Asymmetric aziridination with chiral allyl aminosulfoxonium ylides: synthesis of alkenyl aziridine carboxylates and palladium-catalyzed E,trans/E,cis-isomerization of an alkenyl aziridine

Chiral cyclic and acyclic allyl aminosulfoxonium ylides have been generated from aminosulfoxonium-substituted β,γ-unsaturated α-amino acids (method A) and 1-alkenyl aminosulfoxonium salts (method B) upon treatment with DBU. Their application to the asymmetric aziridination of N-tert-butyl-sulfonyl imino ester, generated either in situ (method A) or externally added (method B), gave the corresponding alkenyl aziridine carboxylates with medium to high diastereoselectivity and enantioselectivity. A highly stereoselective Pd(0)-catalyzed isomerization of an E,trans-configured alkenyl aziridine methanol derivative to its E-cis-isomer is described, which proceeded with retention of the double bond configuration.     

Near-infrared absorbing Ru(ii) complexes act as immunoprotective photodynamic therapy (PDT) agents against aggressive melanoma

Mounting evidence over the past 20 years suggests that photodynamic therapy (PDT), an anticancer modality known mostly as a local treatment, has the capacity to invoke a systemic antitumor immune response, leading to protection against tumor recurrence. For aggressive cancers such as melanoma, where chemotherapy and radiotherapy are ineffective, immunomodulating PDT as an adjuvant to surgery is of interest. Towards the development of specialized photosensitizers (PSs) for treating pigmented melanomas, nine new near-infrared (NIR) absorbing PSs based on a Ru(ii) tris-heteroleptic scaffold [Ru(NNN)(NN)(L)]Cl_n, were explored. Compounds 2, 6, and 9 exhibited high potency toward melanoma cells, with visible EC₅₀ values as low as 0.292–0.602 μM and PIs as high as 156–360. Single-micromolar phototoxicity was obtained with NIR-light (733 nm) with PIs up to 71. The common feature of these lead NIR PSs was an accessible low-energy triplet intraligand (³IL) excited state for high singlet oxygen (¹O₂) quantum yields (69–93%), which was only possible when the photosensitizing ³IL states were lower in energy than the lowest triplet metal-to-ligand charge transfer (³MLCT) excited states that typically govern Ru(ii) polypyridyl photophysics. PDT treatment with 2 elicited a pro-inflammatory response alongside immunogenic cell death in mouse B16F10 melanoma cells and proved safe for in vivo administration (maximum tolerated dose = 50 mg kg⁻¹). Female and male mice vaccinated with B16F10 cells that were PDT-treated with 2 and challenged with live B16F10 cells exhibited 80 and 55% protection from tumor growth, respectively, leading to significantly improved survival and excellent hazard ratios of ≤0.2.

Ru(ii) photosensitizers (PSs) destroy aggressive melanoma cells, triggering an immune response that leads to protection against tumor challenge and mouse survival.     

输液管的非线性振动、分叉与混沌——现状与展望

围绕输液管的非线性振动、分叉与混沌问题，对近几年来的主要研究工作加以综述并提出预测，其中包括运动方程中非线性项的归纳与讨论、非线性动力分析的一些现代计算方法、定常流速下输液管的分叉与混沌行为、振荡流速下输液管的参数共振以及今后值得进一步研究的某些问题．     

A radiative transfer model for surface radiation budget studies

A high resolution spectral radiative transfer model of the troposphere for computing downwelling radiance and flux density at the surface in the 5–200 μm region has been developed. The model is fast and accurate and takes into consideration all major and minor constituents active in this region, namely, water vapor, carbon dioxide, ozone, nitrous oxide, and methane. It uses the quasi-random band model of absorption for computing atmospheric transmittances due to various bands. Continuum absorption by water vapor in the 8–14 μm region has also been taken into account.The model has been used to examine the sensitivity of downwelling flux to variations of surface water vapor pressure (or surface relative humidity), water vapor scale-height and concentrations of other gaseous constituents of the atmosphere. In addition, sensitivity to changes in a number of cloud parameters, namely, fractional cloud cover, cloud hieght, and high-cloud emissivity, has also been examined. Results obtained with the present model compare well with those from other empirical and semi-empirical correlations. The present work demonstrates, for the first time, the feasibility of using a high-resolution narrow-band model for computing this flux for a meteorological application.     

Electronic spectra of parafluorobromobenzene

The electronic absorption spectrum of parafluorobromobenzene is reported together with its band shape and molecular geometry. The electronic transition is found to be the 2900–2400 Å system and the analysis consistent with other paraheterohalogenated benzenes. The intense bands, including 0–0, are double headed and areB-type in nature.A-type vibronic bands are also observed although less intense than theB-type bands. In all 9 excited states and 5 ground state fundamentals could be assigned.     

Two sum theorems for topological spaces

Two general criterias for the union of topological spaces of a given type to be also of the same type, are presented.     

Real time out-of-plane vibration measurement/monitoring using Talbot interferometry

In the present paper, application of Talbot interferometry for real-time vibration measurement is investigated. Experiments were conducted to measure/monitor out-of-plane motion of a vibrating loudspeaker membrane. Experimental results demonstrate that by using Talbot interferometry out-of-plane vibrations as well as phase lag between driving force and membrane oscillation can be measured.