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981.
982.
FS Freitas JN Clifford E Palomares AF Nogueira 《Physical chemistry chemical physics : PCCP》2012,14(34):11990-11993
In this paper we focus on the effect of carboxylated thiophene small molecules as interface modifiers in TiO(2)/P3HT hybrid solar cells. Our results show that small differences in the chemical structure of these molecules, for example, the presence of the -CH(2)- group in the 2-thiopheneacetic acid (TAA), can greatly increase the TiO(2) surface wettability, improving the TiO(2)/polymer contact. This effect is important to enhance exciton splitting and charge separation. 相似文献
983.
Sinthuvanich C Veiga AS Gupta K Gaspar D Blumenthal R Schneider JP 《Journal of the American Chemical Society》2012,134(14):6210-6217
Several cationic antimicrobial peptides (AMPs) have recently been shown to display anticancer activity via a mechanism that usually entails the disruption of cancer cell membranes. In this work, we designed an 18-residue anticancer peptide, SVS-1, whose mechanism of action is designed to take advantage of the aberrant lipid composition presented on the outer leaflet of cancer cell membranes, which makes the surface of these cells electronegative relative to the surface of noncancerous cells. SVS-1 is designed to remain unfolded and inactive in aqueous solution but to preferentially fold at the surface of cancer cells, adopting an amphiphilic β-hairpin structure capable of membrane disruption. Membrane-induced folding is driven by electrostatic interaction between the peptide and the negatively charged membrane surface of cancer cells. SVS-1 is active against a variety of cancer cell lines such as A549 (lung carcinoma), KB (epidermal carcinoma), MCF-7 (breast carcinoma), and MDA-MB-436 (breast carcinoma). However, the cytotoxicity toward noncancerous cells having typical membrane compositions, such as HUVEC and erythrocytes, is low. CD spectroscopy, appropriately designed peptide controls, cell-based studies, liposome leakage assays, and electron microscopy support the intended mechanism of action, which leads to preferential killing of cancerous cells. 相似文献
984.
Andersson CS Öhrström M Popović-Bijelić A Gräslund A Stenmark P Högbom M 《Journal of the American Chemical Society》2012,134(1):123-125
The essential catalytic radical of Class-I ribonucleotide reductase is generated and delivered by protein R2, carrying a dinuclear metal cofactor. A new R2 subclass, R2c, prototyped by the Chlamydia trachomatis protein was recently discovered. This protein carries an oxygen-activating heterodinuclear Mn(II)/Fe(II) metal cofactor and generates a radical-equivalent Mn(IV)/Fe(III) oxidation state of the metal site, as opposed to the tyrosyl radical generated by other R2 subclasses. The metal arrangement of the heterodinuclear cofactor remains unknown. Is the metal positioning specific, and if so, where is which ion located? Here we use X-ray crystallography with anomalous scattering to show that the metal arrangement of this cofactor is specific with the manganese ion occupying metal position 1. This is the position proximal to the tyrosyl radical site in other R2 proteins and consistent with the assumption that the high-valent Mn(IV) species functions as a direct substitute for the tyrosyl radical. 相似文献
985.
Manuel A. Leiva G. Ma. Consuelo Araya Ana Maria Alvarado Rodrigo J. Seguel 《Accreditation and quality assurance》2012,17(1):53-63
The present work presents a measurement uncertainty evaluation according to Guide to the Expression of Uncertainty in Measurement
(GUM) of the concentration of the cations K+ and Li+ and anions NO3−2 and SO4−2 in fine airborne particulate matter, refers to particles less than 2.5 μm in diameter (PM2.5), as measured by ion chromatography (US-EPA 300 method). The GUM method is not typically used to report uncertainty. In general,
the analytical results only report the measurement’s standard deviation under repetition as an uncertainty; thus, not all
sources of uncertainty are considered. In this work, the major sources of uncertainty regarding the measurements were identified
as contributions to linear least square regression lines, repeatability, precision, and trueness. The expanded uncertainty
was approximately 20% for anions and cations. The largest contribution to uncertainty was found to be repeatability. 相似文献
986.
