全文获取类型
收费全文 | 255篇 |
免费 | 9篇 |
专业分类
化学 | 187篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 37篇 |
物理学 | 35篇 |
出版年
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 1篇 |
2015年 | 10篇 |
2014年 | 7篇 |
2013年 | 9篇 |
2012年 | 14篇 |
2011年 | 22篇 |
2010年 | 15篇 |
2009年 | 6篇 |
2008年 | 15篇 |
2007年 | 21篇 |
2006年 | 21篇 |
2005年 | 16篇 |
2004年 | 21篇 |
2003年 | 16篇 |
2002年 | 8篇 |
2001年 | 3篇 |
2000年 | 5篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有264条查询结果,搜索用时 15 毫秒
51.
Adnan S. Abu‐Surrah Tony Debaerdemaeker Wolfgang Huhn Bernhard Rieger Martti Klinga Timo Repo Markku Leskel 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):e42-e43
In the title compound, [Pd(CH3)2(C27H26P2)]·0.5C7H8, the Pd atom is at the centre of an approximately square‐planar arrangement of two P atoms and two methyl groups. The P—Pd—P angle [93.19 (3)°] is significantly larger than that in the corresponding dichloride complex [Pd(dppp)Cl2]. The toluene molecule is disordered across an inversion centre. 相似文献
52.
Markku Kallio Markku Kuula Sami Oinonen 《European Journal of Operational Research》2012,217(2):428-438
In this paper, we consider investments in eucalyptus plantations in Brazil. For such projects, we discuss real options valuation in the place conventional methods such as IRR or NPV, possibly with CAPM. Traditionally, real options valuation assumes complete markets and neglects market imperfections. Yet, market frictions, such as transaction costs, interest rate spreads, and restricted short positions, can play an important role. We extend real options valuation to allow incomplete and imperfect markets. The value is obtained as a competitive price, given markets of competing investment opportunities, such as real and financial assets. Under perfect and complete markets, such valuation method is consistent with conventional real options theory. Stochastic programming and standard software is used for valuation of eucalyptus plantations. We estimate the underlying interdependent diffusion processes of stock market, interest rates, exchange rates and pulpwood price, and derive novel expressions of stochastic integrals to be employed in scenario generation for discrete time stochastic programming. 相似文献
53.
Totti Laitinen Sara Herrero Martín Jevgeni Parshintsev Tuulia Hyötyläinen Kari Hartonen Marja-Liisa Riekkola Markku Kulmala José Luis Pérez Pavón 《Journal of chromatography. A》2010,1217(1):151-159
Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations. 相似文献
54.
We show, using rigorous diffraction theory, that resonance gratings can be used to transfer partial spatial correlation to partial polarization even if the incident light beam is fully polarized. The phenomenon is based on the fact that either of the two orthogonal polarization components can be coupled into the leaky waveguide mode, leading to a strong phase delay, while the other one is reflected without being coupled into the grating. Numerical demonstrations are based on a Gaussian Schell-model beam and a grating analysis performed by rigorous Fourier modal method. 相似文献
55.
Kari Kopra Alessio Ligabue Qi Wang Markku Syrjänpää Olga Blaževitš Stefan Veltel Arjan J. van Adrichem Pekka Hänninen Daniel Abankwa Harri Härmä 《Analytical and bioanalytical chemistry》2014,406(17):4147-4156
A quenching resonance energy transfer (QRET) assay for small GTPase nucleotide exchange kinetic monitoring is demonstrated using nanomolar protein concentrations. Small GTPases are central signaling proteins in all eukaryotic cells acting as a “molecular switches” that are active in the GTP-state and inactive in the GDP-state. GTP-loading is highly regulated by guanine nucleotide exchange factors (GEFs). In several diseases, most prominently cancer, this process in misregulated. The kinetics of the nucleotide exchange reaction reports on the enzymatic activity of the GEF reaction system and is, therefore, of special interest. We determined the nucleotide exchange kinetics using europium-labeled GTP (Eu-GTP) in the QRET assay for small GTPases. After GEF catalyzed GTP-loading of a GTPase, a high time-resolved luminescence signal was found to be associated with GTPase bound Eu-GTP, whereas the non-bound Eu-GTP fraction was quenched by soluble quencher. The association kinetics of the Eu-GTP was measured after GEF addition, whereas the dissociation kinetics could be determined after addition of unlabeled GTP. The resulting association and dissociation rates were in agreement with previously published values for H-RasWt, H-RasQ61G, and K-RasWt, respectively. The broader applicability of the QRET assay for small GTPases was demonstrated by determining the kinetics of the Ect2 catalyzed RhoAWt GTP-loading. The QRET assay allows the use of nanomolar protein concentrations, as more than 3-fold signal-to-background ratio was achieved with 50 nM GTPase and GEF proteins. Thus, small GTPase exchange kinetics can be efficiently determined in a HTS compatible 384-well plate format. Figure
? 相似文献
56.
