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1.
2.
Zojer E Beljonne D Pacher P Brédas JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(11):2668-2680
Quadrupolar-type substitution of pi-conjugated chromophores with donor and acceptor groups has been shown to increase their two-photon absorption (TPA) response by up to two orders of magnitude. Here, we apply highly correlated quantum-chemical calculations to evaluate the impact of the nature of conjugated bridge and the charge-transfer distance on that enhancement. We compare chromophores with phenylenevinylene-, thienylenevinylene-, polyene-, and indenofluorene-type backbones substituted by dimethylamino and cyano groups. In all compounds, we find a strongly TPA-active A(g) state (either 2A(g) or 3A(g)) in the low-energy region, as well as a higher lying TPA-active state (mA(g)) at close to twice the energy of the lowest lying one-photon allowed state; the smaller energy detuning in the mA(g) states results in very large TPA cross sections delta. We also investigate the influence of the degree of ground-state polarization on TPA. Independent of the nature of the backbone and the donor-acceptor separation, delta displays the same qualitative evolution with a maximum before the cyanine-like limit; the highest TPA cross sections are calculated for distirylbenzene- and polyene-based systems. 相似文献
3.
Zusammenfassung Staub- und Aerosolproben werden im Stickstoffstrom im Temperaturbereich 25–420° C einer temperaturprogrammierten thermischen Desorption unterworfen. Die flüchtigen organischen Komponenten werden mittels FID summarisch als volatile organic carbon (VOC) bestimmt. Die Eichung des Analysators erfolgt durch ein Aliphaten-Standardgemisch. Bei Probemengen von 50–100g Aerosol ist eine Bestimmung des VOC-Gehaltes mit einer Reproduzierbarkeit vons=3,5–7 rel.% möglich. Die Nachweisgrenze der Methode liegt für Aerosolproben bei 0,3g VOC.
Determination of volatile organic components in atmospheric aerosol samples by thermal desorption and FID-detection
Summary Atmospheric dust and aerosol samples are treated in a nitrogen carrier gas stream at the temperature range 25–420° C by temperature programmed desorption. The volatile organic components are detected by FID. Calibration of the analyzer is carried out with a standard mixture of aliphatic hydrocarbons. The result is expressed as volatile organic carbon (VOC). The reproducibility of the method for aerosol samples (sample weight 50–100g) is in the range of 3,5–7% r. s. d. The detection limit of the method is 0,3g VOC.相似文献
4.
B. Wellegehausen K. Mossavi A. Egbert B. N. Chichkov H. Welling 《Applied physics. B, Lasers and optics》1996,63(5):451-461
Different approaches for the generation of coherent VUV and XUV radiation with a 400 fs KrF excimer-laser system are studied. In nonlinear optical experiments it is shown that four-wave difference-frequency mixing in Xe, using a near two-photon resonance with the KrF laser radiation, is well suited for the generation of tunable VUV radiation in the range 130–200 nm. Conversion efficiencies of 2% and output energies up to 260 J have been demonstrated. Further prospects to achieve J energies are discussed. Using this VUV source and the KrF laser, powerful XUV radiation can be generated by different low-order frequency mixing processes. In first experiments on this subject, direct frequency tripling of the KrF laser pulse has resulted in 14 J XUV radiation at 83 nm.For the realization of soft-X-ray lasers, specific advantages of short-pulse KrF drivers are discussed. Novel scenarios based on a hybrid KrF/Ti: sapphire laser system and multiphoton resonant excitation are considered.Prof. F. P. Schäfer on the occasion of his 65th birthday. 相似文献
5.
