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151.
Fabio Fenili Clara Rigamonti Alberto Bossi Paolo Ferruti Amedea Manfredi Stefano Maiorana Clara Baldoli Silvia Cauteruccio Emanuela Licandro Elisabetta Ranucci 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4704-4710
A tetrathia‐[7]‐helicene bearing in the 2 and 13 positions cyanovinyl groups was used as comonomer in the Michael‐type polyaddition reaction with N,N′‐bis(β‐mercaptoethyl)piperazine. This led to a new polymer bearing tetrathia‐[7]‐helicene units regularly distributed along the polymer backbone, which may be regarded as the first example of a new family of potentially useful nonlinear optical materials. All products were structurally characterized by 1H and 13C NMR spectroscopy. Differential scanning calorimetry characterizations revealed the presence, in both monomeric and polymeric helicenes, of glass‐transition like temperatures, associated to some conformational variation of the helicene units. The optical properties, the film formation and the morphology of the polymer‐containing tetratia‐[7]‐helicenes were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
152.
Ranieri A Monari S Sola M Borsari M Battistuzzi G Ringhieri P Nastri F Pavone V Lombardi A 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):17831-17835
Mimochrome VI (MC-VI) is a synthetic heme peptide containing a helix-heme-helix sandwich motif designed to reproduce the catalytic activity of heme oxidases. The thermodynamics of Fe(III) to Fe(II) reduction and the kinetics of the electron-transfer process for MC-VI immobilized through hydrophobic interactions on a gold electrode coated with a nonpolar SAM of decane-1-thiol have been determined through cyclic voltammetry. Immobilization slightly affects the reduction potential of MC-VI, which under these conditions electrocatalytically turns over molecular oxygen. This work sets the premise for the exploitation of totally synthetic mimochrome-modified electrode surfaces for clinical and pharmaceutical biosensing. 相似文献
153.
Livraghi S Corazzari I Paganini MC Ceccone G Giamello E Fubini B Fenoglio I 《Chemical communications (Cambridge, England)》2010,46(44):8478-8480
A safe UV filter may be obtained by inhibiting the photo-generation of free radicals through modification of the surface of TiO(2) nanoparticles with carbon. 相似文献
154.
155.
The salts [S(NMe2)3][MF6] (M = Nb, 2a; M = Ta, 2b) and [S(NMe2)3][M2F11] (M = Nb, 2c; M = Ta, 2d) have been prepared by reacting MF5 (M = Nb, 1a; M = Ta, 1b) with [S(NMe2)3][SiMe3F2] (TASF reagent) in the appropriate molar ratio. The solid state structure of 2b has been ascertained by X-ray diffraction. The 1:1 molar ratio reactions of 1a with a variety of organic compounds (L) give the neutral adducts NbF5L [L = Me2CO, 3a; L = MeCHO, 3b; L = Ph2CO, 3c; L = tetrahydrofuran (thf), 3d; L = MeOH, 3e; L = EtOH, 3f; L = HOCH2CH2OMe, 3g; L = Ph3PO, 3h; L = NCMe, 3i] in good yields. The complexes MF5L [M = Nb, L = HCONMe2, 3j; M = Nb, L = (NMe2)2CO, 3k; M = Ta, L = (NMe2)2CO, 3l; M = Nb, L = OC(Me)CHCMe2, 3m] have been detected in solution in admixture with other unidentified products, upon 2:1 molar reaction of 1 with the appropriate reagent L. The ionic complexes [NbF4(tht)2][NbF6], 4a, and [NbF4(tht)2][Nb2F11], 4b, have been obtained by combination of tetrahydrothiophene (tht) and 1a, in 1:1 and 2:3 molar ratios, respectively. The treatment of 1 with a two-fold excess of L leads to the species [MF4L4][MF6] [M = Nb, L = HCONMe2, 5a; M = Ta, L = HCONMe2, 5b; M = Nb, L = thf, 5c; M = Ta, L = thf, 5d; M = Nb, L = OEt2, 5e]. The new complexes have been fully characterised by NMR spectroscopy. Moreover, the revised 19F NMR features of the known compounds MF5L [M = Ta, L = Me2CO, 3n; M = Ta, L = Ph2CO, 3o; M = Ta, L = MePhCO, 3p; M = Ta, L = thf, 3q; M = Nb, L = CH3CO2H, 3r; M = Nb, L = CH2ClCO2H, 3s; M = Ta, L = CH2ClCO2H, 3t], TaF4(acac), TaF4(Me-acac) and [TaF(Me-acac)3][TaF6] (Me-acac = methylacetylacetonato anion) are reported. 相似文献
156.
157.
Gustavo Merola Stefano Gentili Franco Tagliaro Teodora Macchia 《Analytical and bioanalytical chemistry》2010,397(7):2987-2995
A simple procedure combining headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC/MS)
to detect and quantify amphetamines, ketamine, methadone, cocaine, cocaethylene and ∆9-tetrahydrocannabinol (THC) in hair is described. This procedure allows, in a single sample, even scant, analysis of drugs
requiring different analytical conditions. A hair sample (10 mg) is washed and subjected to acidic hydrolysis. Then the HS-SPME
is carried out (10 min at 90 °C) for amphetamines, ketamine, methadone, cocaine and cocaethylene. For derivatization of analytes,
the fibre is introduced into the headspace of another closed vial containing acetic anhydride. After a chromatographic run,
an alkaline hydrolysis for THC analysis is carried out in the same vial containing the hair sample previously used. For adsorption,
the solid-phase microextraction needle is inserted into the headspace of the vial and the fibre is exposed for 30 min at 150 °C.
