Cyclization of free radicals at the C-7 position of ethyl indole-2-carboxylate derivatives: an entry to a new class of Duocarmycin Analogues

Aryl free-radicals generated at the C-7 position of ethyl indole-2-carboxylates bearing N-allyl and propargylic groups triggered intramolecular cyclizations to furnish a new class of Duocarmycin analogues, formal ethyl pyrrolo[3,2,1-ij]quinoline-2- carboxylate derivatives, through the less favorable 6-endo-trig cyclization mode.     

Electrochemical materials science: calculation vs. experiment as predictive tools in tailoring intrinsically conducting polythiophenes

A series of 3-(p-X-phenyl)thiophene monomers (X = −H, –CH₃, –OCH₃, –COCH₃, –COOC₂H₅, –NO₂) was electrochemically polymerized to furnish polymer films that could be reversibly reduced and oxidized (n- and p-doped). The oxidation potentials of the monomers and formal potentials of the n- and p-doping processes of polymers were correlated with resonance and inductive effects of the substituents on the phenyl ring as well as the ionization potentials of the monomers calculated via density function theory, which correspond to the energies for generating radical cations during oxidative processes.     

Activation cross-sections for209Bi(n,α)206Tl reaction

Cross-section for²⁰⁹Bi(n, α)²⁰⁶Tl reaction at incident neutron energies 340±150 keV and 575±235 keV have been measured to be 1.26±0.18 μb and 1.55±0.23 μb, respectively. The activation technique was used for measuring the cross-sections. These values have been compared with theoretical values based on Hauser Feshbach Statistical Model.     

On the elastoplastic cyclic analysis of plane beam structures using a flexibility-based finite element approach

This paper presents the extension of a flexibility-based large increment method (LIM) for the case of cyclic loading. In the last few years, LIM has been successfully tested for solving a range of non-linear structural problems involving elastoplastic material models under monotonic loading. In these analyses, the force-based LIM algorithm provided robust solutions and significant computational savings compared to the displacement-based finite element approach by using fewer elements and integration points. Although in cyclic analysis a step-by-step solution procedure has to be adopted to account for the plastic history, LIM will still have many advantages over the traditional finite element method. Before going into the basic idea of this extension, a brief discussion regarding LIM governing equations is presented followed by the proposed solution procedure. Next, the formulation is specified for the treatment of the elastic perfectly plastic beam element. The local stage for the beam behavior is discussed in detail and the required improvement for the LIM methodology is described. Illustrative truss and beam examples are presented for different non-linear material models. The results are compared with those obtained from a standard displacement method and again highlight the potential benefits of the proposed flexibility-based approach.     

Uncovering molecular processes in crystal nucleation and growth by using molecular simulation

Exploring nucleation processes by molecular simulation provides a mechanistic understanding at the atomic level and also enables kinetic and thermodynamic quantities to be estimated. However, whilst the potential for modeling crystal nucleation and growth processes is immense, there are specific technical challenges to modeling. In general, rare events, such as nucleation cannot be simulated using a direct "brute force" molecular dynamics approach. The limited time and length scales that are accessible by conventional molecular dynamics simulations have inspired a number of advances to tackle problems that were considered outside the scope of molecular simulation. While general insights and features could be explored from efficient generic models, new methods paved the way to realistic crystal nucleation scenarios. The association of single ions in solvent environments, the mechanisms of motif formation, ripening reactions, and the self-organization of nanocrystals can now be investigated at the molecular level. The analysis of interactions with growth-controlling additives gives a new understanding of functionalized nanocrystals and the precipitation of composite materials.     

沸石负载Ni催化剂在甲烷干重整中的稳定性(英文)

Ni/γ-Al2O3 , Ni/Y-zeolite, and Ni/H-ZSM-5 catalysts were prepared using the incipient wetness impregnation method. Their catalytic performance in dry reforming of methane was studied. The fresh and used catalysts and deposited carbon were characterized using H2 temperature-programmed reduction, temperature-programmed oxidation, N2 adsorption-desorption, X-ray diffraction, and thermogravimetric analysis. The H-ZSM-5-supported Ni catalyst proved to be more stable than the other two catalysts, as it had the lowest carbon deposition.     

