AP2M1 Supports TGF-β Signals to Promote Collagen Expression by Inhibiting Caveolin Expression

The extracellular matrix (ECM) is important for normal development and disease states, including inflammation and fibrosis. To understand the complex regulation of ECM, we performed a suppressor screening using Caenorhabditis elegans expressing the mutant ROL-6 collagen protein. One cuticle mutant has a mutation in dpy-23 that encodes the μ2 adaptin (AP2M1) of clathrin-associated protein complex II (AP-2). The subsequent suppressor screening for dpy-23 revealed the lon-2 mutation. LON-2 functions to regulate body size through negative regulation of the tumor growth factor-beta (TGF-β) signaling pathway responsible for ECM production. RNA-seq analysis showed a dominant change in the expression of collagen genes and cuticle components. We noted an increase in the cav-1 gene encoding caveolin-1, which functions in clathrin-independent endocytosis. By knockdown of cav-1, the reduced TGF-β signal was significantly restored in the dpy-23 mutant. In conclusion, the dpy-23 mutation upregulated cav-1 expression in the hypodermis, and increased CAV-1 resulted in a decrease of TβRI. Finally, the reduction of collagen expression including rol-6 by the reduced TGF-β signal influenced the cuticle formation of the dpy-23 mutant. These findings could help us to understand the complex process of ECM regulation in organism development and disease conditions.     

Efficient Visible-to-UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting.     

Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF_2α and 1,15-PGF_2α lactones, many 1,15-lactones of E₂, E₃, F₂, F₃, A₂, and A₃ were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9β-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9β-PG analogs and future applications, are also discussed.     

Heteroalleles in Common Wheat: Multiple Differences between Allelic Variants of the Gli-B1 Locus

The Gli-B1-encoded γ-gliadins and non-coding γ-gliadin DNA sequences for 15 different alleles of common wheat have been compared using seven tests: electrophoretic mobility (EM) and molecular weight (MW) of the encoded major γ-gliadin, restriction fragment length polymorphism patterns (RFLPs) (three different markers), Gli-B1-γ-gliadin-pseudogene known SNP markers (Single nucleotide polymorphisms) and sequencing the pseudogene GAG56B. It was discovered that encoded γ-gliadins, with contrasting EM, had similar MWs. However, seven allelic variants (designated from I to VII) differed among them in the other six tests: I (alleles Gli-B1i, k, m, o), II (Gli-B1n, q, s), III (Gli-B1b), IV (Gli-B1e, f, g), V (Gli-B1h), VI (Gli-B1d) and VII (Gli-B1a). Allele Gli-B1c (variant VIII) was identical to the alleles from group IV in four of the tests. Some tests might show a fine difference between alleles belonging to the same variant. Our results attest in favor of the independent origin of at least seven variants at the Gli-B1 locus that might originate from deeply diverged genotypes of the donor(s) of the B genome in hexaploid wheat and therefore might be called “heteroallelic”. The donor’s particularities at the Gli-B1 locus might be conserved since that time and decisively contribute to the current high genetic diversity of common wheat.     

Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Fabrication and characterization of hot-pressed B-rich boron carbide

Boron carbide has a wide solubility range owing to the substitution of B and C atoms in the crystal. In this study, boron carbides with different stoichiometric ratios were prepared using a hot-pressing sintering method, and the influences of the B/C atomic ratio on the microstructures and properties were explored in detail. X-ray diffraction analysis showed that excessive B atoms caused lattice expansion. Raman spectroscopy analysis showed disordered substitution of B atoms in the chains and icosahedra. Analysis of the densification process and microstructure evolution revealed that the addition of B promoted densification, and more stacking faults and twins occurred in B-rich boron carbide, and result in the densification mechanism gradually changes from atomic diffusion mechanism driven by thermal energy to plastic deformation mechanism dominated by the proliferation of dislocation and substructures. The introduction of chemical composition changes by dissolving excessive B into boron carbide further affected the microstructure and consequently the mechanical properties. The Vickers hardness, modulus, and sound velocity all decreased with the increase in B content. Moreover, the fracture toughness improved with increased B content. The flexural strength of the samples was optimised at the B/C stoichiometric ratio of 6.1.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

High-pressure synthesis,crystal structure,and physical properties of NaAlB14 single crystals

Pure NaAlB₁₄ single crystals were successfully synthesized directly from Na, Al, and B at high pressure and high temperature, different from the previously reported method, that is, synthesized from Na₂B₄O₇, Al, and B. The growth of NaAlB₁₄ single crystals was promoted by increasing the reaction temperature. The atomic structures of NaAlB₁₄ single crystal along the [100], [010], [001], and [021] axes were characterized by using a scanning transmission electron microscope. The Raman spectra of NaAlB₁₄ were investigated theoretically and experimentally, and they showed the expected oscillations of the covalent framework. In addition, photoluminescence spectra indicated that NaAlB₁₄ is a semiconductor luminescence material with red (1.68 eV) and near-infrared (1.50 and 1.36 eV) emission characteristics. The band structure revealed that NaAlB₁₄ is an indirect band gap semiconductor with a wide band gap of 2.22 eV.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.