The conformational propensities of the proline analogue bearing a phenyl substituent attached to the β carbon, in either a cis or a trans configuration relative to the carbonyl group, have been investigated. The behaviour of cis- and trans(βPh)Pro has been compared with that of proline in homochiral and heterochiral dipeptide sequences. NMR and IR studies as well as X-ray diffraction analysis provide evidence that the β-phenyl substituent does not disrupt the tendency of proline to occupy the i+1 position of a β-turn. The puckering of the pyrrolidine ring is significantly affected by the presence of the aromatic substituent, which tends to occupy positions that minimize steric repulsions. As a consequence, this substituent adopts specific well-defined orientations, which are more restricted for the cis derivative. Interactions between this aromatic group and that in the adjacent phenylalanine residue may be responsible for some of the conformational differences observed among the different peptides studied. 相似文献
987.
Mitomycin C (MMC) is a potent antitumour agent that forms a covalent bond with the 2-amino group of selected guanines in the minor groove of double-stranded DNA following intracellular reduction of its quinone ring and opening of its aziridine moiety. At some 5'-CG-3' (CpG) steps the resulting monofunctional adduct can evolve towards a more deleterious bifunctional lesion, which is known as an interstrand crosslink (ICL). MMC reactivity is enhanced when the cytosine bases are methylated (5 MC) and decreased when they are replaced with 5-F-cytosine (5FC) whereas the stereochemical preference of alkylation changes upon decarbamoylation. We have studied three duplex oligonucleotides of general formula d(CGATAAXGCTAACG) in which X stands for C, 5MC or 5FC. Using a combination of molecular dynamics simulations in aqueous solution, quantum mechanics and continuum electrostatics, we have been able to (i) obtain a large series of snapshots that facilitate an understanding in atomic detail of the distinct stereochemistry of monoadduct and ICL formation by MMC and its decarbamoylated analogue, (ii) provide an explanation for the altered reactivity of MMC towards DNA molecules containing 5MC or 5FC, and (iii) show the distinct accommodation in the DNA minor groove of the different covalent modifications, particularly the most cytotoxic C1α and C1β ICLs. 相似文献
988.
Elena Bonetti Giovanna Bonfanti Riccarda Rossi 《Journal of Differential Equations》2012,253(2):438-462
In this paper, we investigate a contact problem between a viscoelastic body and a rigid foundation, when both the effects of the (irreversible) adhesion and of the friction are taken into account. We describe the adhesion phenomenon in terms of a damage surface parameter according to Frémond?s theory, and we model unilateral contact by Signorini conditions, and friction by a nonlocal Coulomb law. All the constraints on the internal variables as well as the contact and the friction conditions are rendered by means of subdifferential operators, whence the highly nonlinear character of the resulting PDE system. Our main result states the existence of a global-in-time solution (to a suitable variational formulation) of the related Cauchy problem. It is proved by an approximation procedure combined with time discretization. 相似文献
989.
We develop an agent-based computational model in which the urban informal sector acts as a buffer where rural migrants can earn some income while queuing for higher paying modern-sector jobs. In the model, the informal sector emerges as a result of rural-urban migration decisions of heterogeneous agents subject to social influence in the form of neighboring effects of varying strengths. Besides using a multinomial logit choice model that allows for agent idiosyncrasy, explicit agent heterogeneity is introduced in the form of socio-demographic characteristics preferred by modern-sector employers. We find that different combinations of the strength of social influence and the socio-economic composition of the workforce lead to very different urbanization and urban informal sector shares. In particular, moderate levels of social influence and a large proportion of rural inhabitants with preferred socio-demographic characteristics are conducive to a higher urbanization rate and a larger informal sector. 相似文献
990.