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排序方式: 共有136条查询结果,搜索用时 15 毫秒
1.
2.
Vilas-Boas M Freire C de Castro B Christensen PA Hillman AR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(1):139-150
Electrogenerated polymers based on the nickel(II) complex 2,3-dimethyl-N,N'-bis(salicylidene)butane-2,3-diaminatonickel(II), poly[Ni(saltMe)], were characterised by in situ FTIR and UV/Vis spectroscopy and ex-situ EPR spectroscopy in order to gain insights into film structure, electronic states and charge conduction. The role of the nickel ions during film oxidation was probed by using EPR to study naturally abundant Ni and 61Ni-enriched polymers. The data from all the spectroscopic techniques are consistent, and clearly indicate that polymerisation and redox switching are associated with oxidative ligand based processes; coulometry suggests that one positive charge was delocalised through each monomer unit. EPR provided evidence for the non-direct involvement of the metal in polymer oxidation: the polymer is best described as a polyphenylene-type compound (conducting polymer), rather than an aggregation of nickel complexes (redox polymer), and the main charge carriers are identified as polarons. An explanation for the high electrochemical stability and conductivity of poly[Ni(saltMe)] with respect to that of poly[Ni(salen)] is proposed. based on stereochemical repulsion between monomeric units; this can impose a less compact supramolecular structure on polymers with bulkier substituents. 相似文献
3.
Breaux GA Hillman DA Neal CM Benirschke RC Jarrold MF 《Journal of the American Chemical Society》2004,126(28):8628-8629
Calorimetry measurements (using a method based on multicollision induced dissociation) have been performed for unsupported gallium clusters, Gan+ (n = 30-50 and 55). Melting transitions have been identified from spikes in the heat capacities recorded as a function of temperature. There are enormous fluctuations in the melting temperatures and the heats of fusion with cluster size. Clusters with n = 31, 33, 37, and 45-47 are "magic melters" with particularly well-defined melting transitions. There is a strong correlation between the heats of fusion, entropies of fusion, and the stabilities of the clusters. However, these quantities are not strongly correlated with the melting temperatures. 相似文献
4.
Gwi Suk Heo Patrick E. Hillman Richard A. Bartsch 《Journal of heterocyclic chemistry》1982,19(5):1099-1103
Interactions of nitrosonium tetrafluoroborate and hexafluorophosphate with 18-crown-6, 15-crown-5, and 12-crown-4 in dichloromethane, acetonitrile, and nitromethane have been probed by a combination of proton magnetic resonance spectroscopy, infrared spectroscopy, and conductance measurements. The stoichiometrics of the crown ether-nitrosonium salt complexes were one mole of 18-crown-6 per mole of nitrosonium salt and two moles of 12-crown-4 per mole of nitrosonium salt in all solvents. For 15-crown-5, the one-to-one stoichiometry observed in acetonitrile and nitromethane changed to two moles of crown ether per mole of nitrosonium salt in dichloromethane. The nature of these complexes is discussed. Treatment of a solution of equimolar nitrosonium hexafluorophosphate and 18-crown-6 in dichloromethane with water produced hydronium hexafluorophosphate-18-crown-6 complex. 相似文献
5.
The nucleation and growth of polythiophene films on gold electrodes has been studied using potentiostatic steps. The mechanism has been deduced and estimates made of the kinetic parameters. Dissolution of the gold substrate at potentials where thiophene polymerisation occurs is suppressed by the initial rapid formation of a monolayer of polymer. The data indicate that formation of bulk film occurs by the instantaneous nucleation and three-dimensional growth of polymer on top of this monolayer. Rate constants for growth parallel to the surface on the bare gold substrate and the covering polymer layer are surprisingly very similar. Growth perpendicular to the surface is slightly more rapid, typically by a factor of 1.5–3, although it is less dependent on potential. The high density of nuclei results in their overlap at an early stage, after which growth is only possible perpendicular to the surface. Within a narrow potential range, the observation of maxima and minima in current-time transients is interpreted in terms of the “death” and “rebirth” of growing centres. 相似文献
6.
Stanley Bruckenstein Alex Fensore Zhufen Li A.Robert Hillman 《Journal of Electroanalytical Chemistry》1994,370(1-2)
Absolute resonant frequency measurements were made on gold-coated AT-cut quartz crystals with one face in contact with a series of liquids. The effect of surface roughness and liquid properties (viscosity and density) was analyzed in terms of a “trapped liquid” model. In this model, liquid present in surface imperfections is viewed as rigidly coupled mass. In some of the literature this density-dependent, but not viscosity-dependent, term is viewed as being additive to the hydrodynamic shift seen for a smooth surface. Data obtained using 1 μm and 5 μm surface finish crystals are inconsistent with the predictions of the trapped liquid model. This suggests hydrodynamic coupling between liquid internal and external to the crevices. Despite the lack of a theoretical model for the liquid motion, it is possible to compensate for frequency variations resulting from changing liquid properties and for roughness effects by making direct measurements of the resonant frequency difference between two crystals exposed to the same solution. This novel procedure works to the extent that the two crystals have similar surface topographies. Compensation is excellent for 1 μm finish crystals and good for 5 μm finish crystals. 相似文献
7.
