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91.
Ranjit Bag Sourav Kar Suvam Saha Suman Gomosta Beesam Raghavendra Thierry Roisnel Sundargopal Ghosh 《化学:亚洲杂志》2020,15(6):780-786
Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe2(CO)9] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl4] (Cp*=η5‐C5Me5) and [LiBH4?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ3‐BH)2H2{Cp*W(CO)2}2{Fe(CO)2}] ( 1 ) and bis‐borylene, [(μ3‐BH)2{Cp*W(CO)2}2{Fe(CO)3}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru3(CO)12]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ3‐BH)2{WCp*(CO)2}2{Ru(CO)3}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co2(CO)8] with nido‐[(RhCp*)2(B3H7)], which afforded triply‐bridging bis‐borylene species [(μ3‐BH)2(RhCp*)2Co2(CO)4(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; 1H, 11B, 13C NMR spectroscopy; IR spectroscopy and mass spectrometry. 相似文献
92.
Thierry K. Slot N. Raveendran Shiju Gadi Rothenberg 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(48):17433-17436
We present a new device for quantifying gases or gas mixtures based on the simple principle of bubble counting. With this device, we can follow reaction kinetics down to volume step sizes of 8–12 μL. This enables the accurate determination of both time and size of these gas quanta, giving a very detailed kinetic analysis. We demonstrate this method and device using ammonia borane hydrolysis as a model reaction, obtaining Arrhenius plots with over 300 data points from a single experiment. Our device not only saves time and avoids frustration, but also offers more insight into reaction kinetics and mechanistic studies. Moreover, its simplicity and low cost open opportunities for many lab applications. 相似文献
93.
A new simple chronoamperometry methodology was developed for the ultrasensitive determination of lead ions using a PEDOT:PSS coated graphite carbon electrode. The polymer was directly coated on a graphite carbon electrode and characterized using simple cycle voltammetric measurements. The presence of lead ions induced a cathodic peak starting at −550 ± 10 mV vs. Ag/AgCl, and an anodic peak starting at −360 ± 10 mV vs. Ag/AgCl. Electroaccumulation of lead ions onto the PEDOT:PSS modified electrode was performed at −650 mV vs. Ag/AgCl for 30 s in a pH 2.2 hydrochloric acid solution. Chronoamperometry measurements were carried out at −350 mV vs. Ag/AgCl allowing the oxidation of accumulated lead. Using this method, lead ions were detected for concentrations ranging between 2.0 nmol L−1 and 0.1 μmol L−1 (R2 = 0.999). The detection limit was calculated to be 0.19 nmol L−1 and the quantification limit of 0.63 nmol L−1. The method was shown to be highly precise and sensitive, negligible interference was detected from other metal ions. The proposed method was successfully applied for the detection of lead ions in vegetables. 相似文献
94.
Massicot F Iriarte AM Brigaud T Lebrun A Portella C 《Organic & biomolecular chemistry》2011,9(2):600-603
The diketone 2-fluoro-2-(trifluoromethyl)-1-phenylhexane-1,5-dione 3 was synthesized by a Mukaiyama Michael type reaction from the corresponding tetrafluoroenol silyl ether prepared from pentafluoropropiophenone. This diketone was treated under basic conditions and was converted, depending on the stoichiometry of the base, into the surprisingly stable ketol 4-fluoro-4-(trifluoromethyl)-3-hydroxy-3-phenylcyclohexanone 4 as a single diastereomer (catalytic KOH) or to the biphenylol 6-(trifluoromethyl)biphenyl-3-ol (excess KOH, THF) 5. Solvolysis of the trifluoromethyl group (anionic activation) occurred using excess KOH in alcohol. The corresponding cyclohexenone derivative 7, the usual product of Robinson annulation, might be prepared in good yield via mesylation of the ketol. Thus various unprecedented fluorinated cyclohexane and aromatic derivatives were achieved in a few steps from the commercially available pentafluoropropiophenone. 相似文献
95.
