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101.
Franco Cataldo Pietro Ragni Susana Iglesias-Groth Arturo Manchado 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(2):573-580
The sulphur-containing proteinaceous amino acids l-cysteine, l-cystine and l-methionine were irradiated in the solid state to a dose of 3.2 MGy. This dose corresponds to that delivered by radionuclide
decay in a timescale of 1.05 × 109 years to the organic matter buried at a depth >20 m in comets and asteroids. The purity of the sulphur-containing amino acids
was studied by differential scanning calorimetry (DSC) before and after the solid state radiolysis and the preservation of
the chirality after the radiolysis was studied by chirooptical methods (optical rotatory dispersion, ORD) and by FT-IR spectroscopy.
Although the high radiation dose of 3.2 MGy delivered, all the amino acids studied show a high radiation resistance. The best
radiation resistance was offered by l-cysteine. The radiolysis of l-cysteine leads to the formation of l-cystine. The radiation resistance of l-methionine is not at the level of l-cysteine but also l-methionine is able to survive the dose of 3.2 MGy. Furthermore in all cases examined the preservation of chirality after
radiolysis was clearly observed by the ORD spectroscopy although a certain level of radioracemization was measured in all
cases. The radioracemization is minimal in the case of l-cysteine and is more pronounced in the case of l-methionine. In conclusion, the study shows that the sulphur-containing amino acids can survive for 1.05 × 109 years and, after extrapolation of the data, even to the age of the Solar System i.e. to 4.6 × 109 years. 相似文献
102.
Arturo González-Hernández 《Journal of organometallic chemistry》2011,696(21):3436-3439
The reaction between the dihydride of decacarbonyltriosmium [H2Os3(CO)10] and phenyl arsine oxide (PAO) in benzene yields only one product [Os3(O)9(μ-H){μ-PhAs(O)OAsPh}] (1), which is characterized by high resolution mass spectrometry (HRMS), Fast Atomic Bombardment Mass Spectrometry (FAB)+, IR, 1H and 13C NMR, and single crystal X-ray diffraction. The solid state X-ray diffraction study of compound (1) shows that the molecule is polycyclic and has an osmium triangle with a bridging hydride bonded to a PhAs(O)-O-AsPh ligand. 相似文献
103.
Tamboli V Defant A Mancini I Tosi P 《Rapid communications in mass spectrometry : RCM》2011,25(4):526-532
Resveratrol is a polyphenolic compound found in plants and human foods which has shown biological activities including chemoprevention, acting through a mechanism which involves the reduction of Cu(II) species. By electrospray ionization (ESI) mass spectrometry we have produced and detected the resveratrol-copper complexes [Resv+Cu](+), [Resv+Cu+H(2)O](+) and [2Resv+Cu](+) by using a resveratrol/CuSO(4) solution in CH(3)CN/H(2)O. The most stable structures of the detected complexes have been calculated at the B3LYP/6-311G(d) level of theory. Resveratrol interacts with the copper ion through nucleophilic carbon atoms on the aromatic ring and the alkenyl group. The fact that only singly charged ions were observed implies that Cu(II) is reduced to Cu(I) in the ESI process. For investigating the structure-reactivity correlation, we have carried out a similar study on the synthetic analogue dihydroresveratrol (DHResv). For the latter only the [DHResv+Cu](+) complex has been detected. 相似文献
104.
Zelenka K Trnka T Tišlerová I Monti D Cinti S Naitana ML Schiaffino L Venanzi M Laguzzi G Luvidi L Mancini G Nováková Z Šimák O Wimmer Z Drašar P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13743-13753
Solvent-driven aggregation of a series of porphyrin derivatives was studied by UV/Vis and circular dichroism spectroscopy. The porphyrins are characterised by the presence in the meso positions of steroidal moieties further conjugated with glucosyl groups. The presence of these groups makes the investigated macrocycles amphiphilic and soluble in aqueous solvent, namely, dimethyl acetamide/water. Aggregation of the macrocycles is triggered by a change in bulk solvent composition leading to formation of large architectures that express supramolecular chirality, steered by the presence of the stereogenic centres on the periphery of the macrocycles. The aggregation behaviour and chiroptical features of the aggregates are strongly dependent on the number of moieties decorating the periphery of the porphyrin framework. In particular, experimental evidence indicates that the structure of the steroid linker dictates the overall chirality of the supramolecular architectures. Moreover, the porphyrin concentration strongly affects the aggregation mechanism and the CD intensities of the spectra. Notably, AFM investigations reveal strong differences in aggregate morphology that are dependent on the nature of the appended functional groups, and closely in line with the changes in aggregation mechanism. The suprastructures formed at lower concentration show a network of long fibrous structures spanning over tens of micrometres, whereas the aggregates formed at higher concentration have smaller rod-shaped structures that can be recognised as the result of coalescence of smaller globular structures. The fully steroid substituted derivative forms globular structures over the whole concentration range explored. Finally, a rationale for the aggregation phenomena was given by semiempirical calculations at the PM6 level. 相似文献
105.
