Divergent strategy for the synthesis of bottlebrush polymers via postpolymerization modification of macromonomer

A simple and divergent synthetic strategy of bottlebrush polymers (BBPs) is presented, consisting of postpolymerization modification of a macromonomer and grafting-through polymerization. Beginning with a single macromonomer, its direct modification could build a library of macromonomers with an identical chain length, thus guaranteeing the precision in the synthesis of BBPs. In this study, a newly designed norbornenyl-terminated poly(methyl acrylate) (NB-PMA) is proposed as a chemically robust template. Ti-mediated transesterification of NB-PMA successfully produces structurally diverse polyacrylates while maintaining the terminal norbornenyl group intact. All macromonomers obtained from transesterification possess a good grafting-through ring-opening metathesis polymerization reactivity, furnishing homo, random, and block BBPs in a controllable manner. Moreover, atomic force microscopy analysis supports the controlled side-chain length distribution in the resulting BBPs.     

Simplified global fault accommodation control design of uncertain nonlinear systems with unknown time-varying powers

This paper addresses the problem of global robust fault accommodation tracking for a class of uncertain nonlinear systems with unknown powers and actuator faults. It is assumed that the powers of the concerned system are unknown time-varying functions, all system nonlinearities are unknown, and unknown actuator faults depend on the time-varying power of a control input. A fault accommodation state-feedback controller is explicitly constructed based on the nonlinear error transformation technique using time-varying performance functions. Global tracking with the preselected performance bounds is established in the presence of unknown time-varying powers and unexpected actuator faults. Different from the previous results dealing with the problem of unknown time-varying powers, the proposed tracking strategy does not require the knowledge of the bounds of the time-varying powers and the nonlinear bounding functions of system nonlinearities. An underactuated mechanical system is simulated to validate the effectiveness of the proposed theoretical approach.     

Subdominant H60 antigen-specific CD8 T-cell response precedes dominant H4 antigen-specific response during the initial phase of allogenic skin graft rejection

In allogeneic transplantation, including the B6 anti-BALB.B settings, H60 and H4 are two representative dominant minor histocompatibility antigens that induce strong CD8 T-cell responses. With different distribution patterns, H60 expression is restricted to hematopoietic cells, whereas H4 is ubiquitously expressed. H60-specific CD8 T-cell response has been known to be dominant in most cases of B6 anti-BALB.B allo-responses, except in the case of skin transplantation. To understand the mechanism underlying the subdominance of H60 during allogeneic skin transplantation, we investigated the dynamics of the H60-specific CD8 T cells in B6 mice transplanted with allogeneic BALB.B tail skin. Unexpectedly, longitudinal bioluminescence imaging and flow cytometric analyses revealed that H60-specific CD8 T cells were not always subdominant to H4-specific cells but instead showed a brief dominance before the H4 response became predominant. H60-specific CD8 T cells could expand in the draining lymph node and migrate to the BALB.B allografts, indicating their active participation in the anti-BALB.B allo-response. Enhancing the frequencies of H60-reactive CD8 T cells prior to skin transplantation reversed the immune hierarchy between H60 and H4. Additionally, H60 became predominant when antigen presentation was limited to the direct pathway. However, when antigen presentation was restricted to the indirect pathway, the expansion of H60-specific CD8 T cells was limited, whereas H4-specific CD8 T cells expanded significantly, suggesting that the temporary immunodominance and eventual subdominance of H60 could be due to their reliance on the direct antigen presentation pathway. These results enhance our understanding of the immunodominance phenomenon following allogeneic tissue transplantation.     

Activation of α-Fe2O3 for Photoelectrochemical Water Splitting Strongly Enhanced by Low Temperature Annealing in Low Oxygen Containing Ambient

Photoelectrochemical (PEC) water splitting is a promising method for the conversion of solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite (α-Fe₂O₃) is one of the most attractive materials for a highly efficient charge carrier generation and collection due to its large specific surface area and the short minority carrier diffusion length. In the present work, the PEC water splitting performance of nanostructured α-Fe₂O₃ is investigated which was prepared by anodization followed by annealing in a low oxygen ambient (0.03 % O₂ in Ar). It was found that low oxygen annealing can activate a significant PEC response of α-Fe₂O₃ even at a low temperature of 400 °C and provide an excellent PEC performance compared with classic air annealing. The photocurrent of the α-Fe₂O₃ annealed in the low oxygen at 1.5 V vs. RHE results as 0.5 mA cm⁻², being 20 times higher than that of annealing in air. The obtained results show that the α-Fe₂O₃ annealed in low oxygen contains beneficial defects and promotes the transport of holes; it can be attributed to the improvement of conductivity due to the introduction of suitable oxygen vacancies in the α-Fe₂O₃. Additionally, we demonstrate the photocurrent of α-Fe₂O₃ annealed in low oxygen ambient can be further enhanced by Zn-Co LDH, which is a co-catalyst of oxygen evolution reaction. This indicates low oxygen annealing generates a promising method to obtain an excellent PEC water splitting performance from α-Fe₂O₃ photoanodes.     

Hydrogen production and photocatalytic activity of g-C3N4/Co-MOF (ZIF-67) nanocomposite under visible light irradiation

Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C₃N₄ nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C₃N₄ surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C₃N₄/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H₂) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H₂ production of the g-C₃N₄/ZIF-67 composite was 2084 μmol g⁻¹, which is 3.84 folds greater than that of bare g-C₃N₄ (541 μmol g⁻¹).     

A look at bonds and bonding

Structural Chemistry - Even after roughly a century of quantum theory, there is still debate, sometimes rather contentious, as to the nature of the chemical bond—or is it bonds, or is it...     

Ionic liquids: Promising green solvents for lignocellulosic biomass utilization

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