For derivatization of analytes, the fibre is introduced into the headspace of another closed vial containing N-methyl-N-(trimethylsilyl)trifluoroacetamide. The GC/MS parameters were the same for both chromatographic runs. The linearity was proved
to be between 0.01 and 10.00 ng/mg. The repeatability (intra- and interday precision) was below 10% as the coefficient of
variation for all compounds. The accuracy, as the relative recovery, was 96.2–103.5% (spiked samples) and 88.6–101.7% (quality
control sample). The limit of detection ranged from 0.01 to 0.12 ng/mg, and the limit of quantification ranged from 0.02 to
0.37 ng/mg. Application of the procedure to real hair samples is described. To the best of our knowledge, the proposed procedure
combining HS-SPME and GC/MS is the first one be to successfully applied to the simultaneous determination of most of the common
recreational drugs, including THC, in a single hair sample. 相似文献
158.
Stefano Gialanella Fabrizio Girardi Gloria Ischia Ivan Lonardelli Maurizio Mattarelli Maurizio Montagna 《Journal of Thermal Analysis and Calorimetry》2010,102(3):867-873
This study deals with some microstructural and crystallographic aspects of the thermally induced transformation of goethite
(α-FeOOH) into hematite (α-Fe2O3), occurring at about 300 °C. Powder specimens of goethite have been annealed in air at different temperatures, ranging from
200 °C up to 1,000 °C. The resulting products have been analyzed for a complete characterization of the changes brought about
by the thermal treatments, using a multianalytical approach, based on: thermogravimetry, differential thermal analysis, transmission
electron microscopy, Raman spectroscopy, and X-ray diffraction. At lower temperatures, the transition to hematite produces
no important changes in size and shape of the original goethite grains. Recrystallization, and partial sintering, occurs only
at temperatures in excess of 800 °C. The relevant evolution of pores present in both phases has been also considered, as it
may provide important indications on the actual formation mechanism of hematite. 相似文献
159.
Pham TN Griffin JM Masiero S Lena S Gottarelli G Hodgkinson P Filip C Brown SP 《Physical chemistry chemical physics : PCCP》2007,9(26):3416-3423
(2h)J(NN) hydrogen-bond mediated J couplings are measured in the solid state for two synthetic deoxyguanosine derivatives by (15)N MAS NMR spin-echo experiments. The use of rotor-synchronised Hahn-echo pulse train (RS-HEPT) (1)H decoupling, with a duty cycle of 6%, allows spin-echo durations out to 200 ms, hence enabling the accurate determination of J couplings as small as 3.8 Hz. A single-crystal X-ray diffraction structure exists for the shorter alkyl chain derivative dG(C(3))(2): the observation of significantly different (2h)J(NN) couplings, 6.2 +/- 0.4 and 7.4 +/- 0.4 Hz, for the two resolved N7 resonances is to be expected given the NH...N hydrogen-bonding distances of 2.91 and 2.83 A for the two distinct molecules in the asymmetric unit cell. For the longer alkyl chain derivative, dG(C(10))(2), for which there is no single-crystal diffraction structure, a (15)N refocused INADEQUATE spectrum (Pham et al., J. Am. Chem. Soc., 2005, 127, 16018-16019) has demonstrated the presence of N2-H...N7 intermolecular hydrogen-bonds indicative of a quartet-like structure. The (2h)J(NN) hydrogen-bond mediated J coupling of 5.9 +/- 0.2 Hz is at the lower end of the range (5.9-8.2 Hz) of (2h)J(NN) couplings determined from solution-state NMR of guanosine quartets in quadruplex DNA. A full discussion of the determination of error bars on the fitted parameters is given; specifically, error bars determined by a non-linear fitting (using the covariance matrix) or in a Monte-Carlo fashion are found to give effectively identical results. 相似文献
160.
Leoni S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(36):10022-10029
Finding new pathways to novel materials is an open challenge in modern solid-state chemistry. Among the reasons that still prevent a rational planning of synthetic routes is the lack of an atomistic understanding at the moment of phase formation. Metastable phases are, in this respect, powerful points of access to new materials. For the synthetic efforts to fully take advantage of such peculiar intermediates, a precise atomistic understanding of critical processes in the solid state in its many facets, that is, nucleation patterns, formation and propagation of interfaces, intermediate structures, and phase growth, is mandatory. Recently we have started a systematic theoretical study of phase transitions, especially of processes with first-order thermodynamics, to reach a firm understanding of the atomistic mechanisms governing polymorphism in the solid state. A clear picture is emerging of the interplay between nucleation patterns, the evolution of domain interfaces and final material morphology. Therein intermediate metastable structural motifs with distinct atomic patterns are identified, which become exciting targets for chemical synthesis. Accordingly, a new way of implementing simulation strategies as a powerful support to the chemical intuition is emerging. Simulations of real materials under conditions corresponding to the experiments are shedding light onto yet elusive aspects of solid-solid transformations. Particularly, sharp insights into local nucleation and growth events allow the formulation of new concepts for rationalizing interfaces formed during phase nucleation and growth. Structurally different and confined in space, metastable interfaces occurring during polymorph transformations bring about distinct diffusion behavior of the chemical species involved. More generally, stable structures emerge as a result of the concurrence of the transformation mechanism and of chemical reactions within the phase-growth fronts. 相似文献