to methoxide deformylation followed by acid treatment. In addition, 1,6,7,8 - tetrahydroazocines can be converted to pyrrolizidines under bromination conditions. The intriguing chemical process which occur under the conditions outlined above are described. 相似文献
88.
Chemical Reduction of CO2 to Different Products during Photo Catalytic Reaction on TiO2 under Diverse Conditions: an Overview
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The chemical reduction of CO_2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials.The conversion of CO_2 into useful substances is essential in developing al- ternative fuels and various raw materials for different in- dustries.This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO_2.In this article an overview of the growth taken place so far in the field of CO_2 chemical reduction is pre- sented.The discussion comprises of photochemical meth- ods for the development of different products,viz.CO, CH_3O_H and CH_4,through chemical reduction of CO_2. This includes the use of photo catalysts,mainly TiO_2, and the role of a hole scavenger(such as 2-propanol)for this purpose. 相似文献
89.
90.
Amphiphilic diblock copolymers consisting of a hydrophobic polystyrene block (PS) and a hydrophilic poly(ethylene oxide)
block (PEO) with block sizes of 1000 or 3000 g/mol for both blocks were studied at the air/water and toluene/water interface.
Measurements of the film pressure π of spread monolayers at the water surface reveal two limiting regimes of the π−a
m isotherms, in which the mean molecular area a
m is determined either by the size of the hydrophilic or the hydrophobic blocks of the PS-PEO molecules. The interfacial activity
of the block copolymers at the toluene/water interface was studied by measuring the interfacial tension σ over a wide range
of concentrations. Pronounced differences in the temperature dependence of the interfacial tension were observed, depending
mostly on the block length of the hydrophilic PEO block. From the temperature dependence of σ it is inferred that for the
block copolymers with the PEO block size of 3000 g/mol the phase inversion temperature (PIT) is well above 60 °C while for
those with a PEO block size of 1000 g/mol the PIT is below or near 25 °C in the toluene/water system.
Received: 5 February 1998 Accepted: 16 February 1998 相似文献