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101.
Solid-phase microextraction (SPME) is an organic solvent-free sample preparation tool suitable for direct adsorption of analytes from the headspace or the aqueous phase of a matrix followed by desorption into a gas chromatograph (GC) or high-performance liquid chromatograph (HPLC) for subsequent analysis. The SPME technique is designed to accommodate the use of fibers coated with different polymers suitable for the extraction of chemicals with varied hydrophobic and polar properties. Also, the technique can minimize interference from other artefacts associated with complex samples, such as those encountered in biological matrices or reaction mixtures. The preceding characteristics of SPME make the technique suitable for real-time measurements of intermediate reaction products and, thus, able to provide insight into the fate of target chemicals and their degradation pathways. In the present article, the current state of knowledge on the use of SPME-GC and SPME-HPLC in the determination of frequently encountered environmental chemicals and their (bio)transformation pathways are critically reviewed. Future opportunities of SPME in real time in situ process monitoring such as the use of agricultural feed stocks to bio-based industrial products termed henceforth "process analytical chemistry" are also discussed. 相似文献
102.
A crucial point in the implementation of meshless methods such as the meshless local Petrov–Galerkin (MLPG) method is the evaluation of the domain integrals arising over circles in the discrete local weak form of the governing partial differential equation. In this paper we make a comparison between the product Gauss numerical quadrature rules, which are very popular in the MLPG literature, with cubature formulas specifically constructed for the approximation of an integral over the unit disk, but not yet applied in the MLPG method, namely the spherical, the circularly symmetrical and the symmetric cubature formulas. The same accuracy obtained with 64×64 points in the product Gauss rules may be obtained with symmetric quadrature formulas with very few points. 相似文献
103.
Philipp Gotico Bernard Boitrel Rgis Guillot Marie Sircoglou Annamaria Quaranta Zakaria Halime Winfried Leibl Ally Aukauloo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4552-4557
Inspired by nature's orchestra of chemical subtleties to activate and reduce CO2, we have developed a family of iron porphyrin derivatives in to which we have introduced urea groups functioning as multipoint hydrogen‐bonding pillars on the periphery of the porphyrinic ring. This structure closely resembles the hydrogen‐bond stabilization scheme of the carbon dioxide (CO2) adduct in the carbon monoxide dehydrogenase (CODH). We found that such changes to the second coordination sphere significantly lowered the overpotential for CO2 reduction in this family of molecular catalysts and importantly increased the CO2 binding rate while maintaining high turnover frequency (TOF) and selectivity. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO2 reduction. 相似文献
104.
Alkoxy-functionalized butadienyl- and styrylboronic esters have been synthesized starting from alpha,beta-unsaturated acetals. These derivatives readily cross-couple with aryl substrates, and the obtained products can be transformed under mild conditions into aromatic ketones, achieving the same result as an acylation reaction. [reaction: see text] 相似文献
105.
Annamaria Montanari 《Journal of Differential Equations》2004,202(2):306-331
We introduce a new class of curvature PDOs describing relevant properties of real hypersurfaces of . In our setting, the pseudoconvexity and the Levi form play the same role as the convexity and the real Hessian matrix play in the real Euclidean one. Our curvature operators are second-order fully nonlinear PDOs not elliptic at any point. However, when computed on generalized s-pseudoconvex functions, we shall show that their characteristic form is nonnegative definite with kernel of dimension one. Moreover, we shall show that the missing ellipticity direction can be recovered by taking into account the CR structure of the hypersurfaces. These properties allow us to prove a strong comparison principle, leading to symmetry theorems for domains with constant curvatures and to identification results for domains with comparable curvatures. 相似文献
106.
Annamaria?Montanari Daniele?MorbidelliEmail author 《Calculus of Variations and Partial Differential Equations》2017,56(2):36
We characterize the subRiemannian cut locus of the origin in the free Carnot group of step two with three generators, giving a new, independent proof of a result by Myasnichenko (J Dyn Control Syst 8(4):573-597, 2002). We also calculate explicitly the cut time of any extremal path and the distance from the origin of all points of the cut locus. Furthermore, by using the Hamiltonian approach, we show that the cut time of strictly normal extremal paths is a smooth explicit function of the initial velocity covector. Finally, using our previous results, we show that at any cut point the distance has a corner-like singularity. 相似文献
107.
