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61.
Pierpaolo Bruscolini Carla Buzano Alessandro Pelizzola Marco Pretti 《Macromolecular Symposia》2002,181(1):261-274
Poly(N-isopropylacrylamide) (PNIPAM) in dilute aqueous solution undergoes a collapse transition from coil to globule on increasing temperature. Such coil-to-globule collapse is usually considered analogous to the cold renaturation of small globular proteins. In this paper we propose a theoretical approach that is able to reproduce, in a semi-quantitative way, the unusual behavior of PNIPAM, and the observed thermodynamic properties. The procedure is based on two main steps: (i) the characterization of single monomer hydration thermodynamics, interpreted by a balance between the removal of monomer-monomer interactions and the addition of water-monomer interactions, and (ii) a simplified analysis of a lattice self-avoiding walk (SAW) model, which allows to account for the configurational entropy in a controlled way, and hence to relate the microscopic interactions to the “macroscopic” behavior of the polymer chain. The results show that the temperature dependence and magnitude of the interaction parameters that best fit experimental data validate a recently proposed qualitative interpretation of the mechanism of collapse transition for PNIPAM. The latter result turns out to be relevant to support the analogy with the cold renaturation of small globular proteins, and to clarify some important aspects of protein thermodynamics. 相似文献
62.
Pierpaolo Cordone Hari Krishna Namballa Wayne Wesley Harding 《Journal of heterocyclic chemistry》2020,57(10):3709-3713
Heterocycles that bear the novel 5,6,14,14a-tetrahydro-8H-benzo[6,7][1,4]thiazepino[3,4-a]isoquinoline and the 5,6,14,14a-tetrahydro-8H-13l2-benzo[6,7][1,4]diazepino[3,4-a]isoquinoline frameworks were synthesized in a facile manner. These tetrahydroprotoberberine (THPB)-inspired scaffolds demonstrate selective affinity for the σ1R in contrast to the naturally occurring THPB congeners that show D1R and σ2R selectivity. 相似文献
63.
Tiziano Ghisu Francesco Cambuli Pierpaolo Puddu Natalino Mandas Pranay Seshadri Geoffrey T. Parks 《Meccanica》2018,53(14):3437-3456
In recent years, a number of authors have studied entropy generation in Wells turbines. This is potentially a very interesting topic, as it can provide important insights into the irreversibilities of the system, as well as a methodology for identifying, and possibly minimizing, the main sources of loss. Unfortunately, the approach used in these studies contains some crude simplifications that lead to a severe underestimation of entropy generation and, more importantly, to misleading conclusions. This paper contains a re-examination of the mechanisms for entropy generation in fluid flow, with a particular emphasis on RANS equations. An appropriate methodology for estimating entropy generation in isolated airfoils and Wells turbines is presented. Results are verified for different flow conditions, and a comparison with theoretical values is presented. 相似文献
64.
Sanchita Paul Dr. Pierpaolo Morgante Dr. Samantha N. MacMillan Prof. Jochen Autschbach Prof. David C. Lacy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(40):e202201042
This work details the synthesis, characterization, and catalytic activity of reactive low-coordinate organozinc complexes. The complexes activate hydrogen and they appear to be more active in hydrogenation of ketones and imines than their tridentate pincer analogs. This is thought, in part, to be due to the lack of trailing third phosphorus arm present in previous work. DFT computations reveal a sigma-bond metathesis mechanism is comparable to an alternative aromatization/dearomatization metal-ligand cooperative mechanism. 相似文献
65.
66.
Pierpaolo Ferrante 《应用数学学报(英文版)》2018,34(2):373-385
This paper is aimed at investigating the transient losses in the M/M/1/1 Erlang loss system. We evaluate the explicit form of the probability distribution of the number of losses in the time interval [0, t) and provide two alternative representations: one based on the iterated derivatives of hyperbolic sinus and cosine and the other on the spherical modified Bessel function of the second kind. The mathematical structures of the transient loss rate and of the transient probability of losing all customers are described and several analytical properties are derived. 相似文献
67.
68.
Carmine Coluccini Pierangelo Metrangolo Marco Parachini Dario Pasini Giuseppe Resnati Pierpaolo Righetti 《Journal of polymer science. Part A, Polymer chemistry》2008,46(15):5202-5213
Well‐defined macromolecules have been obtained through free‐radical cyclopolymerization and cyclocopolymerization of difunctional and acrylic‐like monomers, which contained “push‐pull” supramolecular chromophores, able to form 1:1 complexes with Eu3+ ions in solution. The monomeric molecular modules are built around bismalonate crown ethers in a convergent fashion, in which one of the malonate moiety is derivatized as the ylidene malonate push‐pull fragment, and the other malonate moiety is elaborated to introduce two polymerizable and acrylic‐like substituents. The free‐radical induced cyclopolymerization of these monomers, or their cyclocopolymerization with UV/Vis “silent” but structurally related monomers, afforded macromolecular architectures characterized by GPC, NMR and DSC techniques. UV/Vis titration studies, performed with Eu(OTf)3 as the supramolecular probe, revealed how adjacent chromophores within the polymeric backbone are virtually independent from each other, and how the binding ability towards the probe of these multivalent, highly packed cyclopolymeric architectures, although reduced, is still clearly detectable. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5202–5213, 2008 相似文献
69.
Previous research has shown a strong correlation of protein folding rates to the native state geometry, yet a complete explanation for this dependence is still lacking. Here we study the rate-geometry relationship with a simple statistical physics model, and focus on two classes of model geometries, representing ideal parallel and antiparallel structures. We find that the logarithm of the rate shows an almost perfect linear correlation with the "absolute contact order", but the slope depends on the particular class considered. We discuss these findings in the light of experimental results. 相似文献
70.
For the abelian self‐dual Chern‐Simons‐Higgs model we address existence issues of periodic vortex configurations—the so‐called condensates—of nontopological type as k → 0, where k > 0 is the Chern‐Simons parameter. We provide a positive answer to the longstanding problem on the existence of nontopological condensates with magnetic field concentrated at some of the vortex points (as a sum of Dirac measures) as k → 0, a question that is of definite physical interest. © 2015 Wiley Periodicals, Inc. 相似文献