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71.
In this screening study in vitro, two polymer‐conjugated, square‐planar platinum(II) complexes bound to the carrier via a single primary amine ligand were tested for antineoplastic activity against the HeLa human cervical epithelioid carcinoma cell line. In the first of these conjugates, 1‐Pt , the spacer connecting the metal complex with the carrier backbone is a short oligo(ethylene oxide) segment, whereas a long poly(ethylene oxide) chain represents the spacer unit in the second conjugate, 2‐Pt . IC50 data, expressed as conjugate concentration at 50% cell growth inhibition, are 48 µg Pt ml−1 for 1‐Pt and 120 µg Pt ml−1 (estimated) for 2‐Pt , the long tether in the latter conjugate presumably causing retarded enzymic release and lysosomal membrane crossing of the monomeric complex. The IC50 value of 1‐Pt is close to that (44 µg Pt ml−1) of a similar conjugate of an earlier investigation, 3‐Pt , in which the metal is chelated by two carrier‐attached, cis‐oriented amino groups in conformance with the ligand arrangement in cisplatin. It thus appears that, in the carrier‐bound state, both monoamine‐ and cis‐diamine‐coordinated platinum(II) complexes of suitable structures may well show similar biological performance patterns. Copyright© 1999 John Wiley & Sons, Ltd. 相似文献
72.
Matrix effect in bio-analysis of illicit drugs with LC-MS/MS: Influence of ionization type, sample preparation, and biofluid 总被引:2,自引:0,他引:2
Dams R Huestis MA Lambert WE Murphy CM 《Journal of the American Society for Mass Spectrometry》2003,14(11):1290-1294
The purpose of the present work was to evaluate the synergistic effect of ionization type, sample preparation technique, and bio-fluid on the presence of matrix effect in quantitative liquid chromatography (LC)-MS/MS analysis of illicit drugs by post-column infusion experiments with morphine (10-microg/mL solution). Three bio-fluids (urine, oral fluid, and plasma) were pretreated with four sample preparation procedures [direct injection, dilution, protein precipitation, solid-phase extraction (SPE)] and analyzed by both LC-electrospray ionization (ESI)-MS/MS and LC-atmospheric pressure chemical ionization (APCI)-MS/MS. Our results indicated that both ionization types showed matrix effect, but ESI was more susceptible than APCI. Sample preparation could reduce (clean up) or magnify (pre-concentrate) matrix effect. Residual matrix components were specific to each bio-fluid and interfered at different time points in the chromatogram. We evaluated matrix effect in an early stage of method development and combined optimal ionization type and sample preparation technique for each bio-fluid. Simple dilution of urine was sufficient to allow for the analysis of the analytes of interest by LC-APCI-MS/MS. Acetonitrile protein precipitation provided both sample clean up and concentration for oral fluid analysis, while SPE was necessary for extensive clean up of plasma prior to LC-APCI-MS/MS. 相似文献
73.
Voss CV Gruber CC Faber K Knaus T Macheroux P Kroutil W 《Journal of the American Chemical Society》2008,130(42):13969-13972
Black and white are opposites as are oxidation and reduction. Performing an oxidation, for example, of a sec-alcohol and a reduction of the corresponding ketone in the same vessel without separation of the reagents seems to be an impossible task. Here we show that oxidative cofactor recycling of NADP (+) and reductive regeneration of NADH can be performed simultaneously in the same compartment without significant interference. Regeneration cycles can be run in opposing directions beside each other enabling one-pot transformation of racemic alcohols to one enantiomer via concurrent enantioselective oxidation and asymmetric reduction employing defined alcohol dehydrogenases with opposite stereo- and cofactor-preference. Thus, by careful selection of appropriate enzymes, NADH recycling can be performed in the presence of NADP (+) recycling to achieve overall, for example, deracemisation of sec-alcohols or stereoinversion representing a possible concept for a "green" equivalent to the chemical-intensive Mitsunobu inversion. 相似文献
74.
For each sequence P=(p1(t),p2(t),...){\mathcal{P}=(p_1(t),p_2(t),\dots)} of polynomials we define a characteristic series of groups, called the derived series localized at
P{\mathcal{P}}. These group series yield filtrations of the knot concordance group that refine the (n)-solvable filtration. We show that the quotients of successive terms of these refined filtrations have infinite rank. The
new filtrations allow us to distinguish between knots whose classical Alexander polynomials are coprime and even to distinguish
between knots with coprime higher-order Alexander polynomials. This provides evidence of higher-order analogues of the classical
p(t)-primary decomposition of the algebraic concordance group. We use these techniques to give evidence that the set of smooth
concordance classes of knots is a fractal set. 相似文献
75.
Frank W. Crow Wayne K. Duholke Gary E. Martin Richard F. Smith Thomas J. Thamann Anne M. Cooper John W. Hallberg James R. Blinn Constance G. Chidestere 《Journal of heterocyclic chemistry》1999,36(4):1049-1055
The structure of a novel, thermally-induced degradant of the antibiotic pirlimycin is presented. The degradant was discovered during thermal stress stability testing of pirlimycin. The structure was determined using high resolution mass spectrometry, ms/ms fragmentation, and extensive nmr studies including a combination of homonuclear TOCSY and gradient, inverse-detected 2-D nmr experiments which included GHSQC and GHMBC. All nmr, high resolution ms and ms/ms fragmentation data are consistent with loss of a molecule of HCl during a ring closure involving one of the hydroxyl moieties from the sugar portion of the molecule forming a tetrahydrofurano[3,2-b]perhydropyran ring structure. The X-ray crystal structure is reported for pirlimycin. Using this structure molecular modelling studies are performed which demonstrate the feasibility of the formation of the new structure. 相似文献
76.