The determination of seven arsenic species in seafood was performed using ion exchange chromatography on an IonPac AS7 column with inductively coupled plasma mass spectrometry detection after microwave assisted extraction. The effect of five parameters on arsenic extraction recoveries was evaluated in certified reference materials. The recoveries of total arsenic and of arsenic species with the two best extraction media (100% H2O and 80% aqueous MeOH) were generally similar in the five seafood certified reference materials considered. However, because MeOH co-elutes with arsenite, which would result in a positively biased arsenite concentration, the 100% H2O extraction conditions were selected for validation of the method. Figures of merit (linearity, LOQs (0.019-0.075 mg As kg−1), specificity, trueness (with recoveries between 82% (As(III)) and 104% (As(V) based on spikes or certified concentrations), repeatability (3-14%), and intermediate precision reproducibility (9-16%) of the proposed method were satisfactory for the determination of arsenite, monomethylarsonic acid, dimethylarsinic acid, arsenate, arsenobetaine and arsenocholine in fish and shellfish. The performance criteria for trimethylarsine oxide, however, were less satisfactory. The method was then applied to 65 different seafood samples. Arsenobetaine was the main species in all samples. The percentage of inorganic arsenic varied between 0.4-15.8% in shellfish and 0.5-1.9% at the utmost in fish. The main advantage of this method that uses only H2O as an extractant and nitric acid as gradient eluent is its great compatibility with the long-term stability of both IEC separation and ICP-MS detection. 相似文献
96.
Kevin Grollier Arnaud De Zordo-Banliat Flavien Bourdreux Dr. Bruce Pegot Dr. Guillaume Dagousset Dr. Emmanuel Magnier Dr. Thierry Billard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):6028-6033
The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two-step strategy based on a metal-free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88 %, which raised to 98 % in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physicochemical characterization of these emerging groups was performed by determining their Hansch–Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95 %. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives. 相似文献
97.
98.
Le Bihan T Duewel HS Figeys D 《Journal of the American Society for Mass Spectrometry》2003,14(7):719-727
We have developed an on-line strong cation exchange (SCX)-ESI-MS/MS platform for the rapid identification of proteins contained in mixtures. This platform consists of a SCX precolumn followed by a nanoflow SCX column on-line with an electrospray ion trap mass spectrometer. We also used this platform to study the dynamics of peptide separation/extraction by SCX, in particular to understand the parameters affecting the performance of SCX in multidimensional chromatography. For example, we have demonstrated that the buffer typically used for tryptic digestion of protein mixtures can have a detrimental effect on the chromatographic behaviour of peptides during SCX separations, thereby affecting certain peptide quantitation approaches that rely on reproducible peptide fractionation. We have also demonstrated that band broadening results when a step (discontinuous) gradient approach is used to displace peptides from the SCX precolumn, reducing the separation power of SCX in multidimensional chromatography. In contrast, excellent chromatographic peak shapes are observed when a defined (continuous) gradient is used. Finally, using a tryptic digest of a protein extract derived from human K562 cells, we observed that larger molecular weight peptides are identified using this on-line SCX approach compared to the more conventional reverse phase (RP) LC/MS approach. Both methods used in tandem complement each other and can lead to a greater number of peptide identifications from a given sample. 相似文献
99.
Siham El FangourAlexandre Guy Jean-Pierre VidalJean-Claude Rossi Thierry Durand 《Tetrahedron letters》2003,44(10):2105-2108
The first synthesis of the two enantiomers of phytoprostane F1 methyl ester 1 and 2 is described using the syn-anti-syn alcoxy ester 3 as starting material. 相似文献
100.
Clément Ghiazza Vincent Debrauwer Dr. Cyrille Monnereau Lhoussain Khrouz Dr. Maurice Médebielle Dr. Thierry Billard Dr. Anis Tlili 《Angewandte Chemie (International ed. in English)》2018,57(36):11781-11785
The first visible‐light‐mediated synthesis of trifluoromethylselenolated arenes under metal‐free conditions is reported. The use of an organic photocatalyst enables the trifluoromethylselenolation of arene diazonium salts using the shelf‐stable reagent trifluoromethyl tolueneselenosulfonate at room temperature. The reaction does not require the presence of any additives and shows high functional‐group tolerance, covering a very broad range of starting materials. Mechanistic investigations, including EPR spectroscopy, luminescence investigations, and cyclic voltammetry allow rationalization of the reaction mechanism. 相似文献