Development of a Mild and Versatile Directed Cycloaddition Approach to Pyridines

The aza-Diels–Alder cycloaddition of 1,2,4-triazines with alkynes offers a rapid and convenient method for the synthesis of highly substituted pyridines, but often requires harsh conditions and long reaction times. The present study offers a solution to these limitations by use of a temporary tether established by a Lewis acid–base complexation of in situ generated alkynylboranes and triazines bearing a Lewis basic donor. The cycloaddition reactions take place within 20 min at 40 °C and provide direct access to a broad range of pyridines with complete and predictable regiocontrol. The carbon[BOND]boron bond can be further functionalised by cross-coupling allowing further functionality to be introduced after cycloaddition

Extended π-conjugated pyrene derivatives: structural, photophysical and electrochemical properties

This article presents a set of extended π-conjugated pyrene derivatives, namely 1,3-di(arylethynyl)-7-tert-butylpyrenes, which were synthesized by a Pd-catalyzed Sonogashira coupling reaction of 1,3-dibromo-7-tert-butylpyrenes with the corresponding arylethynyl group in good yields. Despite the presence of the tert-butyl group located at the 7-position of pyrene, X-ray crystallographic analyses show that the planarity of the Y-shaped molecules still exhibits strong face-to-face π-π stacking in the solid state; all of the compounds exhibit blue or green emission with high quantum yields (QYs) in dichloromethane. DFT calculations and electrochemistry revealed that this category of compound possesses hole-transporting characteristics. In addition, with strong electron-donating (-N(CH₃)₂) or electron-withdrawing (-CHO) groups in 2 d or 2 f, these molecules displayed efficient intramolecular charge-transfer (ICT) emissions with solvatochromic shifts from blue to yellow (green) on increasing the solvent polarity. Furthermore, the compounds 2 d and 2 f possess strong CT characteristics

Language shift and language maintenance among the Bidayuh younger generation at Kampung Semeba, Kuching, Sarawak / Beatrice Paul Diring

The Bidayuh people in Kampung Semeba are in the process of assimilating themselves into the 21st Century through the world of globalization. These changes create new challenges for them and their dialects, for they have to master the prominent languages like Bahasa Malaysia and English for better prospect in socio status, economy, education, harmonious relations with other ethnic groups and political stability. In the pursuit, the Bidayuh of Kampung Semeba slowly shift their indigenous language to the dominant language. Thus,the research aims to investigate factors that possibly contribute to language shift among the Bidayuh community in Kampung Semeba. This study employs qualitative and quantitative methods. The study reveals that the language policy such as Bahasa Malaysia, English and other dominant languages like Sarawak Local Malay Dialect and Iban Language hasten the people of Kampung Semeba to shift their language. The study is significant especially to the younger generation as they were found to use a lot of borrowed words from other languages

The NORBI table makes students understand the verb have / Beatrice Paul Diring

The purpose ofthis study was to investigate whether the ESL learners in tire upper primary school understand the verb ‘have’ using the NORBI table. Factors causing the understanding ofthe verb ‘have’ using the NORBI table were also identified. In addition, a correlation result between attitude toward the English Language and the learning of the NORBI table were also conducted. Demographic characteristics such as gender, age, race and parental occupations were tested to determine if there were any significant differences. There were 50 students of SK St David Bumbok ranging of 11 and 12 years of age becoming the samples of the study. This study found out that 42 per cent like learning English but surprisingly they scored better results in the test after using the NORBI table. There were no significant differences between demographic characteristics except for attitude toward speaking, reading and other sources of learning English, learning other skills in English, learning grammar and the NORBI table. Overall, the result of the study has shown positive relationship between the understandings of the verb ‘have’ using the NORBI table

Linear oligofluorene-BODIPY structures for fluorescence applications

A family of linear oligofluorene-BODIPY structures, containing either a ter- or quaterfluorene unit, have been prepared, in which the attachment of the oligofluorene chain to the BODIPY unit is switched between the meso-and beta-positions. Each member of this family was investigated by UV-vis absorption and photoluminescence spectroscopy, cyclic voltammetry and thermal studies (TGA and DSC) to determine their suitability as emissive layers in hybrid luminescent devices. One candidate was then successfully deployed as a down converter to convert UV to visible light

Light responsive metal-organic frameworks as controllable CO-releasing cell culture substrates

A new carbon monoxide (CO)-releasing material has been developed by embedding a manganese carbonyl complex, MnBr(bpydc)(CO)3 (bpydc = 5, 5′-dicarboxylate-2, 2′-bipyridine) into a highly robust Zr(iv)-based metal-organic framework (MOF). Efficient and controllable CO-release was achieved under exposure to low intensity visible light. Size-controllable nanocrystals of the photoactive MOF were obtained and their CO-releasing properties were correlated with their crystal sizes. The photoactive crystals were processed into cellular substrates with a biocompatible polymer matrix, and the light-induced delivery of CO and its subsequent cellular uptake were monitored using a fluorescent CO-probe. The results discussed here demonstrate a new opportunity to use MOFs as macromolecular scaffolds towards CO-releasing materials and the advantage of MOFs for high CO payloads, which is essential in future therapeutic applications

RPEL family rhoGAPs link Rac/Cdc42 GTP loading to G-actin availability

RPEL proteins, which contain the G-actin binding RPEL motif, coordinate cytoskeletal processes with actin dynamics. We show that the ArhGAP12- and ArhGAP32-family GTPase activating proteins are RPEL proteins. We determine the structure of the ArhGAP12/G-actin complex, and show that G-actin contacts the RPEL motif and GAP domain sequences. G-actin inhibits ArhGAP12 GAP activity, and this requires the G-actin contacts identified in the structure. In melanoma cells, ArhGAP12 suppresses basal Rac and Cdc42 activity, F-actin assembly, invadopodia formation, and experimental metastasis. In B16 melanoma cells, ArhGAP12 mutants defective for G-actin binding exhibit more effective downregulation of Rac.GTP loading following HGF stimulation, and enhanced Rac-dependent processes, including invadopodia formation. Potentiation or disruption of G-actin/ArhGAP12 interaction, by treatment with the actin-binding drugs latrunculin B or cytochalasin D, has corresponding effects on Rac.GTP loading. G-actin interaction with RPEL family rhoGAPs thus provides a negative feedback loop that couples Rac activity to actin dynamic

A de novo strategy for predictive crystal engineering to tune excitonic coupling

In molecular solids, the intense photoluminescence (PL) observed for solvated dye molecules is often suppressed by nonradiative decay processes introduced by excitonic coupling to adjacent chromophores. We have developed a strategy to avoid this undesirable PL quenching by optimizing the chromophore packing. We integrated the photoactive compounds into metal-organic frameworks (MOFs) and tuned the molecular alignment by introducing adjustable “steric control units” (SCUs). We determined the optimal alignment of core-substituted naphthalenediimides (cNDIs) to yield highly emissive J-aggregates by a computational analysis. Then, we created a large library of handle-equipped MOF chromophoric linkers and computationally screened for the best SCUs. A thorough photophysical characterization confirmed the formation of J-aggregates with bright green emission, with unprecedented photoluminescent quantum yields for crystalline NDI-based materials. This data demonstrates the viability of MOF-based crystal engineering approaches that can be universally applied to tailor the photophysical properties of organic semiconductor materials