Adnan S. Abu‐Surrah Martti Klinga Timo Repo Markku Leskel Tony Debaerdemaeker Bernhard Rieger 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):e44-e45
The title compound was formed upon slow evaporation of a solution of the solvated dicationic complex bis(acetonitrile)bis[1,2‐bis(diphenyl‐phosphino)ethane]palladium(II) bis(tetrafluoroborate) in deuterated chloroform. The dinucleur palladium complex forms triclinic crystals and there is an inversion center between the Pd atoms. Compared to the corresponding monomeric compound, the Cl—Pd—Cl angles decrease upon briding from 94.19 (7) to 86.96 (4)°. 相似文献
57.
Paula Aulaskari Markku Ahlgrn Pirjo Vainiotalo Esko Pohjala 《Journal of heterocyclic chemistry》2000,37(1):87-93
New high yield preparation methods were developed for the pharmaceutically interesting compounds, 1‐benzyl‐, 1‐methyl‐, and 1H‐5‐[(2‐oxo‐2‐phenyl)ethyl]imidazoles 1a‐c , respectively. The title compounds were synthesized by four different methods using various starting materials. Two of the methods involved transformation reactions of the key intermediates, 1‐substituted‐5‐[(2‐nitro‐2‐phenyl)ethenyl]imidazoles 2a‐c and 1‐substituted‐5‐[(2‐nitro‐2‐phenyl)ethyl]imidazoles 3a‐c , while the other two utilized the oxidation of 1‐substituted‐5‐[(2‐hydroxy‐2‐phenyl)ethyl]imidazoles 4a‐c , with chromic oxide, and the umpolung reaction of benzaldehyde followed by a condensation reaction of the umpolung intermediate with imidazolecarboxaldehydes 6a‐c. 相似文献
58.
Vehkamäki H McGrath MJ Kurtén T Julin J Lehtinen KE Kulmala M 《The Journal of chemical physics》2012,136(9):094107
The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster. 相似文献
59.
Ebben CJ Shrestha M Martinez IS Corrigan AL Frossard AA Song WW Worton DR Petäjä T Williams J Russell LM Kulmala M Goldstein AH Artaxo P Martin ST Thomson RJ Geiger FM 《The journal of physical chemistry. A》2012,116(32):8271-8290
This article summarizes and compares the analysis of the surfaces of natural aerosol particles from three different forest environments by vibrational sum frequency generation. The experiments were carried out directly on filter and impactor substrates, without the need for sample preconcentration, manipulation, or destruction. We discuss the important first steps leading to secondary organic aerosol (SOA) particle nucleation and growth from terpene oxidation by showing that, as viewed by coherent vibrational spectroscopy, the chemical composition of the surface region of aerosol particles having sizes of 1 μm and lower appears to be close to size-invariant. We also discuss the concept of molecular chirality as a chemical marker that could be useful for quantifying how chemical constituents in the SOA gas phase and the SOA particle phase are related in time. Finally, we describe how the combination of multiple disciplines, such as aerosol science, advanced vibrational spectroscopy, meteorology, and chemistry can be highly informative when studying particles collected during atmospheric chemistry field campaigns, such as those carried out during HUMPPA-COPEC-2010, AMAZE-08, or BEARPEX-2009, and when they are compared to results from synthetic model systems such as particles from the Harvard Environmental Chamber (HEC). Discussions regarding the future of SOA chemical analysis approaches are given in the context of providing a path toward detailed spectroscopic assignments of SOA particle precursors and constituents and to fast-forward, in terms of mechanistic studies, through the SOA particle formation process. 相似文献
60.
Chernichenko K Nieger M Leskelä M Repo T 《Dalton transactions (Cambridge, England : 2003)》2012,41(30):9029-9032
Two 2-[bis(pentafluorophenyl)boryl]-N,N-dialkylanilines reported here exemplify a new class of intramolecular frustrated B/N Lewis pairs. A structure closely related to this class structure was synthesized in 2003 by Piers et al. but was unable to activate H(2). The new aminoboranes can activate hydrogen at near ambient conditions; besides, one of them can hydrogenate imines and enamines in a catalytic fashion demonstrating the validity of the original Piers' approach to hydrogen activation with ansa-aminoboranes. 相似文献