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81.
Sidath Wijesinghe Sabina Maskey Dvora Perahia Gary S. Grest 《Journal of Polymer Science.Polymer Physics》2016,54(5):582-588
The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality have been studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro‐optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro‐optical properties which are critical in current and potential uses. This study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonyl PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent, whereas in water and implicit poor solvent, the nonyl side chains are collapsed toward the PPE backbone. Rotation around the aromatic ring is fast and no long range correlations are seen within the backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 582–588 相似文献
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84.
Cold reaction valleys in the radioactive decay of superheavy nuclei 286112, 292114, and 296116 are studied taking Coulomb and Proximity Potential as the interacting barrier. It is found that in addition to alpha particle, 8Be, 14C, 28Mg, 34Si, 50Ca, etc. are optimal cases of cluster radioactivity since they lie in the cold valleys. Two other regions of deep minima centered on 208Pb and 132Sn are also found. Within our Coulomb and Proximity Potential Model half-life times and other characteristics such as barrier penetrability, decay constant for clusters ranging from alpha particle to 68Ni are calculated. The computed alpha half-lives match with the values calculated using Viola-Seaborg-Sobiczewski systematics. The clusters 8Be and 14C are found to be most probable for emission with T 1/2 < 1030 s. The alpha-decay chains of the three superheavy nuclei are also studied. The computed alpha-decay half-lives are compared with the values predicted by Generalized Liquid Drop Model and they are found to match reasonably well. 相似文献
85.
Hu Liu Leon M. Smith II Yunyu Mao Weitao Pan Yong‐Jiang Xu Sabina Burdzovic‐Wizeman 《合成通讯》2013,43(3):347-354
An improved route for the preparation of highly functionalized 5,6‐dihydro‐pyrimido[4,5‐b][1,4]oxazepine 1a in multigram quantities was developed. This new methodology was highlighted by the proper methoxy disposition via a regioselective methylation of 2,4,5‐trihydroxy‐benzaldehyde followed by a magnesium sulfate–promoted cyclization. 相似文献
86.
Nicolò Dossi Rosanna Toniolo Evandro Piccin Sabina Susmel Andrea Pizzariello Gino Bontempelli 《Electroanalysis》2013,25(11):2515-2522
A simple method is described to discriminate between analytes comigrating under on‐plate separation conditions, whose electrochemical behavior displays different reversible characters. It is based on the use of dual electrode detectors pencil‐drawn at the end of paper‐based fluidic channels defined by hydrophobic barriers. Simultaneous detection of comigrating species is achieved by applying to the upstream pencil‐drawn working electrode a potential for the oxidation (or reduction) of both analytes, while to the downstream pencil‐drawn working electrode a potential is imposed for the reverse process involving the product of the sole analyte undergoing a reversible enough electrochemical process. The performance of these inexpensive devices was preliminarily optimized by adopting hexacyanoferrate(II) as prototype species undergoing a reversible anodic process at carbon electrodes. They were then used as dual electrode detectors for thin‐layer chromatographic runs conducted on paper‐based microfluidic devices. Two types of synthetic solutions, one containing different contents of dopamine (DA) and ascorbic acid (AA) and the other of paracetamol (PA) and AA, were chosen as model samples. This choice was prompted us by the fact that in both cases these analytes comigrated under the adopted experimental conditions and required similar enough oxidation potentials. Nevertheless, DA and PA underwent reversible enough anodic processes while an irreversible electrochemical reaction is involved in the AA oxidation. Satisfactory results were found for both couples of target analytes, whose simultaneous detection was achieved within 230 s and was characterized by good enough repeatability and sensitivity. In particular, this approach appears to be well suited for the rapid and inexpensive assembling of electrochemical detectors for flow analysis systems. 相似文献
87.
Direct analysis of free bilirubin in human and animal blood serum samples is reported for the first time. A state-of-the-art system comprised of newly developed high-performance liquid chromatography (HPLC) on reverse-phase (RP) C18 support coupled with thermal lens spectrometric detection (TLS), based on excitation at λ = 457.9 nm by an argon laser was used for this purpose. This HPLC-TLS method enabled a baseline separation of all three structural isomers of bilirubin (XIII-α, IX-α and III-α) and the respective degradation products in isocratic mode in fewer than 7 min. The method excels in ultra-high sensitivity with limit of detection (LOD) and limit of quantitation (LOQ) of 90 pM and 250 pM, respectively. Moreover, this method also affords high precision and accuracy, with correlation coefficients R2 > 0.997 over a broad linear range (0.250–150 nM) and R2 = 0.9998 in a concentration range of clinical interest (0.500–25 nM). The method's boosted sensitivity enabled to streamline sample preparation to just one serum ultrafiltration step, which made qualitative evaluation of sample preparation possible for the first time. The performance of the HPLC-TLS method was assessed to have 20-fold enhanced sensitivity when compared to a comparable method incorporating HPLC coupled with diode array detector (DAD), which is also a novel method by itself, and could be applied for free bilirubin determination in patients with elevated bilirubin levels. 相似文献
88.
