全文获取类型
收费全文 | 817篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 646篇 |
晶体学 | 5篇 |
力学 | 18篇 |
数学 | 77篇 |
物理学 | 105篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 35篇 |
2021年 | 49篇 |
2020年 | 27篇 |
2019年 | 37篇 |
2018年 | 21篇 |
2017年 | 18篇 |
2016年 | 27篇 |
2015年 | 35篇 |
2014年 | 46篇 |
2013年 | 65篇 |
2012年 | 66篇 |
2011年 | 79篇 |
2010年 | 40篇 |
2009年 | 34篇 |
2008年 | 47篇 |
2007年 | 51篇 |
2006年 | 41篇 |
2005年 | 26篇 |
2004年 | 24篇 |
2003年 | 14篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 8篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1969年 | 1篇 |
1965年 | 2篇 |
排序方式: 共有851条查询结果,搜索用时 15 毫秒
11.
Zorica M. Bugar?i? Vera M. Divac Mariana P. Gavrilovi? 《Monatshefte für Chemie / Chemical Monthly》2007,40(9):985-988
An efficient protocol for the preparation of phenylselenoethers from unsaturated alcohols using phenylselenenyl halides at
room temperature was developed. The procedure employs phenylselenenyl chloride and bromide, some Δ 4- and Δ 5-alkenols and Ag2O, as an additive, to generate the tetrahydropyrans or tetrahydrofurans. This method permits the preparation of cyclic phenylselenoethers
in high yields and under extremely mild conditions. 相似文献
12.
Boris Shivachev Rosica Petrova Petja Marinova Neyko Stoyanov Anife Ahmedova Mariana Mitewa 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):o211-o215
The crystal structures of four cycloalkanespiro‐4′‐imidazolidine‐2′,5′‐dithiones, namely cyclopentanespiro‐4′‐imidazolidine‐2′,5′‐dithione {systematic name: 1,3‐diazaspiro[4.4]nonane‐2,4‐dithione}, C7H10N2S2, cyclohexanespiro‐4′‐imidazolidine‐2′,5′‐dithione {systematic name: 1,3‐diazaspiro[4.5]decane‐2,4‐dithione}, C8H12N2S2, cycloheptanespiro‐4′‐imidazolidine‐2′,5′‐dithione {systematic name: 1,3‐diazaspiro[4.6]undecane‐2,4‐dithione}, C9H14N2S2, and cyclooctanespiro‐4′‐imidazolidine‐2′,5′‐dithione {systematic name: 1,3‐diazaspiro[4.7]dodecane‐2,4‐dithione}, C10H16N2S2, have been determined. The three‐dimensional packing in all of the structures is based on closely similar chains, in which hydantoin moieties are linked through N—H⋯S hydrogen bonding. The size of the cycloalkane moiety influences the degree of its deformation. In the cyclooctane compound, the cyclooctane ring assumes both boat–chair and boat–boat conformations. 相似文献
13.
Alvisi D Blart E Bonini BF Mazzanti G Ricci A Zani P 《The Journal of organic chemistry》1996,61(20):7139-7146
The palladium-catalyzed desilylation-arylation of substituted vinylsilanes by p-iodoanisole in the presence of bidentate phosphine ligands is described. Apart from enhancing the rate of the reaction considerably, heteroatom-based functional groups in the vinylsilane moiety have a profound influence on the regiochemistry. A catalytic cycle for the chelation-controlled desilylation-arylation reaction involving five- and six-membered chelate rings is proposed. 相似文献
14.
Rasa Pauliukaite Mariana Emilia Ghica Madalina Barsan Christopher M. A. Brett 《Journal of Solid State Electrochemistry》2007,11(7):899-908
The polymer redox mediator, poly(neutral red) (PNR), has been synthesised and characterised electrochemically to investigate
the best electropolymerisation and mediation conditions for application in enzyme biosensors and to clarify the mechanism
of action. Neutral red was electropolymerised by potential cycling on carbon film electrode substrates by allowing the monomer
to be oxidised during the full 20 cycles of polymerisation or reducing the positive limit of the potential window after the
first 2 cycles to impede monomer oxidation with a view to obtaining longer polymer chains and a lesser degree of branching.
Comparison was made with glassy carbon substrates. The PNR films on carbon film electrodes were characterised using cyclic
voltammetry and electrochemical impedance spectroscopy, as well as in glucose biosensors prepared with PNR. Glucose oxidase
enzyme was immobilised by encapsulation in silica sol-gel and compared with that obtained by cross-linking with glutaraldehyde.
The biosensors were evaluated by chronoamperometry in 0.1 M phosphate buffer saline solution, pH 7.0, and showed evidence
of electron transfer between the enzyme cofactor flavin adenine dinucleotide and PNR dissolved in the enzyme layer competing
with PNR-mediated electrochemical degradation of H2O2 formed during the enzymatic process.
This paper is dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday. 相似文献
15.
