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101.
Protons on water molecules are strongly affected by paramagnetic ions. Since the acid-base properties of water facilitate rapid proton exchange, a single proton nuclear magnetic resonance (NMR) signal is seen in aqueous solutions of paramagnetic ions. Proton relaxation times are significantly affected by paramagnetic species and the readily detectable single signal serves as a powerful amplifier of the information contained concerning the protons in the paramagnetic environment. Where water molecules coordinated to free paramagnetic ions and to metal complexes of ligands that form non-labile (on the NMR time scale) complexes, the effects on water in the two environments can be distinguished. This can provide information on the nature of the ligand binding sites. The example of Cu2+ bound to the Laurentian humic acid mixture reported here using convenient low field NMR relaxometers shows that the information can enrich our understanding of complexation and speciation in the presence of complex mixture ligands characteristic of natural water systems. In this case, the data underline the role of aggregation and conformation in defining the complexation sites. 相似文献
102.
Vassilis Saliakas Christos Chatzidoukas Apostolos Krallis Dimitris Meimaroglou Costas Kiparissides 《大分子反应工程》2007,1(1):119-136
In the present study, two numerical methods, namely the orthogonal collocation on finite elements and the fixed pivot technique, are employed to calculate the MWD in an MMA free‐radical batch suspension polymerization reactor operating up to very high conversions (e.g., ≥95%). The theoretical MWD predictions are directly compared with experimentally measured MWDs, obtained from a pilot‐scale batch MMA suspension polymerization reactor. It is shown that there is a very good agreement between model predictions and experimental measurements on both monomer conversion and MWD. Subsequently, two different time‐optimal temperature trajectories are calculated to obtain a polymer having either a narrow or a bimodal MWD in minimum batch time. The calculated time optimal trajectories are then applied, as set point temperature changes, to a pilot plant batch polymerization reactor. It is shown that the measured MWDs are in very good agreement with the off‐line calculated optimal MWDs.
103.
This review is a brief account on the application of a novel methodology to the quality control and authentication of extra-virgin olive oil. This methodology is based on the derivatization of the labile hydrogens of functional groups, such as hydroxyl and carboxyl groups, of olive oil constituents with the phosphorus reagent 2-chloro-4,4,5,5-tetramethyldioxaphospholane, and the use of the (31)P chemical shifts to identify the phosphitylated compounds. Various experimental aspects such as pertinent instrumentation, sample preparation, acquisition parameters and properties of the phosphorus reagent are reviewed. The strategy to assign the (31)P signals of the phosphitylated model compounds and olive oil constituents by employing 1D and 2D NMR experiments is presented. Finally, the capability of this technique to assess the quality and the genuineness of extra-virgin olive oil and to detect fraud is discussed. 相似文献
104.
Apostolos Krallis Prokopis Pladis Costas Kiparissides 《Macromolecular theory and simulations》2007,16(6):593-609
In the present study a population balance approach is described to follow the time evolution of bivariate molecular weight‐long chain branching (MW‐LCB) distributions in high pressure low density polyethylene autoclaves. The model formulation is based on a sectional grid method, the so‐called fixed pivot technique (FPT). According to this method, the ‘live’ and ‘dead’ polymer chain populations are assigned to a selected number of discrete points. Then, the resulting dynamic discrete‐continuous molar species equations for ‘live’ and ‘dead’ polymer chains are solved at the specified grid points. It is shown that a very good agreement exists between theoretical results and experimental data which proves the capability of the FPT method in calculating the joint MW‐LCB distribution for branched polymers.
105.
106.
Nikos Hadjichristidis Yiannis Poulos Apostolus Avgeropoulos 《Macromolecular Symposia》1998,132(1):207-220
The synthesis of non linear block copolymers of the type (BA)2B (3-miktoarm star copolymer), (BA)3B (4-miktoarm star copolymer), (BA)3B(AB)3 (super H-shaped), B2AB2 (H-shaped) and (B,A)A(B,A) (π-shaped), where A is polyisoprene 1,4 and B is polystyrene was performed using anionic polymerization techniques and suitable chlorosilane chemistry. Characterization data showed that the samples are molecularly and compositionally homogeneous. TEM, SAXS and SANS were used to study the microphase behavior of the copolymers. For all samples, the results were analyzed in the frame of the theoretical predictions given by Milner and taking into account the results from previous studies on the A2B and A3B miktoarm star copolymers. 相似文献
107.
Apostolos Thoma 《代数通讯》2013,41(3):805-821
Let C be a monomial curve in three dimensional projective space over a field of characteristic zero . We give a necessary criterion for a monomial curve to be set theoretic complete intersection on bihomogeneous surfaces. Using this criterion we prove several results concerning the arithmetically Cohen-Macaulay property for monomial curves. 相似文献
108.
Estimating the probabilities by which different events might occur is usually a delicate task, subject to many sources of inaccuracies. Moreover, these probabilities can change over time, leading to a very difficult evaluation of the risk induced by any particular decision. Given a set of probability measures and a set of nominal risk measures, we define in this paper the concept of robust risk measure as the worst possible of our risks when each of our probability measures is likely to occur. We study how some properties of this new object can be related with those of our nominal risk measures, such as convexity or coherence. We introduce a robust version of the Conditional Value-at-Risk (CVaR) and of entropy-based risk measures. We show how to compute and optimize the Robust CVaR using convex duality methods and illustrate its behavior using data from the New York Stock Exchange and from the NASDAQ between 2005 and 2010. 相似文献
109.
Apostolos N. Burnetas 《Annals of Operations Research》2013,208(1):515-529
We consider series of M/M/m queues with strategic customer behavior. Customers arrive to the first queue and decide whether to enter the system or balk and, if they enter, up to which queue to proceed before departing. Each customer makes an independent decision, with the objective of maximizing her total net benefit, which is equal to the value of service minus a cost due to expected delay. We formulate the customer decision as a game and identify the unique symmetric Nash equilibrium strategy, which is expressed in a backward recursive form. We also analyze the problem of maximizing the total customer welfare and establish the relationship between the equilibrium and the welfare maximizing strategies. 相似文献
110.
In the present work we examine a series of hypervalent molecules, namely, FClO(x) (x = 1-3), Cl(3)PO, Cl(3)PCH(2), Cl(3)CClO, and C(ClO)(4), through single-reference [CCSD(T)] and multireference (MRCI) ab initio methods, the principal aim being the deciphering of their binding pattern. Our electronic structure calculations consistently show that the bonding occurs through an electron pair transfer from the Cl or P atoms of the molecules considered to the (1)D state of the O atom(s). We strongly believe that the term "hypervalency" when viewed from an unbiased side and with a critical eye reveals a simple chemical bonding situation that is in conformity with a scientific parsimony that dissolves the mythology of an enormous class of molecular systems that are categorized under the term hypervalent. 相似文献