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Aza-Flavanone Decreases Parkinsonism in the Drosophila melanogaster Parkin Mutant.
A highly atroposelective synthesis of nonbiaryl N-C atropisomers was achieved via direct aminations of 1,3-benzenediamines with azodicarboxylates enabled by chiral phosphoric acid catalysis. A series of N-substituents, benzene-substituents and azodicarboxylates were well tolerated, generating N-C atropisomers with high configurational stability. The facile derivatizations and utilizations of the chiral products as novel chiral organocatalysts demonstrate the value of these reactions.Effective treatment of brain metastases is hindered by the blood-brain barrier (BBB) and the rapid development of resistance to drug therapy. Moreover, the clinical application of general formulations is hampered by biological barriers and biological elimination. To tackle this challenge, we report a feasible approach for the assembly of polymer-covalent organic framework (COF) nanocomposites into 150 nm thin platelets as a drug delivery vehicle for enhanced retention in brain tumours. Using intravital imaging, we demonstrate that these polymer-COF nanocomposites are able to traverse the BBB in mice and achieve direct tumour accumulation in intracranial orthotopic models of brain metastasis from renal cancer (BMRC). These nanocomposites can target brain tumour cells and respond to tumour microenvironmental characteristics, including acidic and redox conditions. Intracranial tumour acidity triggers the breakdown of the nanoassemblies to polymer-COF nanocomposites due to the presence of borate bonds. Furthermore, in vivo studies on the nanocomposites showed enhanced brain tumour-targeting efficiency and therapeutic effects compared to those of free-drug dosing. Mice treated with drug-loaded polymer-COF nanocomposites also show protection from systemic drug toxicity and improved survival, demonstrating the preclinical potential of this nanoscale platform to deliver novel combination therapies to BMRC and other central nervous system (CNS) tumours.Catanionic mixtures are commonly used in applications due to synergetic properties of both cationic and anionic surfactants. To better understand the mechanism of the micellization process of salt-free catanionic surfactants, alkyltrimethylammonium alkanecarboxylates, [CxMe3N]+[Cy]-, with medium to long alkyl chains on both cation and anion (x,y = 6-10), were investigated in aqueous solution by density and zeta potential measurements, isothermal titration calorimetry (ITC), and dielectric relaxation spectroscopy (DRS). The obtained ITC data was analysed with the help of a two-step model equation, yielding the thermodynamic parameters, micelle charge and aggregation numbers. Comparison with the "parent" decyltrimethylammonium chloride and sodium decanoate reveals that combined dehydration of both alkyl chains increases entropy upon micellization. In the first step neutral smaller micelles with partly dehydrated alkyl chains are formed, while in the second step larger charged micelles with fully dehydrated alkyl chains are equally favourable. At low temperature both formations are thermodynamically equivalent, while with increasing temperature neutral micelles become more entropically favourable and charged micelles more enthalpically favourable. The resulting average micelle charge and average aggregation number are decreasing with temperature. From the DRS spectra, effective hydration numbers of the free monomers and micelles were deduced and are comparable to the "parent" cationic surfactant micelles.Recent studies suggest chain adsorption in the melt may be responsible for a number of property changes in thin films by making correlations between the residual adsorbed layer thickness hads(t) measured after a given solvent washing procedure as a function of annealing time t of the film at an elevated temperature prior to this solvent rinse. click here This procedure, frequently called "Guiselin's experiment", refers to the thought experiment proposed in a 1992 theoretical treatment by Guiselin that assumed chain segments in contact with the surface are irreversibly adsorbed whereby unadsorbed chains could be washed away by solvent without disturbing the adsorbed substrate contact points in the melt. In the present work, we review this recent literature, identifying and experimentally testing a common protocol for forming adsorbed layers hads(t) from solvent washing melt films. We find hads(t) curves to be far less reproducible and reliable than implied in the literature, strongly dependent on solvent washing and substrate cleaning conditions, and annealing at elevated temperatures is unnecessary as densification of films sitting at room temperature makes the glassy film harder to wash off, leaving behind hads of comparable thickness. This review also summarizes literature understanding developed over several decades of study on polymer adsorption in solution, which experimentally demonstrated that polymer chains in solution are highly mobile, diffusing and exchanging on the surface even in the limit of strong adsorption, contradicting Guiselin's assumption. Preformed adsorbed layers of different thicknesses hads are shown to not affect the average glass transition temperature or physical aging of 30 nm thick films. In summary, a number of open questions and implications are discussed related to thin films and polymer nanocomposites.Metal-semiconductor junctions are essential contacts for semiconductor devices, but high contact junction resistance is a limiting operational factor. link2 Here, we establish an ohmic contact of low resistance of less then 4 × 10-6 Ω cm2 between platinum and n-type Si (111)-H surfaces. This involved Si-O covalent bonding a monolayer of graphene oxide (GO) to the Si surface followed by electrochemical reduction to form reduced graphene oxide (rGO). Current-voltage plots demonstrate that the GO/rGO transformation is associated with a change from a rectifying to an ohmic contact. The process is a viable method for constructing semiconductor-rGO interfaces and demonstrates that GO/rGO monolayers can be used as