Huangdemant8804

Molecular self-assembly is a spontaneous natural process resulting in highly ordered nano to microarchitectures. We report temperature-independent formation of robust stable membranes obtained by the spontaneous interaction of intrinsically disordered elastin-like polypeptides (ELPs) with short aromatic peptides at temperatures both below and above the conformational transition temperature of the ELPs. The membranes are stable over time and display durability over a wide range of parameters including temperature, pH, and ultrasound energy. The morphology and composition of the membranes were analyzed using microscopy. These robust structures support preosteoblast cell adhesion and proliferation as well as pH-dependent cargo release. Simple noncovalent interactions with short aromatic peptides can overcome conformational restrictions due to the phase transition to facilitate the formation of complex bioactive scaffolds that are stable over a wide range of environmental parameters. This approach offers novel possibilities for controlling the conformational restriction of intrinsically disordered proteins and using them in the design of new materials.Plasmon-enhanced photocatalytic coupling reactions have been used as model systems in surface-enhanced Raman spectroscopy and tip-enhanced Raman spectroscopy (TERS) research for decades. However, the role of reactive arrangement on efficiency of these model reactions has remained largely unknown to date often leading to conflicting interpretations of experimental results. Herein, we use an interdisciplinary toolbox of nanoscale TERS imaging in combination with molecular-resolution ambient scanning tunnelling microscopy (STM) and density functional theory (DFT) modeling to investigate the role of reactive arrangement in photocatalytic coupling of 4-nitrobenzenethiol (4-NTP) to p,p'-dimercaptoazobisbenzene on single-crystal and polycrystalline Au surfaces for the first time. TERS imaging with 3 nm resolution clearly revealed a significantly higher catalytic efficiency inside a kinetically driven disordered phase of the 4-NTP adlayer on Au compared to the thermodynamically stable ordered phase. Furthermore, molecular level details of the self-assembled structures in the disordered and ordered phases obtained using ambient high-resolution STM enabled an unambiguous structure-reactivity correlation of photocatalytic coupling. Finally, quantitative mechanistic insights obtained from DFT modeling based on the accurate parameters determined from STM imaging emphatically confirmed that a combination of steric hindrance effect and energetic barrier leads to a lower reaction efficiency in the ordered phase of the 4-NTP adlayer. This fundamental study establishes the first direct structure-reactivity correlation in photocatalytic coupling and highlights the critical role of reactive arrangement in the efficiency of on-surface coupling reactions in heterogeneous catalysis at large.Hydrated electron (eaq-)-induced reduction protocols have bright prospects for the decomposition of recalcitrant organic pollutants. However, traditional eaq- production involves homogeneous sulfite photolysis, which has a pH-dependent reaction activity and might have potential secondary pollution risks. In this study, a heterogeneous UV/diamond catalytic system was proposed to decompose of a typical persistent organic pollutant, perfluorooctanoic acid (PFOA). In contrast to the rate constant of the advanced reduction process (ARP) of a UV/SO32-, the kobs of PFOA decomposition in the UV/diamond system showed only minor pH dependence, ranging from 0.01823 ± 0.0014 min-1 to 0.02208 ± 0.0013 min-1 (pH 2 to pH 11). As suggested by the electron affinity (EA) and electron configuration of the diamond catalyst, the diamond catalyst yields facile energetic photogenerated electron emission into water without a high energy barrier after photoexcitation, thus inducing eaq- production. The impact of radical scavengers, electron spin resonance (ESR), and transient absorption (TA) measurements verified the formation of eaq- in the UV/diamond system. The investigation of diamond for ejection of energetic photoelectrons into a water matrix represents a new paradigm for ARPs and would facilitate future applications of heterogeneous catalytic processes for efficient recalcitrant pollutant removal by eaq-.Akt is a Ser/Thr protein kinase that regulates cell growth and metabolism and is considered a therapeutic target for cancer. Regulation of Akt by membrane recruitment and post-translational modifications (PTMs) has been extensively studied. The most well-established mechanism for cellular Akt activation involves phosphorylation on its activation loop on Thr308 by PDK1 and on its C-terminal tail on Ser473 by mTORC2. In addition, dual phosphorylation on Ser477 and Thr479 has been shown to activate Akt. Other C-terminal tail PTMs have been identified, but their functional impacts have not been well-characterized. Here, we investigate the regulatory effects of phosphorylation of Tyr474 and O-GlcNAcylation of Ser473 on Akt. We use expressed protein ligation as a tool to produce semisynthetic Akt proteins containing phosphoTyr474 and O-GlcNAcSer473 to dissect the enzymatic functions of these PTMs. We find that O-GlcNAcylation at Ser473 and phosphorylation at Tyr474 can also partially increase Akt's kinase activity toward both peptide and protein substrates. Additionally, we performed kinase assays employing human protein microarrays to investigate global substrate specificity of Akt, comparing phosphorylated versus O-GlcNAcylated Ser473 forms. We observed a high similarity in the protein substrates phosphorylated by phosphoSer473 Akt and O-GlcNAcSer473 Akt. Two Akt substrates identified using microarrays, PPM1H, a protein phosphatase, and NEDD4L, an E3 ubiquitin ligase, were validated in solution-phase assays and cell transfection experiments.Hedgehog (Hh) signaling ligands undergo carboxy terminal sterylation through specialized autoprocessing, called cholesterolysis. Sterylation is brought about intramolecularly in a single turnover by an adjacent enzymatic