Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorption energy of the central, C, N, O, or S atom, the scaling constant depending only on x. A model is proposed to understand this behavior. The scaling model is developed into a general framework for estimating the reaction energies for hydrogenation and dehydrogenation reactions.     

Synthesis of Nitrogen‐Doped Mesoporous Carbon Spheres with Extra‐Large Pores through Assembly of Diblock Copolymer Micelles

The synthesis of highly nitrogen‐doped mesoporous carbon spheres (NMCS) is reported. The large pores of the NMCS were obtained through self‐polymerization of dopamine (DA) and spontaneous co‐assembly of diblock copolymer micelles. The resultant narrowly dispersed NMCS possess large mesopores (ca. 16 nm) and small particle sizes (ca. 200 nm). The large pores and small dimensions of the N‐heteroatom‐doped carbon spheres contribute to the mass transportation by reducing and smoothing the diffusion pathways, leading to high electrocatalytic activity.     

Dual Functioning Thieno‐Pyrrole Fused BODIPY Dyes for NIR Optical Imaging and Photodynamic Therapy: Singlet Oxygen Generation without Heavy Halogen Atom Assistance

We discovered a rare phenomenon wherein a thieno‐pyrrole fused BODIPY dye (SBDPiR690) generates singlet oxygen without heavy halogen atom substituents. SBDPiR690 generates both singlet oxygen and fluorescence. To our knowledge, this is the first example of such a finding. To establish a structure–photophysical property relationship, we prepared SBDPiR analogs with electron‐withdrawing groups at the para‐position of the phenyl groups. The electron‐withdrawing groups increased the HOMO–LUMO energy gap and singlet oxygen generation. Among the analogs, SBDPiR688, a CF₃ analog, had an excellent dual functionality of brightness (82290 m ^?1 cm^?1) and phototoxic power (99170 m ^?1 cm^?1) comparable to those of Pc 4, due to a high extinction coefficient (211 000 m ^?1 cm^?1) and balanced decay (Φ_flu=0.39 and Φ_Δ=0.47). The dual functionality of the lead compound SBDPiR690 was successfully applied to preclinical optical imaging and for PDT to effectively control a subcutaneous tumor.     

Preparation of a Series of 5-Methyl-3-(substituted)-[1,2,4]triazines

Procedures for the synthesis of thirty-six 5-methyl-3-(substituted)-[1,2,4]triazines have been described. These compounds were evaluated for antagonism at metabotropic glutamate receptor subtype 5 (mGluR5). Two compounds, 5b and 3c, were determined to be low micromolar inhibitors of mGluR5.     

A synthetic approach to kingianin A based on biosynthetic speculation

A synthetic approach towards the structurally complex dimer, kingianin A is reported. The strategy involved a cascade of complexity generating reactions, inspired through biosynthetic speculation. A concise protecting group free synthesis of the proposed monomeric precursor pre-kingianin A has been achieved using a tandem Stille cross-coupling reaction and electrocyclisation process. However, preliminary studies of the key dimerisation reaction have been conducted, which indicate that the process is not spontaneous, raising questions as to the origin of this complex natural product.     

Light charged particle emission and fission in238U+238U collisions at 1,740 MeV

Inclusive⁴He and⁴H energy spectra and heavy fragment coincidence correlations have been measured for reactions of 7.31 MeV/u²³⁸U with²³⁸U and^?197Au targets. The H/He production cross sections are in the range 15–26 mb, and their emission spectra are very similar for the two systems. The observed strong kinematic shifts with angle are reproduced in shape and magnitude by Monte Carlo simulations of particle evaporation from projectile-like and target-like fragments, indicating competition between charged particle emission and sequential fission. No evidence is found for high energy charged particle emission associated with ultra-highZ composite systems. Heavy fragment measurements indicate an abundance of quasielastic and deeply inelastic reaction fragments, as well as sequential fission of target and projectile nuclei. For²³⁸U nuclei, the fission occurs predominantly in an asymmetric mode, reminiscent of fission at low excitation energy. For²³⁸+²³⁸U reactions in the vicinity of the grazing angle, the frequency of single sequential fission (with survival of the partner fragment) is twice as large as double sequential fission in which both the target and projectile undergo fission. In²³⁸U+¹⁹⁷Au reactions, the survival probability of the heavy fragments is even greater. The surprisingly high survival probabilities of high-Z fragments imply a preponderance of very soft collisions in these very-heavy-ion reactions, at least at energies not very far over the Coulomb barrier.     

Empirical method for the prediction of business executive jet cabin noise levels

As a result of flight noise measurements made at various locations in the cabin of the standard lined/no interior Westwind model 1124 business executive jet, it was possible to develop an empirical method for predicting the overall sound pressure level (OASPL) at any required location in the cabin. The cabin overall sound level in decibels (linear) may be found from nomographs related to aircraft altitude, mach number or velocity. The noise spectrum at any location may be found from a reference spectrum shape corrected for local parameters. The accuracy of the prediction method, verified by additional tests, was found to be ± 1 dB.