Raffertyhinrichsen1403

A fine-tuned balanced between osteoblast maturation, differentiation and viability was observed.The synergistic combination of gene therapy and photothermal therapy (PTT) has been widely investigated as a promising strategy for cancer treatment. To deliver genes and photothermal agents simultaneously and accurately to a tumor site, a microneedle (MN) patch co-loaded with p53 DNA and IR820 was fabricated by a two-step casting method. Hyaluronic acid was chosen as a matrix and p53 DNA and IR820 were mainly loaded into the tips to enhance utilization and reduce waste. The MN patch could efficiently penetrate the stratum corneum, and dissolve rapidly to release p53 DNA and IR820 in the subcutaneous tumor site. Due to the efficient photothermal efficacy of IR820, the temperature of the tumor site where the MN patch was applied increased by 14.7 °C under near-infrared light irradiation. The MN patch showed excellent antitumor effects in vivo owing to the synergistic effect of gene therapy and PTT. Consequently, the p53 DNA/IR820 MN patch may be a promising synergistic strategy for subcutaneous tumor treatments.We demonstrate that the conductance switching of benzo-bis(imidazole) molecules upon protonation depends on the lateral functional groups. The protonated H-substituted molecule shows a higher conductance than the neutral one (Gpro > Gneu), while the opposite (Gneu > Gpro) is observed for a molecule laterally functionalized by amino-phenyl groups. These results are demonstrated at various scale lengths self-assembled monolayers, tiny nanodot-molecule junctions and single molecules. From ab initio theoretical calculations, we conclude that for the H-substituted molecule, the result Gpro > Gneu is correctly explained by a reduction of the LUMO-HOMO gap, while for the amino-phenyl functionnalized molecule, the result Gneu > Gpro is consistent with a shift of the HOMO, which reduces the density of states at the Fermi energy.Peptide backbone amide substitution can dramatically alter the conformational and physiochemical properties of native sequences. Although uncommon relative to N-alkyl substituents, peptides harboring main-chain N-hydroxy groups exhibit unique conformational preferences and biological activities. Here, we describe a versatile method to prepare N-hydroxy peptide on solid support and evaluate the impact of backbone N-hydroxylation on secondary structure stability. Based on previous work demonstrating the β-sheet-stabilizing effect of α-hydrazino acids, we carried out an analogous study with N-hydroxy-α-amino acids using a model β-hairpin fold. In contrast to N-methyl substituents, backbone N-hydroxy groups are accommodated in the β-strand region of the hairpin without energetic penalty. An enhancement in β-hairpin stability was observed for a di-N-hydroxylated variant. Our results facilitate access to this class of peptide derivatives and inform the use of backbone N-hydroxylation as a tool in the design of constrained peptidomimetics.tert-Butyl-p-benzoquinone (TBBQ), a metabolite of tert-butylhydroquinone from food, has cytotoxicity, the underlying mechanism of which is not clear. In this study, the viability of RAW 264.7 cells exposed to TBBQ at concentrations of 0.5-10 μg mL-1 was assayed by MTT. Results suggest that TBBQ decreased the viability in a dose-dependent manner. Monodansylcadaverine (MDC) staining results indicate the occurrence of autophagy induced by TBBQ, which was manifested by activation of LC3-II concurrent with the increased levels of Beclin1 and reduced levels of p62. Elevated lipid peroxide and decreased SOD activity by TBBQ exposure suggest the overproduction of ROS, which may account for the increase in the genotoxic stress protein p53. Both upregulation of p53 and reduction of Akt levels inhibited mTOR, which activated autophagy. Addition of 3-MA counteracted the impact of TBBQ on ATG proteins and cell viability. All of these results suggest that TBBQ induces autophagy of RAW 264.7 cells principally by inhibition of the Akt/mTOR signaling pathway, and they implicate ROS in this regulation.Supramolecular self-assembly allows components to organize themselves into regular patterns by using non-covalent interactions to find the lowest-energy configuration. However, self-assembling organic and inorganic building blocks together into an ordered framework remains a challenge due to the difficulties in rationally interfacing two dissimilar materials. Herein, we report on the host-guest ensemble of polyoxometalates (POMs) using cyclodextrins (CDs) as the trapping agent to form POM@γ-CD entities. Two unprecedented super cubic isostructures, Co/Cu-PW12O40-γ-CD, were obtained. this website The self-assembly has been observed both in solution (MS, 1D NMR and 2D DOSY) and in the solid state. Single-crystal X-ray diffraction reveals that in a unit cell, the inner (POM@γ-CD)12 cube is encapsulated by the outer (POM@γ-CD)24 cube. Besides, due to the rather large spherical voids, two (POM@γ-CD)24 cubes are interspersed together. Preliminary investigations of the redox properties of the [PW12O40]3- encapsulated in the γ-cyclodextrins indicate that the redox properties of the trianion are largely retained, yet an additional electrochemical stabilization is observed. The adduct reported here opens the door to a new generation of hybrid materials with tuned structures and customized functionalities.Direct synthesis of a nano-structured carbon hybrid consisting of vertically aligned carbon nanograsses on top of boron-doped nanocrystalline diamond is demonstrated and the carbon hybrid is further applied as an electrode material