domain, called HhC, which is found in precursor Hh proteins only. Previous attempts to identify antagonists of the intramolecular activity of HhC have yielded inhibitors that bind HhC irreversibly through covalent mechanisms, as is common for protein autoprocessing inhibitors. Here, we report an exception to the "irreversibility rule" for autoprocessing inhibition. Using a fluorescence resonance energy transfer-based activity assay for HhC, we screened a focused library of sterol-like analogues for noncovalent inhibitors and identified and validated four structurally related molecules, which were then used for structure-activity relationship studies. The most effective derivative, tBT-HBT, inhibits HhC noncovalently with an IC50 of 300 nM. An allosteric binding site for tBT-HBT, encompassing residues from the two subdomains of HhC, is suggested by kinetic analysis, mutagenesis studies, and photoaffinity labeling. The inhibitors described here resemble a family of noncovalent, allosteric inducers of HhC paracatalysis which we have described previously. The inhibition and the induction appear to be mediated by a shared allosteric site on HhC.Amides are important functional synthons that have been widely used in the construction of peptides, natural products, and drugs. The C-N bond cleavage provides the direct method for amide conversion. However, amides, especially secondary amides, tend to be chemically inert due to the resonance of the amide bond. Here, we describe an efficient Pd-catalyzed transamidation and decarbonylation of multiamide structure molecules through C-N bond cleavage with excellent chemoselectivity. The transamidation of secondary amides and the decarbonylation of phthalimide provide meaningful tools for the modification of amino acid derivatives. Nesuparib price Moreover, further transformations of azidation and C(sp3)-H monoarylation emphasized the potential utility of this selective C-N bond cleavage method.Edges of low-dimensional quantum systems have profound effects on both fundamental research and device functionality. Real-space investigation of the microscopic edge structures and understanding the edge-modulated electronic properties are of great essence. Here we report the nanoscale structural reconstruction at the atomically sharp edge of a charge-density-wave (CDW) correlated insulator 1T-NbSe2 and the induced electronic properties. We find the CDW unit cells at the edge of single layer (SL) 1T-NbSe2 evolve from the well-defined CDW order in bulk and spontaneously reconstruct into the quartet along the edge. Moreover, we capture an anomalous electronic superstructure along the edge, the periodicity of which is four times that of ordinary CDW lattice. Our findings provide a way to design the one-dimensional electronic superstructure in 2D quantum materials.Zinc is a prospective metal for biodegradable cardiovascular stent applications, but the excessively released Zn2+ during degradation remains a huge challenge in biocompatibility. Considerable efforts have been made to develop a high-efficient surface modification method, while maintaining adhesion strength, mechanical support, and vascular compatibility. Biomimetic polydopamine (PDA) can adhere to Zn tightly, subsequently achieving robust chemical bonds with poly(lactic-co-glycolic acid) (PLGA) coating. However, the deposition of PDA on Zn depends on the controlled conditions such as a sensitive pH and a long period of time. Herein, we introduce vacuum ultraviolet-ozone (VUV/O3) assist-deposition technology to accelerate the polymerization of PDA on pure Zn, which shortens the process to 40 min at a moderate pH of 8.5 and improves the deposition rate by 1-2 orders of magnitude under sufficient active oxygen species (ROS). Additionally, PLGA/PDA coating enhances the corrosion resistance, and their effective protection maintains the mechanical properties after long-term corrosion. Moreover, the controlled Zn2+ release contributes to the superior in vitro biocompatibility, which inhibits the hemolysis rate and smooth muscle cell (SMC) proliferation. The enhanced endothelial cell (EC) proliferation is promising to promote the re-endothelialization, avoiding in-stent restenosis and neointimal hyperplasia. Such modified Zn might be a viable candidate for the treatment of cardiovascular diseases.An expanded heterohelicene consisting of three BN2-embedded [4]helicene subunits (V-DABNA-Mes) has been synthesized by one-shot triple borylation. The key to success is the excessive use of boron tribromide in an autoclave. Based on the multiple resonance effect of three boron and six nitrogen atoms, V-DABNA-Mes exhibited a narrowband sky-blue thermally activated delayed fluorescence with a full width at half-maximum of 16 nm. The resonating π-extension minimized the singlet-triplet energy gap and enabled rapid reverse intersystem crossing with a rate constant of 4.4 × 105 s-1. The solution-processed organic light-emitting diode device, employed as an emitter, exhibited a narrowband emission at 480 nm with a high external quantum efficiency of 22.9%.Ribonucleotide reductase (RNR) is an essential enzyme with a complex mechanism of allosteric regulation found in nearly all living organisms. Class I RNRs are composed of two proteins, a large α-subunit (R1) and a smaller β-subunit (R2) that exist as homodimers, that combine to form an active heterotetramer. Aquifex aeolicus is a hyperthermophilic bacterium with an unusual RNR encoding a 346-residue intein in the DNA sequence encoding its R2 subunit. We present the first structures of the A. aeolicus R1 and R2 (AaR1 and AaR2, respectively) proteins as well as the biophysical and biochemical characterization of active and inactive A. aeolicus RNR. While the active oligomeric state and activity regulation of A. aeolicus RNR are similar to those of other characterized RNRs, the X-ray crystal structures also reveal distinct features and adaptations. Specifically, AaR1 contains a β-hairpin hook structure at the dimer interface, which has an interesting π-stacking interaction absent in other members of the NrdAh subclass, and its ATP cone houses two ATP molecules.