Thrombin contributes to the injury development and neurological deficit after acute subdural hemorrhage in rats only in collaboration with additional blood-derived factors

Background

Acute subdural hemorrhage (ASDH) is a severe consequence of traumatic brain injury. The occurrence of subdural blood increases the lethality of these patients independent of the amount of blood or elevated intracranial pressure. Thrombin is one of the potential harmful blood components. Possible harmful effects of thrombin are mediated via the Protease-activated-receptor-1 (PAR1) and thus, translating the acute Thrombin release after ASDH into cell loss. The objectives of the present study were twofold, namely to examine (1) the impact of direct thrombin inhibition in the acute phase after hemorrhage on the long-term histological and functional deficits and (2) the early inhibition of PAR1 activation by thrombin with the selective antagonist SCH79797 on lesion volume at 14 days after ASDH. The effects of thrombin on the lesion size were investigated in two separate experiments via (1) direct thrombin inhibition in the subdural infused blood (Argatroban 600 µg) as well as by (2) intraventricular injection of the PAR-1 antagonist SCH79797 (1 µg or 5 µg). Lesion volume and behavior deficits using a neurological deficit score and a motor function test (beam balance test) were analyzed as outcome parameters at 14 days after injury.

Results

59 Male Sprague–Dawley rats received a subdural infusion of 300 µl autologous blood or sham operation. Lesion volume at 14 days after ASDH tended to be smaller in the Argatroban-treated group when compared to the vehicle group (8.1?±?1.1 vs. 10.1?±?2.3 mm², n.s.). Motor deficits in the beam balance test were not significantly less severe in the Argatroban-treated group. Animals treated with SCH79797 also showed a trend towards dose-dependent decreased lesion volume in comparison to the vehicle-treated group (1 μg: 4.3?±?0.7 mm³; 5 μg: 3.8?±?1.1 mm³; vehicle: 6.5?±?2.0 mm³, n.s).

Conclusions

Thrombin inhibition in the subdural blood and local cerebral blockade of PAR-1 cause a tendency towards reduced lesion volume or functional recovery. All results show a trend in favor of the acute treatment on the outcome parameters. Our results suggests that thrombin could be an important blood-derived factor during acute subdural hemorrhage that translates its deleterious effects in concert with other blood-induced factors.

     

Thermodynamical analysis of heat transfer of gravity-driven fluid flow via fractional treatment: an analytical study

Journal of Thermal Analysis and Calorimetry - This paper presents that how the characteristics of thermal radiation depend on the temperature of unsteady gravity-driven thermal convection flow of...     

Self-Organization of Lipid-Porphyrin Conjugates at the Air/Water Interface

Lipid-porphyrin conjugates are versatile compounds which can self-assemble into liposome-like structures with multifunctional properties. Most of the conjugates that have been described so far, consisted in grafting pyropheophorbide-a (Pyro-a) or other porphyrin derivatives through the esterification of the hydroxyl group in the sn-2 position of a lysophosphatidylcholine. However, despite the versatility of these conjugates, less is known about the impact of the lipid backbone structure on their 2D phase behavior at the air/water interface and more precisely on their fine structures normal to the interface as well as on their in-plane organization. Herein, we synthesized a new lipid-porphyrin conjugate (PyroLSM) based on the amide coupling of Pyro-a to a lysosphingomyelin backbone (LSM) and we compared its interfacial behavior to that of Pyro-a and Pyro-a conjugated lysophosphatidylcholine (PyroLPC) using Langmuir balance combined to a variety of other physical techniques. Our results provided evidence on the significant impact of the lipid backbone on the lateral packing of the conjugates as well as on the shape and size of the formed domains. Compared to Pyro-a and PyroLPC monolayers, PyroLSM exhibited the highest lateral packing which highlights the role of the lipid backbone in controlling their 2D organization which in turn may impact the photophysical properties of their assemblies.     

The Chemistry of N-substituted benzotriazoles. Part 22 [1]: Transformations of 1-(trimethylsilylmethyl)benzotriazole

1-(Trimethylsilylmethyl)benzotriazole is readily prepared from benzotriazole and chloromethyltrimethylsilane. It undergoes fluoride-catalyzed desilylation with carbonyl compounds and forms an anion that can be alkylated and acylated readily and undergoes Peterson olefination. 1-(Cyclohexylidenemethyl)benzotriazole is lithiated exclusively at the α carbon atom, and the anion can be cleanly alkylated. 1-(α-Acylalkyl)benzotriazoles are reduced to ketones with zinc and acid. The stability of 1-alkenylbenzotriazoles to hydrolysis has been studied.