Mariana Antunes Vieira Bernhard Welz Adilson Jos Curtius 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):251-2067
A simple and reliable method for the determination of arsenic in sediment and in coal without sample digestion, based on hydride generation from slurry samples is proposed. After grinding the samples to a particle size of 50 μm, the sample powder was mixed with aqua regia and hydrofluoric acid in an ultrasonic bath for 30 min. After diluting the mixture with hydrochloric acid, the slurry was allowed to stand for 48 h, and an aliquot was used for hydride generation with sodium borohydride. More than 80% of the arsenic was leached to the aqueous phase under these conditions, except for one sediment sample with very high silica content. The generated arsine was collected in a graphite tube, treated with 0.5 mg of iridium as a permanent modifier, and the arsenic determination was carried out by electrothermal atomic absorption spectrometry. The same tube could be used for at least 160 cycles without any re-treatment. The greatest advantage of the method was that only a minimum of reagents and sample handling were required, reducing the risks of contamination and/or analyte loss. However, the addition calibration technique had to be used in order to obtain results within the 95% confidence level for 11 certified reference materials, 5 sediments, 5 coals and one coal fly ash. One certified sediment slurry was spiked with the analyte and the resulting addition calibration curve was used for the analysis of the certified sediments. Similarly, one certified coal was used to obtain the addition calibration curve for the coal and coal fly ash samples. The recoveries of the certified values, except for one sediment, were between 91 and 115%. The limits of detection in the samples were 0.54 and 0.7 μg g−1 for the coal and sediment samples, respectively, obtained for 1 ml of slurry containing 1 mg of sample. 相似文献
16.
The activity of enzyme I (EI), the first protein in the bacterial PEP:sugar phosphotransferase system, is regulated by a monomer–dimer equilibrium where a Mg2+-dependent autophosphorylation by PEP requires the homodimer. Using inactive EI(H189A), in which alanine is substituted for the active-site His189, substrate binding effects can be separated from those of phosphorylation. Whereas 1 mM PEP (with 2 mM Mg2+) strongly promotes dimerization of EI(H189A) at pH 7.5 and 20 °C, 5 mM pyruvate (with 2 mM Mg2+) has the opposite effect. A correlation between the coupling of N- and C-terminal domain unfolding, measured by differential scanning calorimetry, and the dimerization constant for EI, determined by sedimentation equilibrium, is observed. That is, when the coupling between N- and C-terminal domain unfolding produced by 0.2 or 1.0 mM PEP and 2 mM Mg2+ is inhibited by 5 mM pyruvate, the dimerization constant for EI(H189A) decreases from >108 to <5 × 105 or 3 × 107 M−1, respectively. With 2 mM Mg2+ at 15–25 °C and pH 7.5, PEP has been found to bind to one site/monomer of EI(H189A) with KA′106 M−1 (ΔG′=−33.7±0.2 kJ mol−1 and ΔH=+16.3 kJ mol−1 at 20 °C with ΔCp=−1.4 kJ K−1 mol−1). The binding of PEP to EI(H189A) is synergistic with that of Mg2+. Thus, physiological concentrations of PEP and Mg2+ increase, whereas pyruvate and Mg2+ decrease the amount of dimeric, active, dephospho-enzyme I. 相似文献
17.
A Partial Statistically Incorporation of Ca2+ into the Ba6Nd2Al4O15-Type: Ba5CaLa2Fe4O15 Using high temperature reactions we succeeded in incorporating Ca2+ into the Ba6Nd2Al4O15 type. Single crystal X-ray methods reveal a partly ordered alkaline earth distribution. Ba2+ and Ca2+ occupy face connected MO6-octahedra as well as a further point position together with La3+ ions (space group C−P63mc; a = 11.770; c = 7.039 Å; Z = 2). 相似文献
18.
The electron impact mass spectra of the 4-formyl-1, 3-dihydro-2H-imidazole-2-thione, its six 1-methyl(n-propyl, n-hexyl)-3-methyl(phenyl)-disubstptuted derivatives, and the 1,3-dihydro-1-phenyl-2H-imidazole-2-thiome are discussed. The fragmentation pattern is strongly influenced by the alkyl or phenyl N-substituents, as well as by the length of the alkyl chain. The odd-electron ions containing an N-phenyl substituent, but not a propyl or hexyl group, eject a hydrogen atom from the phenyl ring, while the presence of a long alkyl chain greatly enhances the loss of the sulphyhydryl radical and facilitates the expulsion of several alkenes, and alkyl and alkenyl radicals. 相似文献
19.
Eva Martínez-Ahumada Mariana L. Díaz-Ramírez Miriam de J. Velsquez-Hernndez Vojtech Jancik Ilich A. Ibarra 《Chemical science》2021,12(20):6772
MOFs are promising candidates for the capture of toxic gases since their adsorption properties can be tuned as a function of the topology and chemical composition of the pores. Although the main drawback of MOFs is their vulnerability to these highly corrosive gases which can compromise their chemical stability, remarkable examples have demonstrated high chemical stability to SO2, H2S, NH3 and NOx. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases. Thus, the interactions of such functional groups (coordinatively unsaturated metal sites, μ-OH groups, defective sites and halogen groups) with these toxic molecules, not only determines the capture properties of MOFs, but also can provide a guideline for the desigh of new multi-functionalised MOF materials. Thus, this perspective aims to provide valuable information on the significant progress on this environmental-remediation field, which could inspire more investigators to provide more and novel research on such challenging task.MOFs are promising candidates for the capture of toxic gases such as SO2, H2S, NH3 and NOx. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases. 相似文献
20.
Mariana Dennehy Oscar V. Quinzani Robert A. Burrow 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):m395-m397
The centrosymmetric title compound, [Ag(C7H4NO2S2)]n, consists of dinuclear units in which two thiosaccharinate anions each bridge two Ag atoms via an endocyclic N atom and an exocyclic S atom across a crystallographic centre of inversion midway between the Ag atoms. The dimeric units are connected via Ag—Sexo interactions to create two‐dimensional networks. The thiosaccharinate anions bridge in a μ3‐S:S:N manner. The Ag...Ag distance can be considered a strong argentophilic interaction. 相似文献