Ludmila C. Fidale Constance Ißbrücker Priscilla L. Silva Camila M. Lucheti Thomas Heinze Omar A. El Seoud 《Cellulose (London, England)》2010,17(5):937-951
Although cellulose acetates, CAs, are extensively employed there is scant information about the systematic dependence of their properties on their degree of substitution, DS; this is the subject of the present work. Nine CAs samples, DS from
0.83 to 3.0 were synthesized; their films were prepared. The following solvatochromic probes have been employed in order to
determine the empirical polarity, E
T(33); “acidity, α”; “basicity, β”, and “dipolarity/polarizability, π*” of the casted films: 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)
phenolate, WB; 4-nitroaniline; 4-nitroanisole; 4-nitro-N,N-dimethylaniline; 2,6-diphenyl-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, RB. Additionally, two systems, ethanol plus ethyl
acetate (EtOH–EtAc), and cellulose plus cellulose triacetate, CTA, were employed as models for CAs of different DS. Regarding
the model systems, the following was observed: (i) For EtOH–EtAc, the dependence of all solvatochromic parameters on the “equivalent-DS”
of the binary mixture was non-linear because of preferential solvation; (ii) The dependence of E
T(33) on equivalent DS of the cellulose–CTA films is linear, but the slope is smaller than that of the corresponding plot for
CAs. This is attributed to the more efficient hydrogen bonding in the model system, a conclusion corroborated by IR measurements.
The dependence of solvatochromic parameters of CAs on their DS is described by the simple equations; a consequence of the
substitution of the OH by the ester group. The thermal properties of bulk CAs samples were investigated by DSC and TGA; their
dependence on DS is described by simple equations. The relevance of these data to the processing and applications of CAs is
briefly discussed. 相似文献
77.
Shearer TW Smith KS Diaz D Asher C Ramirez J 《Combinatorial chemistry & high throughput screening》2005,8(1):89-98
The high level of attrition of drugs in clinical development has led pharmaceutical companies to increase the efficiency of their lead identification and development through techniques such as combinatorial chemistry and high-throughput (HTP) screening. Since the major reasons for clinical drug candidate failure other than efficacy are pharmacokinetics and toxicity, attention has been focused on assessing properties such as metabolic stability, drug-drug interactions (DDI), and absorption earlier in the drug discovery process. Animal studies are simply too labor-intensive and expensive to use for evaluating every hit, so it has been necessary to develop and implement higher throughput in vitro ADME screens to manage the large number of compounds of interest. The antimalarial drug development program at the Walter Reed Army Institute of Research, Division of Experimental Therapeutics (WRAIR/ET) has adopted this paradigm in its search for a long-term prophylactic for the prevention of malaria. The overarching goal of this program is to develop new, long half-life, orally bioavailable compounds with potent intrinsic activity against liver- and blood-stage parasites. From the WRAIR HTP antimalarial screen, numerous compounds are regularly identified with potent activity. These hits are now immediately evaluated using a panel of in vitro ADME screens to identify and predict compounds that will meet our specific treatment criteria. In this review, the WRAIR ADME screening program for antimalarial drugs is described as well as how we have implemented it to predict the ADME properties of small molecule for the identification of promising drug candidates. 相似文献
78.
Rapid adaptation to foreign-accented English 总被引:1,自引:0,他引:1
This study explored the perceptual benefits of brief exposure to non-native speech. Native English listeners were exposed to English sentences produced by non-native speakers. Perceptual processing speed was tracked by measuring reaction times to visual probe words following each sentence. Three experiments using Spanish- and Chinese-accented speech indicate that processing speed is initially slower for accented speech than for native speech but that this deficit diminishes within one minute of exposure. Control conditions rule out explanations for the adaptation effect based on practice with the task and general strategies for dealing with difficult speech. Further results suggest that adaptation can occur within as few as two to four sentence-length utterances. The findings emphasize the flexibility of human speech processing and require models of spoken word recognition that can rapidly accommodate significant acoustic-phonetic deviations from native language speech patterns. 相似文献
79.
Design of a monolithic piezoelectrically actuated microelectromechanical tunable vertical-cavity surface-emitting laser 总被引:1,自引:0,他引:1
We report the design of a monolithic piezoelectrically actuated microelectromechanical tunable vertical-cavity surface-emitting laser (VCSEL). The main advantages of piezoelectric actuation compared with conventional capacitive techniques are improved wavelength control, reduced external and tilt losses, and lower power supply voltages. The details of the piezoelectric actuation scheme for a 980-nm VCSEL with a variable air gap are described. A tuning range of approximately 35 nm can theoretically be achieved with a 3-V power supply (2 x reduction from that of electrostatic actuation) by use of a 250-microm-long cantilever beam. The proposed actuation mechanism is insensitive to the pull-in phenomenon, therefore improving wavelength control and reducing threshold current. Drastic improvements in power efficiency make it ideal for low-power applications such as all-optical communication, chip-scale atomic clocks, and biological studies. 相似文献
80.