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111.
Manca F Giordano S Palla PL Zucca R Cleri F Colombo L 《The Journal of chemical physics》2012,136(15):154906
Stretching experiments on single molecules of arbitrary length opened the way for studying the statistical mechanics of small systems. In many cases in which the thermodynamic limit is not satisfied, different macroscopic boundary conditions, corresponding to different statistical mechanics ensembles, yield different force-displacement curves. We formulate analytical expressions and develop Monte Carlo simulations to quantitatively evaluate the difference between the Helmholtz and the Gibbs ensembles for a wide range of polymer models of biological relevance. We consider generalizations of the freely jointed chain and of the worm-like chain models with extensible bonds. In all cases we show that the convergence to the thermodynamic limit upon increasing contour length is described by a suitable power law and a specific scaling exponent, characteristic of each model. 相似文献
112.
In the simulation of fast cyclic adsorption processes, to apply the Fickian diffusion model it is necessary to include an
increasing number of numerical discretization points as the cycle time is reduced in comparison to the characteristic diffusional
time constant.
We propose a new numerical method based on the definition of two distinct regions within an adsorbent particle: an outer layer
where the concentration varies significantly with large internal gradients leading to enhanced mass fluxes, and an internal
region where the concentration profile is virtually flat. The proposed method leads to the automated generation of a numerical
grid that has a constant number of elements independent of the process cycle time. The procedure is demonstrated on a model
for the simulation of a heatless dryer pressure swing adsorption process. 相似文献
113.
Stefano Agnello Michael Brand Mathieu F. Chellat Silvia Gazzola Rainer Riedl 《Angewandte Chemie (International ed. in English)》2019,58(11):3300-3345
The natural phenomenon of drug resistance is a widespread issue that hampers the performance of drugs in many major clinical indications. Antibacterial and antifungal drugs are affected, as well as compounds for the treatment of cancer, viral infections, or parasitic diseases. Despite the very diverse set of biological targets and organisms involved in the development of drug resistance, the underlying molecular mechanisms have been identified to understand the emergence of resistance and to overcome this detrimental process. Detailed structural information on the root causes for drug resistance is nowadays frequently available, so next‐generation drugs can be designed that are anticipated to suffer less from resistance. This knowledge‐based approach is essential for fighting the inevitable occurrence of drug resistance. 相似文献
114.
115.
Vincenzo G. Albano Carlo Castellari Cristina Femoni M. Carmela Iapalucci Giuliano Longoni Magda Monari Stefano Zacchini 《Journal of Cluster Science》2001,12(1):75-87
The new Au8{Fe(CO)4}4(P^P)2 and Au6Cu2{Fe(CO)4}4(P^P)2 (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au3{Fe(CO)4}2(P^P)]- anions with Au(SEt2)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2 have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis. 相似文献
116.
Purpurin-18 in combination with light leads to apoptosis or necrosis in HL60 leukemia cells 总被引:2,自引:0,他引:2
Di Stefano A Ettorre A Sbrana S Giovani C Neri P 《Photochemistry and photobiology》2001,73(3):290-296
Photodynamic therapy (PDT), a cancer treatment using a photosensitizer and visible light, has been shown to induce apoptosis or necrosis. We report here that Purpurin-18 (Pu18) in combination with light induces rapid apoptotic cell death in the human leukemia cell line (HL60) at low doses and necrosis at higher concentrations. Cells treated with Pu18 and light under apoptotic conditions exhibited DNA laddering and an increase in both cellular content of subdiploid DNA and externalization of phosphatidylserine (PS), indicating DNA fragmentation and loss of membrane phospholipid asymmetry. In the absence of light activation, Pu18 at nanomolar concentrations had no detectable cytotoxic effect. Caspase-3 activity was increased even after 1 h from treatment with low doses of Pu18 and light. The PS exposure and nuclear features of apoptosis were prevented by treatment of cells before illumination with caspase inhibitors benzyloxycarbonyl-Val-Ala-Asp-fluoromethylketone (Z-VAD-FMK) and benzyloxycarbonyl-Asp-Glu-Val-Asp-fluoromethylketone (Z-DEVD-FMK). Conversely, the caspase-1 inhibitor, acetyl-Tyr-Val-Ala-Asp-aldehyde (Ac-YVAD-CHO) failed to suppress the apoptosis. No protective effect of the three caspase inhibitors was observed when the cells were exposed to necrotic concentrations of Pu18 and light. Our results show that caspase-3, but not caspase-1, is involved in the signaling of apoptotic events in PDT with Pu18-induced apoptosis of HL60 cells. Moreover, both the time course of PS exposure and the effect of caspase inhibitors on it indicate that it is regulated in the same manner as DNA fragmentation. 相似文献
117.
Stefano Federico Tuhina Khan Nicola Relitti Giulia Chemi Margherita Brindisi Simone Brogi Ettore Novellino Daniela M. Zisterer Giuseppe Campiani Sandra Gemma Stefania Butini 《Tetrahedron letters》2018,59(51):4466-4470
We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates. 相似文献
118.
Sfarra Stefano Regi Mauro Tortora Mariagrazia Casieri Cinzia Perilli Stefano Paoletti Domenica 《Journal of Thermal Analysis and Calorimetry》2018,132(2):1367-1387
Journal of Thermal Analysis and Calorimetry - The aim of this work is to evaluate the potentiality of a multi-technique nondestructive approach for characterizing the state of conservation of... 相似文献
119.
Giulia Marsico Barbara A. Pignataro Marco Masi Antonio Evidente Francesca Casella Maria Chiara Zonno Jun-Hyung Tak Jeffrey R. Bloomquist Stefano Superchi Patrizia Scafato 《Tetrahedron》2018,74(28):3912-3923
The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature. 相似文献
120.
Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Au(I) catalysed Suzuki coupling reactions. The synthetic protocol is general, easy and produced either biaryls or heteroaryl arenes in good yields (51 positive examples, average yield 80%). o-Benzenedisulfonimide was recovered at the end of the reactions and was reused to prepare the starting salts for further reactions. Mechanistic insights suggest that the o-benzenedisulfonimide anion act as an electron transfer agent and promotes a catalytic cycle which does not require the presence of photocatalysts or external oxidants. 相似文献