Friedrich Bossert Horst Meyer Egbert Wehinger 《Angewandte Chemie (International ed. in English)》1981,20(9):762-769
The aryldihydropyridines first prepared by Hantzsch almost 100 years ago have recently been found to be highly effective calcium antagonists with suitable pharmacological profiles. An illustrative example is dimethyl-l,4-dihydro-2,6-dimethyl-4-(o-nitrophenyl)pyridine-3,5-dicarboxylate (Nifedipine) which is already employed therapeutically. This substance lowers the frequency of attack of angina pectoris and reduces blood pressure. The discovery of the therapeutic activity of this class of substances initiated renewed investigation of the Hantzsch condensation and the synthesis of numerous 4-aryldihydropyridines and related compounds. Qualitative and quantitative structure/activity relationships of these substances can be deduced from their biological data. 相似文献
6.
Egbert Brockhaus 《Journal of Geometry》1977,10(1-2):106-125
Leißner [2] proved that the class of all incidence structures with similarity-relation coinzides with, the class of the algebraically defined geometries [F,T], where F denotes a neardomain over a subdomain T.In this paper we characterize those geometries, where F is a near-resp. (skew-) field by additional similarity axioms. At first we show that a subdomain T of a neardomain F is itself a neardomain iff–1T and characterize this fact geometrically. As a consequence every subdomain of a near-resp.(skew-) field has to be a near-resp. (skew-) field too. In §4 we get as a corollary that projective planes admit no sharply twice transitive groups of collineations. 相似文献
7.
Encinas S Flamigni L Barigelletti F Constable EC Housecroft CE Schofield ER Figgemeier E Fenske D Neuburger M Vos JG Zehnder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):137-150
The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C3H7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]4+ and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]6- complexes (3 = 2,5-bis(2,2':6',2'-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]4+, [(tpy)Os(3)Os(tpy)]4+ and [(tpy)Ru(3)Ru(3)Ru(tpy)]6+ Complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF6]4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rod-shaped with a distance of about 3 nm between the terminal metal centres. For the polynuclear complexes, the spectroscopic and electrochemical data are in accord with a significant intermetal interaction. All of the complexes are luminescent (phi in the range 10(-4)-10(-2) and tau in the range 6-340 ns, at room temperature), and ruthenium- or osmium-based luminescence properties can be identified. Due to the excited state properties of the various components and to the geometric and electronic properties of the bridge, Ru --> Os directional transfer of excitation energy takes place in the complexes [(tpy)Ru(3)Os(tpy)]4+ (end-to-end) and [(tpy)Ru(3)Os(3)Ru(tpy)]6+ (periphery-to-centre). With respect to the homometallic case, for [(tpy)Ru(3)Os(3)Ru(tpy)]6+ excitation trapping at the central position is accompanied by a fivefold enhancement of luminescence intensity. 相似文献
8.
9.
Constable EC Figgemeier E Housecroft CE Olsson J Zimmermann YC 《Dalton transactions (Cambridge, England : 2003)》2004,(13):1918-1927
The synthesis and electronic properties of dinuclear ([(bipy)2Ru(I)M(terpy)][PF6]4(bipy = 2,2'-bipyridine, terpy = 2,2':6',2'-terpyridine; M = Ru, Os)) and trinuclear ([[(bipy)2Ru(I)]2M][PF6]6 M = Ru, Os, Fe, Co) complexes bridged by 4'-(2,2'-bipyridin-4-yl)-2,2':6',2'-terpyridine (I) have been investigated and are compared with those of mononuclear model complexes. The electrochemical analysis using cyclic voltammetry and differential pulse voltammetry reveals that there are no interactions in the ground state between adjacent metal centres. However, there is strong electronic communication between the 2,2'-bipyridine and 2,2':6',2'-terpyridine components of the bridging ligand. This conclusion is supported by a step-by-step reduction of the dinuclear and trinuclear complexes and the assignment of each electrochemical process to localised ligand sites within the didentate and terdentate domains. The investigation of the electronic absorption and emission spectra reveals an energy transfer in the excited state from the terminating bipy-bound metal centres to the central terpy-bound metal centre. This indicates that the bridge is able to facilitate energy transfer in the excited state between the metal centres despite the lack of interactions in the ground state. 相似文献
10.