Shiran Shahar Pnina Hillman Rachel Lubart Debby Ickowicz Haim Breitbart 《Photochemistry and photobiology》2014,90(5):1077-1083
To acquire fertilization competence, spermatozoa must undergo several biochemical and motility changes in the female reproductive tract, collectively called capacitation. Actin polymerization and the development of hyperactivated motility (HAM) are part of the capacitation process. In a recent study, we showed that irradiation of human sperm with visible light stimulates HAM through a mechanism involving reactive‐oxygen‐species (ROS), Ca2+ influx, protein kinases A (PKA), and sarcoma protein kinase (Src). Here, we showed that this effect of light on HAM is mediated by ROS‐dependent activation of the epidermal growth factor receptor (EGFR). Interestingly, ROS‐mediated HAM even when the EGFR was activated by EGF, the physiological ligand of EGFR. Light irradiation stimulated ROS‐dependent actin polymerization, and this effect was abrogated by PBP10, a peptide which activates the actin‐severing protein, gelsolin, and causes actin‐depolymerization in human sperm. Light‐stimulated tyrosine phosphorylation of Src‐dependent gelsolin, resulting in enhanced HAM. Thus, light irradiation stimulates HAM through a mechanism involving Src‐mediated actin polymerization. Light‐stimulated HAM and in vitro‐fertilization (IVF) rate in mouse sperm, and these effects were mediated by ROS and EGFR. In conclusion, we show here that irradiation of sperm with visible light, enhances their fertilization capacity via a mechanism requiring ROS, EGFR and HAM. 相似文献
8.
I. Kiersztyn L. Neto A. Carneiro J. Tedim C. Freire A. R. Hillman 《Journal of Solid State Electrochemistry》2012,16(9):2849-2860
Poly[Cu(3-MeOsalpd)] films with good physical, chemical and electrochemical stability may be potentiodynamically electrodeposited with high deposition efficiency from acetonitrile solutions of the monomer. Comparative coulometric assays with the Ni-based analogue show that the metal in the salen motif does play a role in the electronic structure of the polymer, but that the electroactive response is ligand (not metal) based. The dynamics of redox switching are ultimately limited by coupled electron/counter ion diffusion, but this process is sufficiently rapid that it influences the voltammetric response only for thick films (Γ >420?nmol?cm?2) at high scan rates. Redox cycling in monomer-free electrolyte shows a voltammetric signature that responds, via interaction with the pseudo-crown ether receptor sites, to the presence of Li+, K+, Mg2+ and Ba2+ ions in solution. The most prominent change is associated with the first anodic peak in the i-E signature. For each of the metal ions considered, this peak potential responds logarithmically to concentration in a manner that varies with individual complexed cation and film thickness and to an extent greater than predicted by the Nernst equation. The film characteristics offer some analytical promise, including a trade-off between sensitivity and dynamic range and signal amplification, possibly due to supramolecular effects. 相似文献
9.
Glottal airflow and transglottal air pressure measurements for male and female speakers in soft, normal, and loud voice 总被引:8,自引:0,他引:8
E B Holmberg R E Hillman J S Perkell 《The Journal of the Acoustical Society of America》1988,84(2):511-529
Measurements on the inverse filtered airflow waveform (the "glottal waveform") and of estimated average transglottal pressure and glottal airflow were made from noninvasive recordings of productions of syllable sequences in soft, normal, and loud voice for 25 male and 20 female speakers. Statistical analyses showed that with change from normal to loud voice, both males and females produced loud voice with increased pressure, accompanied by increased ac flow and increased maximum airflow declination rate. With change from normal voice, soft voice was produced with decreased pressure, ac flow and maximum airflow declination rate, and increased dc and average flow. Within the loudness conditions, there was no significant male-female difference in air pressure. Several glottal waveform parameters separated males and females in normal and loud voice. The data indicate higher ac flow and higher maximum airflow declination rate for males. In soft voice, the male and female glottal waveforms were more alike, and there was no significant difference in maximum airflow declination rate. The dc flow did not differ significantly between males and females. Possible relevance to biomechanical differences and differences in voice source characteristics between males and females and across loudness conditions is discussed. 相似文献
10.
We sharpen a recent result of Paternain and Petean by showingthat a closed 4-manifold which admits a Riemannian metric withzero topological entropy and infinite fundamental group eitheris aspherical or has a finite covering space homeomorphic toS3 x S1 or S2 x S1 x S1. 相似文献