for the fabrication of supercapacitors. The hybrid film combines the dual advantages of sp2 (carbon nanograss) and sp3 (nanocrystalline diamond) bonded carbon, possessing not only the excellent electrical characteristics of sp2 carbon but also the exceptional electrochemical stability of sp3 carbon. As a result, the specific capacitance of the as-prepared hybrid material reaches up to 0.4 F cm-2, one of the highest reported in diamond-based supercapacitors. The entire electrochemical results exhibit enhanced electron transfer efficiency with remarkable stability of 95% of capacitance retention even after 10 000 cycles.Correction for 'Identification and determination of selenocysteine, selenosugar, and other selenometabolites in turkey liver' by Katarzyna Bierla et al., Metallomics, 2020, DOI 10.1039/d0mt00040j.Small molecule monosaccharide analogs (e.g. 4F-GlcNAc, 4F-GalNAc) and acceptor decoys (e.g. ONAP, SNAP) are commonly used as metabolic glycoengineering tools to perturb molecular and cellular recognition processes. Azido-derivatized sugars (e.g. ManNAz, GlcNAz, GalNAz) are also used as bioorthogonal probes to assay the glycosylation status of cells and tissue. With the goal of obtaining a systems-level understanding of how these compounds work, we cultured cells with these molecules and systematically evaluated their impact on (i) cellular nucleotide-sugar levels, and (ii) N-linked glycosylation. To this end, we developed a streamlined, simple workflow to quantify nucleotide-sugar levels using amide-based hydrophilic interaction liquid chromatography (HILIC) separation followed by negative-mode electrospray ionization mass spectrometry (ESI-MS/MS) using an Orbitrap detector. N-Glycans released from cells were also procainamide functionalized and quantified using positive-mode ESI-MS/MS. Results show that all tested compounds changed the baseline nucleotide-sugar levels, with the effect being most pronounced for the fluoro-HexNAc compounds. These molecules depressed UDP-HexNAc levels in cells by up to 80%, while concomitantly elevating UDP-4F-GalNAc and UDP-4F-GlcNAc. While the measured changes in nucleotide-sugar concentration were substantial in many cases, their impact on N-linked glycosylation was relatively small. This may be due to the high nucleotide-sugar concentrations in the Golgi, which far exceed the KM values of the glycosylating enzymes. Thus, the glycosylation system output exhibits 'robustness' even in the face of significant changes in cellular nucleotide-sugar concentrations.A flower cluster structural histidine-functionalized multi-walled carbon nanotube-graphene oxide nanoribbon/Co-Ni LDH (His-MW/LDH) composite was synthesized via the microwave method. In this study, we used His-MW as a carbon material to synthesize the electrode because it not only has the properties of MWCNT-GONR (MW) but also completes the N doping process due to the addition of histidine. His-MW adhered to the LDH flower cluster, and the radius of the composite was found to be nearly 1 μm. The synergistic effects of His-MW and LDH could effectively increase the specific surface areas and conductivity of the composite, thereby endowing it with high specific capacitance (1674 F g-1) and admirable cycling stability (83.33% capacitance retention). Moreover, we assembled an asymmetric supercapacitor, and it possessed 39.47 W h kg-1 at 0.80 kW kg-1 as well as prominent cycling stability (93.81% capacitance retention). This study proves the feasibility of synthesizing the histidine-functionalized carbon derivative/LDH composite by the microwave method. Moreover, we are optimistic that the electrode material can be extensively used in supercapacitors because of its splendid electrochemical properties and facile synthesis.Herein we report a strategy to utilise the bioorthogonal reactivity and phosphorogenic property of iridium(iii) polypyridine nitrone complexes and SNAP-tag protein for the modulation of emission and singlet oxygen (1O2) photosensitisation in live cells.The new Y2Co3Ga9 and Gd3Ru4Al12 type representatives M2T3Al9 (M = Ca, Sr, Eu; T = Ir, Pt) and M3Rh4Al12 (M = Ca, Eu) have been synthesized from the elements by heating the respective elemental compositions in sealed tantalum tubes. The samples were analysed by powder X-ray diffraction to check their purity. By applying different temperature treatments, their phase purity and crystallinity were enhanced. The crystal structures of Ca3Rh4Al12 and Eu3Rh4Al12 (hexagonal Gd3Ru4Al12 type, P63/mmc) as well as Ca2Ir3Al9 and Ca2Pt3Al9 (orthorhombic Y2Co3Ga3 type, Cmcm) were refined from single-crystal X-ray diffraction data. All structures can be described based on distorted cube-like T@Al8 units that are connected to form strands. Additionally, an Al11 supertetrahedral building block can be identified within the structures. While the trigonal bipyramidal core of the cluster contains substantial bonding interactions in the case of the M3Rh4Al12 members, the connection via common edges in the case of the M2Ir3Al9 compounds seems to weaken these interactions. The differences in the bonding situation and the question why these different structure types are formed for the different transition metals has been targeted by quantum-chemical calculations. The calculated formation energy using three different reaction paths suggests that the stability of these phases is highly dependent on the side phases involved, even though Ca3T4Al12 phases are in general thermodynamically more favourable. According to the Bader analysis of the two polyanions, an improved covalent bonding can be observed in the [T4Al12]δ- over the [T3Al9]δ- framework.