Clarissa Coccia Dr. Marta Morana Dr. Arup Mahata Dr. Waldemar Kaiser Dr. Marco Moroni Dr. Benedetta Albini Prof. Pietro Galinetto Dr. Giulia Folpini Prof. Chiara Milanese Prof. Alessio Porta Dr. Edoardo Mosconi Dr. Annamaria Petrozza Prof. Filippo De Angelis Prof. Lorenzo Malavasi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(10):e202318557
Chiral perovskites possess a huge applicative potential in several areas of optoelectronics and spintronics. The development of novel lead-free perovskites with tunable properties is a key topic of current research. Herein, we report a novel lead-free chiral perovskite, namely (R/S−)ClMBA2SnI4 (ClMBA=1-(4-chlorophenyl)ethanamine) and the corresponding racemic system. ClMBA2SnI4 samples exhibit a low band gap (2.12 eV) together with broad emission extending in the red region of the spectrum (∼1.7 eV). Chirality transfer from the organic ligand induces chiroptical activity in the 465–530 nm range. Density functional theory calculations show a Rashba type band splitting for the chiral samples and no band splitting for the racemic isomer. Self-trapped exciton formation is at the origin of the large Stokes shift in the emission. Careful correlation with analogous lead and lead-free 2D chiral perovskites confirms the role of the symmetry-breaking distortions in the inorganic layers associated with the ligands as the source of the observed chiroptical properties providing also preliminary structure-property correlation in 2D chiral perovskites. 相似文献
108.
A comparison of the extraction of clove buds with supercritical carbon dioxide and superheated water 总被引:1,自引:0,他引:1
A. A. Clifford Annamaria Basile Salim H. R. Al-Saidi 《Analytical and bioanalytical chemistry》1999,364(7):635-637
Supercritical carbon dioxide and superheated water (subcritical water above 100 °C under pressure) have both been used to
extract the buds of cloves (Syzygium aromaticum). The yields of eugenol and eugenyl acetate obtained by these methods and also by steam distillation and liquid solvent (Soxhlet)
extraction are similar, but the yields of caryophyllene were lower for the methods using water.
Received: 23 December 1998 / Revised: 26 March 1999 / Accepted: 31 March 1999 相似文献
109.
The explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is of particular interest due to its extreme insensitivity to impact, shock and heat, while providing a good detonation velocity. To determine its fate under environmental conditions, TATB powder was irradiated with simulated sunlight and, in water, under UV light at 254 nm. The hydrolysis of particles submerged in neutral and alkaline solutions was also examined. We found that, by changing experimental conditions (e.g., light source, and mass and physical state of TATB), the intermediates and final products were slightly different. Mono-benzofurazan was the major transformation product in both irradiation systems. Two minor transformation products, the aci-nitro form of TATB and 3,5-diamino-2,4,6-trinitrophenol, were detected under solar light, while 1,3,5-triamino-2-nitroso-4,6-dinitrobenzene, 1,3,5-triamino-2,4-dinitrobenzene and mono-benzofuroxan were produced under UV light. The product identified as 3,5-diamino-2,4,6-trinitrophenol was identical to the one formed in the dark under alkaline conditions (pH 13) and in water incubated at either 50 °C or aged at ambient conditions. Interestingly, when only a few milligrams of TATB were irradiated with simulated sunlight, the aci-isomer and mono-benzofurazan derivative were detected; however, the hydrolysis product 3,5-diamino-2,4,6-trinitrophenol formed only much later in the absence of light. This suggests that the water released from TATB to form mono-benzofurazan was trapped in the interstitial space between the TATB layers and slowly hydrolyzed the relatively stable aci-nitro intermediate to 3,5-diamino-2,4,6-trinitrophenol. This environmentally relevant discovery provides data on the fate of TATB in surface environments exposed to sunlight, which can transform the insoluble substrate into more soluble and corrosive derivatives, such as 3,5-diamino-2,4,6-trinitrophenol, and that some hydrolytic transformation can continue even without light. 相似文献
110.
Dr. Annamaria Panniello Dr. Mariachiara Trapani Dr. Massimiliano Cordaro Carlo Nazareno Dibenedetto Prof. Raffaele Tommasi Dr. Chiara Ingrosso Prof. Elisabetta Fanizza Dr. Roberto Grisorio Prof. Elisabetta Collini Prof. Angela Agostiano Prof. Maria Lucia Curri Dr. Maria Angela Castriciano Dr. Marinella Striccoli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2371-2380
Efficient FRET systems are developed combining colloidal CdSe quantum dots (QDs) donors and BODIPY acceptors. To promote effective energy transfer in FRET architectures, the distance between the organic fluorophore and the QDs needs to be optimized by a careful system engineering. In this context, BODIPY dyes bearing amino-terminated functionalities are used in virtue of the high affinity of amine groups in coordinating the QD surface. A preliminary QD surface treatment with a short amine ligand is performed to favor the interaction with the organic fluorophores in solution. The successful coordination of the dye to the QD surface, accomplishing a short donor–acceptor distance, provides effective energy transfer already in solution, with efficiency of 76 %. The efficiency further increases in the solid state where the QDs and the dye are deposited as single coordinated units from solution, with a distance between the fluorophores down to 2.2 nm, demonstrating the effectiveness of the coupling strategy. 相似文献