Hybrid organic–inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic–inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.
With the aid of ab initio calculations at the MP2 level of theory, we designed a novel class of inorganic salts, M(+)(en)3M3'O(-) (M, M' = Li, Na, and K), by using the M3'O superalkalis. These compounds are the first examples of inorganic salts wherein the superalkali occupies the anionic site, and termed superalkalides. The electronic structural features of the M(+)(en)3M3'O(-) superalkalides are very similar to those of the corresponding M(+)(en)3M'(-) alkalides which have been reported by Zurek (J. Am. Chem. Soc., 2011, 133, 4829). In this study, the calculated NLO properties of M(+)(en)3M3'O(-) and M(+)(en)3M'(-) (M, M' = Li, Na, and K) show that both superalkalides and alkalides have significantly large first hyperpolarizabilities (β0) with the values in the range of 7.80 × 10(3) to 9.16 × 10(4) a.u. and 7.95 × 10(3) to 1.84 × 10(5) a.u., respectively. Computations on the stabilities of M(+)(en)3M3'O(-) and M(+)(en)3M'(-) demonstrate that the M(+)(en)3M3'O(-) superalkalides are preferably stable than the corresponding M(+)(en)3M'(-) alkalides because of the presence of hydrogen bonds in M(+)(en)3M3'O(-). Therefore, the designed superalkalides, M(+)(en)3M3'O(-) (M, M' = Li, Na, and K), with excellent nonlinear optical properties and high stabilities are greatly promising candidates for NLO materials. We hope that this article could attract more research interest in superatom chemistry and for further experimental research.
Ethylene is instrumental to climacteric fruit ripening and EIN3 BINDING F-BOX (EBF) proteins have been assigned a central role in mediating ethylene responses by regulating EIN3/EIL degradation in Arabidopsis. However, the role and mode of action of tomato EBFs in ethylene-dependent processes like fruit ripening remains unclear. Two novel EBF genes, SlEBF3 and SlEBF4, were identified in the tomato genome, and SlEBF3 displayed a ripening-associated expression pattern suggesting its potential involvement in controlling ethylene response during fruit ripening. SlEBF3 downregulated tomato lines failed to show obvious ripening-related phenotypes likely due to functional redundancy among SlEBF family members. By contrast, SlEBF3 overexpression lines exhibited pleiotropic ethylene-related alterations, including inhibition of fruit ripening, attenuated triple-response and delayed petal abscission. Yeast-two-hybrid system and bimolecular fluorescence complementation approaches indicated that SlEBF3 interacts with all known tomato SlEIL proteins and, consistently, total SlEIL protein levels were decreased in SlEBF3 overexpression fruits, supporting the idea that the reduced ethylene sensitivity and defects in fruit ripening are due to the SlEBF3-mediated degradation of EIL proteins. Moreover, SlEBF3 expression is regulated by EIL1 via a feedback loop, which supposes its role in tuning ethylene signaling and responses. Overall, the study reveals the role of a novel EBF tomato gene in climacteric ripening, thus providing a new target for modulating fleshy fruit ripening.
An unprecedented protocol has been developed for the regioselective synthesis of structurally diverse indene derivatives from readily accessible N-benzylic sulfonamides and disubstituted alkynes through FeCl(3)-catalyzed cleavage of sp(3) carbon-nitrogen bonds to generate benzyl cation intermediates. In the presence of 10 mol % of FeCl(3), a broad range of N-benzylic sulfonamides smoothly react with internal alkynes, alkynylcarbonyl compounds, alkynyl chalcogenides, or alkynyl halides to afford various functionalized indene derivatives with extremely high regioselectivity.
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