Ultrabroadband Near-Infrared Transient Absorption Spectrometer with Simultaneous 900-2350†nm Detection.

In this work, we detail an ultrafast pump-probe transient absorption (TA) spectrometer capable of probing the near-infrared (NIR) spectral region from 900 to 2350 nm simultaneously. Two key advances were required to overcome previous spectral window limitations, which typically result from constrained supercontinuum ranges (e.g., 1700 nm) and/or InGaAs detector line rates, especially those with >1700 nm range. First, we generated a broadband NIR supercontinuum using the 1980 nm idler beam of an optical parametric amplifier and implement a unique spectral filtering scheme to balance the detected spectrum. Second, we used a prism-based spectrometer system equipped with high speed InGaAs cameras having ∼2500 nm sensitivity cutoffs. To the best knowledge of the authors, such an extended probe range was previously inaccessible because the combination of two optical geometries either using different supercontinuum crystal materials for generating the NIR and shortwave infrared (SWIR) regions, or using differing pump wavelengths, were required. Finally, we demonstrate the performance and capabilities of the ultrabroadband TA spectroscopy system by presenting data showing ultrafast charge photogeneration in a polymer : fullerene blend thin-film and comparing the results to the literature with a complete agreement.

The unmet needs of older people in Nsawam, Ghana.

Although healthy life expectancy is projected to be increasing among older people in Ghana, a high proportion and number of older people will live with functional disability, warranting their need for long-term care. We explored the expressions used by older people to describe their needs and preference of care and support. Using the descriptive qualitative approach, 14 older people were engaged via semi-structured interviews, and the data were analysed thematically. The study found that older people desired a decent accommodation, preferential healthcare, adequate nutrition, and an opportunity to interact with their peers at social functions. A provision of sufficient financial assistance, adequate healthcare, the periodic organisation of social and group events for older people, and the availability of home care and support could help older people address these needs. The paper reveals the need for interventional research on how a model incorporating social, health and environmental factors even during a pandemic can address older people's varying needs.

Mechanistic elucidation of the tandem Diels-Alder/(3 + 2) cycloadditions in the design and syntheses of heterosteroids.

The potential of azasteroids as novel drug candidates has prompted numerous studies towards the syntheses of heterosteroidal skeletons. The preparation of novel azasteroidal compounds and the modification of substituents on their steroidal skeletons might provide excellent congeners with useful biological properties. We present herein computational investigations on the Diels-Alder/(3 + 2) tandem sequential cycloaddition reaction of 21 distinctive derivatives of furylcinnamate with phenyl azides. First, we performed the computational study on the originally reported reaction of ester-substituted furylcinnamate derivatives 1a2 and 1b2 with phenyl azide (3) under the experimental conditions. We extended the scope of these tandem cycloaddition reactions by studying several variants of 1a1, 1b1, and 1c1 and their reactivity towards 3. In all instances of tandem reactions considered in this study, the Diels-Alder cycloaddition step is the rate-determining step (rds). Electron-withdrawing substituted 1a1, 1b1, and 1c1 decrease the barrier of the rds while electron-donating substituents substantially increase the barrier of the rds. The parent reaction (1a1) selectively proceeds via transition states T5Exa to give tandem adduct 5Exa, the experimentally observed tandem product. In the case of 1b1 and 1c1, the reaction is competitively favored via T4Ex and T5Ex to give corresponding 4Ex and 5Ex (the experimentally observed tandem adducts). The various substituents studied demonstrate that the tandem adduct obtained is highly dependent on the substituents on the Diels-Alder intermediate. Whereas electron-withdrawing groups substantially decrease the barrier of the rds, the direct opposite is true for electron-donating groups. A plot of electrophilicity indices against activation energies obtains a favorable correlation. We also investigated the unreported reactivity of a furylcinnamate (2-1a2) with several nitrile imines. Such a reaction is found to proceed through a similar mechanism as those seen for the phenyl azide. It is observed that di-substituted nitrile imines react with furylcinnamate (2-1a2) at favorable energetics than phenyl azide. Calculated GEDT values unveil that the non-polar solvent (toluene) will stabilize the non-polar reaction through van der waals interactions.

DFT mechanistic studies on the regio-, stereo-, and enantio-selectivity of 1,3 dipolar cycloadditions of quinolinium imides with olefins, maleimides, and benzynes for the synthesis of fused N,N'-heterocycles.

This work investigated computationally the regio-, stereo-, and enantio-selectivity of the reactions of azomethine imines with olefins, maleimides, and benzynes, important reactions towards the synthesis of heteropolycyclic, N,N'-fused, spirocyclic systems, which serve as building blocks for the synthesis of many pharmaceuticals, agrochemicals, and biologically active compounds. The results show that the thermally controlled diastereoselective [3 + 2] cycloaddition reaction between quinolinium imide and methyl acrylate provides two regio-isomers: 1,4-regioisomer (N-C1, C-C2) and 1,3-regioisomer (N-C2, C-C1). The 1,4-regioisomer has cis and trans-stereoisomers while the 1,3-regioisomer has R-enantiomer and S-enantiomer, and the barriers for the formation of these isomers are 5.1, 19.1, 10.7, and 10.5 kcal/mol, respectively. The reaction between quinolinium imide and maleimide leads to the formation of two stereoisomers; cis-isomer and trans-isomer in which the cis-isomer is kinetically and thermodynamically favoured by 6.1 kcal/mol and 8.7 kcal/mol, respectively. The reaction between quinolinium imide and benzyne also leads to the formation of two stereoisomers through one transition state, with a barrier of 3.0 kcal/mol. Global electrophilicity index calculations show that the dipole acts as a good electrophile in the reaction and decreasing or increasing electrophilicity index has no correlation with the activation barriers. Graphical abstractPathways of the 1,3 dipolar cycloadditions of quinolinium imides with olefins, maleimides, and benzynes for the synthesis of fused N,N'-heterocycles.