Sola A Otón F Espinosa A Tárraga A Molina P 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12548-12559
Aldimine 4 bearing a 2-quinolyl group was prepared by aza-Wittig reaction between the triphenyliminophosphorane derived from the 1,1'-diazidoferrocene and 2-formylquinoline. However, aldimine 5, bearing a pyrene ring, was prepared using the most reactive tributyliminophosphorane derivative and the corresponding 1-formylpyrene. On the other hand, formation of aldimine 8 involves a tandem process, Staudinger reaction/intramolecular aza-Wittig reaction, by using directly 1,1'-diazidoferrocene and 2-(diphenylphosphonyl)benzaldehyde. Aldimine 4 behaves as chemosensor molecule for Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) cations through two different channels: electrochemical (ΔE(1/2) = 222-361 mV) and chromogenic (Δλ = 122-153 nm), which can be used for the "naked eye" detection of these metal cations. Aldimine 5 behaves as a highly selective redox (in CH(3)CN) and fluorescent (in CH(3)Cl-DMF) probe for Hg(2+) metal cations even in the presence of a large excess of the other metal cations tested. Aldimine 8 displays electrochemical affinity (ΔE(1/2) = 60-288 mV) to Li(+), Ca(2+), Mg(2+), Zn(2+) and Pb(2+) metal cations, with the phosphorus oxide functionality as a binding site. From the (1)H NMR titration data as well as DFT calculations, different tentative binding modes have been established, for these structurally related ferrocenyl derivatives. 相似文献
106.
A simple but effective dual redox and fluorescent ion pair receptor based on a ferrocene-imidazopyrene dyad 总被引:1,自引:0,他引:1
The ferrocene-imidazopyrene dyad, bearing the imidazole ring as the only receptor site, acts as a redox and optical molecular sensor for ion pairs, exhibiting an easily detectable signal change in the redox potential of the ferrocene/ferrocinium redox couple and in the emission spectrum. Perturbation of the emission spectrum follows the order Pb(2+) > Hg(2+) > Zn(2+) for cations and H(2)PO(4)(-) > AcO(-) for anions. 相似文献
107.
108.
In this article we consider, under a Lévy process model for the stock price, the utility optimization problem for an insider
agent whose additional information is the final price of the stock blurred with an additional independent noise which vanishes
as the final time approaches. Our main interest is establishing conditions under which the utility of the insider is finite.
Mathematically, the problem entails the study of a “progressive” enlargement of filtration with respect to random measures.
We study the jump structure of the process which leads to the conclusion that in most cases the utility of the insider is
finite and his optimal portfolio is bounded. This can be explained financially by the high risks involved in models with jumps. 相似文献
109.
In this paper we introduce the notion of generalized implication for lattices, as a binary function ⇒ that maps every pair of elements of a lattice to an ideal. We prove that a bounded lattice
A is distributive if and only if there exists a generalized implication ⇒ defined in A satisfying certain conditions, and we study the class of bounded distributive lattices A endowed with a generalized implication as a common abstraction of the notions of annihilator (Mandelker, Duke Math J 37:377–386,
1970), Quasi-modal algebras (Celani, Math Bohem 126:721–736, 2001), and weakly Heyting algebras (Celani and Jansana, Math Log Q 51:219–246, 2005). We introduce the suitable notions of morphisms in order to obtain a category, as well as the corresponding notion of congruence.
We develop a Priestley style topological duality for the bounded distributive lattices with a generalized implication. This
duality generalizes the duality given in Celani and Jansana (Math Log Q 51:219–246, 2005) for weakly Heyting algebras and the duality given in Celani (Math Bohem 126:721–736, 2001) for Quasi-modal algebras. 相似文献
110.
Bonicelli MG Giansanti L Ierino M Mancini G 《Journal of colloid and interface science》2011,361(1):1-8
The colloidal dispersion stability of nano-sized graphene sheets in supercritical fluid (SCF) media is very important for developing SCF-based exfoliation and dispersion technologies for stabilization and solubilization of graphenes. We carried out molecular dynamics simulations to elucidate the stability mechanism of graphene in supercritical CO(2) (scCO(2)). The potential of mean force (PMF) between two graphene nanosheets in scCO(2) was simulated, and the effect of scCO(2) density and temperature on the PMF behavior has been investigated. The simulation results demonstrate that there exists a free energy barrier between graphenes in the scCO(2) fluid, possibly obstructing the aggregation of graphenes. The single-layer confined CO(2) molecules between the graphene sheets can induce a dominating repulsion interaction between graphene sheets. At higher scCO(2) fluid density, there are more confined CO(2) molecules within the interplate regions, resulting in a stronger repulsive free energy barrier. The effect of temperature on the PMF is relatively minor. The scCO(2) solvent structure shows layered confined arrangement in the interfacial region near the graphene nanosheets, which is correlated well with the PMF profile curve. 相似文献