Francesco Altomare Sabina Milella Graziana Musceo 《Journal of Evolution Equations》2011,11(4):771-792
Of concern are multiplicative perturbations of the Laplacian acting on weighted spaces of continuous functions on
\mathbbRN, N 3 1{{\mathbb{R}}^{N},\; N\geq1} . It is proved that such differential operators, defined on their maximal domains, are pre-generators of positive quasicontractive
C
0-semigroups of operators that fulfill the Feller property. Accordingly, these semigroups are associated with a suitable probability
transition function and hence with a Markov process on
\mathbbRN{{\mathbb{R}}^{N}} . An approximation formula for these semigroups is also stated in terms of iterates of integral operators that generalize
the classical Gauss-Weierstrass operators. Some applications of such approximation formula are finally shown concerning both
the semigroups and the associated Markov processes. 相似文献
89.
Alessia Di Gilio Jolanda Palmisani Gianrocco Ventrella Laura Facchini Annamaria Catino Niccol Varesano Pamela Pizzutilo Domenico Galetta Massimo Borelli Pierluigi Barbieri Sabina Licen Gianluigi de Gennaro 《Molecules (Basel, Switzerland)》2020,25(24)
Despite promising results obtained in the early diagnosis of several pathologies, breath analysis still remains an unused technique in clinical practice due to the lack of breath sampling standardized procedures able to guarantee a good repeatability and comparability of results. The most diffuse on an international scale breath sampling method uses polymeric bags, but, recently, devices named Mistral and ReCIVA, able to directly concentrate volatile organic compounds (VOCs) onto sorbent tubes, have been developed and launched on the market. In order to explore performances of these new automatic devices with respect to sampling in the polymeric bag and to study the differences in VOCs profile when whole or alveolar breath is collected and when pulmonary wash out with clean air is done, a tailored experimental design was developed. Three different breath sampling approaches were compared: (a) whole breath sampling by means of Tedlar bags, (b) the end-tidal breath collection using the Mistral sampler, and (c) the simultaneous collection of the whole and alveolar breath by using the ReCIVA. The obtained results showed that alveolar fraction of breath was relatively less affected by ambient air (AA) contaminants (p-values equal to 0.04 for Mistral and 0.002 for ReCIVA Low) with respect to whole breath (p-values equal to 0.97 for ReCIVA Whole). Compared to Tedlar bags, coherent results were obtained by using Mistral while lower VOCs levels were detected for samples (both breath and AA) collected by ReCIVA, likely due to uncorrected and fluctuating flow rates applied by this device. Finally, the analysis of all data also including data obtained by explorative analysis of the unique lung cancer (LC) breath sample showed that a clean air supply might determine a further confounding factor in breath analysis considering that lung wash-out is species-dependent. 相似文献
90.
Amperometric Sniffer for Volatile Amines Based on Paper‐Supported Room Temperature Ionic Liquids Enabling Rapid Assessment of Fish Spoilage
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Rosanna Toniolo Nicolò Dossi Rossella Svigely Sabina Susmel Innocenzo G. Casella Gino Bontempelli 《Electroanalysis》2014,26(9):1966-1974
A gas sensors based on a room temperature ionic liquid (RTIL) supported on paper is proposed as amperometric sniffer for monitoring volatile amines (VAs) released from fish samples, in order to gain indication of their state of turning spoiled. It was used as a paper electrochemical detector (PED) for a flow injection system in which controlled headspace volumes in equilibrium with ice‐stored fish samples were directly injected. The performance of this RTIL‐PED sensor was preliminarily tested on synthetic samples of trimethylamine (TMA), dimethylamine (DMA), methylamine (MA) and ammonia (i.e. the main species responsible for the typical flavor of spoiled fish), thus verifying that only TMA, DMA and MA can be detected because NH3 oxidation occurred beyond the solvent discharge. This notwithstanding, detection of the sole TMA, DMA and MA as a whole turned out to be well suited for the rapid assessment of fish spoilage, since during storage the release enhancement for these amines is largely predominant over that of NH3. Repeatable (8 % RSD) sharp peaks were detected for all amines above over a wide range (5–1000 nmol) and a detection limit of a little more than 3 nmol was inferred for a signal‐to‐noise ratio of 3. This approach was applied to the detection of VAs released from real fish samples (sardines), in parallel to the determination of their total volatile basic nitrogen (TVBN), which is a conventional indicator frequently adopted for the chemical quality assessment of fish. A substantially satisfactory agreement was found by comparing the data achieved by these two approaches. 相似文献