active components in tuning the contact resistance of metal-semiconductor junctions.Vertical stacking of two-dimensional materials into layered van der Waals heterostructures has recently been considered as a promising candidate for photocatalytic and optoelectronic devices because it can combine the advantages of the individual 2D materials. Janus transition metal dichalcogenides (JTMDCs) have emerged as an appealing photocatalytic material due to the desirable electronic properties. Hence, in this work, we systematically investigate the geometric features, electronic properties, charge density difference, work function, band alignment and photocatalytic properties of ZnO-JTMDC heterostructures using first-principles calculations. Due to the different kinds of chalcogen atoms on both sides of JTMDC monolayers, two different possible stacking patterns of ZnO-JTMDC heterostructures have been constructed and considered. We find that all these stacking patterns of ZnO-JTMDC heterostructures are dynamically and energetically feasible. Moreover, both ZnO-MoSSe and ZnO-WSSe heterostructures are indirect band gap semiconductors and present type-I and type-II band alignments for model-I and model-II, respectively. The Rashba spin polarization of the ZnO-WSSe heterostructure for model-I is greater than that in the others. Furthermore, valence (conduction) band edge potentials are calculated to understand the photocatalytic behavior of these systems. Energetically favorable band edge positions in ZnO-Janus heterostructures make them suitable for water splitting at zero pH. We found that the ZnO-Janus heterostructures are promising candidates for water splitting with conduction and valence band edges positioned just outside of the redox interval.Polydopamine (PDA) is a bioinspired fascinating polymer which is considered nowadays as a material of choice for designing drug delivery nanosystems. Indeed, PDA exhibits multiple interesting features including simple preparation protocols, biocompatibility, simple functionalization procedures, free radicals scavenging and photothermal/photoacoustic properties. However, because of its heterogeneous structure, clear procedures about PDA nanoparticles synthesis and PEGylation with well-defined and reproducible physicochemical properties such as size, shape and nanomechanics are still needed. In this work, we established tightly controlled experimental conditions to synthesize PDA nanoparticles with well-defined size and yield. This allowed us to identify the factors that affect the most these two parameters and to construct surface response plots with accurate predictive values of size and yield. The nanomechanical properties of PDA NPs exhibiting different sizes have been studied with AFM nanoindentation experiments. Our results demonstrated for the first time that the elasticity of PDA NPs was decreasing with their size. This could be explained by the higher geometric packing order of the stacked oligomeric fractions inside the core of the biggest PDA NPs. Next, in order to determine the best PEGylation experimental conditions of PDA NPs using thiol-terminated PEG that allow grafting the highest polymer density with proteins repelling properties, we have first optimized the PEGylation strategy on PDA films. By using a combination of QCM-D and AFM experiments, we could demonstrate that efficient PEGylation of PDA films could be done even at low PEG concentration but in the presence of NaCl which exerts a salting out effect on PEG chains improving thus the grafting density. Finally, we transposed these experimental conditions to PDA NPs and we could synthesize PEGylated PDA NPs exhibiting high stability in physiological conditions as revealed by FTIR and DLS experiments respectively.PIWI-interacting RNAs (piRNAs) play an important role in gametogenesis, fertility and embryonic development. The current study investigated the effect of different doses of pregnant mare serum gonadotrophin/human chorionic gonadotrophin (PMSG/hCG) and repeated ovarian stimulation (OS) on the expression of the Mili, Miwi, Mael, Tdrd1, Tdrd9, qnd Mitopld genes, which have crucial roles in the biogenesis and function of piRNAs. Here, we found that after treatment with 7.5 I.U. PMSG/hCG and two repeated rounds of OS, both the mRNA and protein levels of Tdrd9, Tdrd1 and Mael showed the greatest decrease in the ovarian tissue, but the plasma E2 levels showed the strongest increases (p less then 0.05). However, we found that the Mitopld, Miwi and Mili gene levels were decreased significantly after treatment with 12.5 I.U. PMSG/hCG. Our results suggested that exogenous gonadotropin administration leads to a significant decrease in the expression of the Mili, Miwi, Mael, Tdrd1, Tdrd9 and Mitopld genes, which are critically important in the piRNA pathway, and the changes in the expression levels of Tdrd9, Tdrd1 and Mael may be associated with plasma E2 levels. New comprehensive studies are needed to reduce the potential effects of OS on the piRNA pathway, which silences transposable elements and maintains genome integrity, and to contribute to the safety of OS.Post-transcriptional regulation via small regulatory RNAs (sRNAs) has been implicated in diverse regulatory processes in bacteria, including virulence. One class of sRNAs, termed trans-acting sRNAs, can affect the stability and/or the translational efficiency of regulated transcripts. link3 In this study, we utilized a collaborative approach that employed data from infection with the Borrelia burgdorferi Tn library, coupled with Tn-seq, together with borrelial sRNA and total RNA transcriptomes, to identify an intergenic trans-acting sRNA, which we designate here as ittA for infectivity-associated and tissue-tropic sRNA locus A. The genetic inactivation of ittA resulted in a significant attenuation in infectivity, with decreased spirochetal load in ear, heart, skin and joint tissues. In addition, the ittA mutant did not disseminate to peripheral skin sites or heart tissue, suggesting a role for ittA in regulating a tissue-tropic response. RNA-Seq analysis determined that 19 transcripts were differentially expressed in the ittA mutant relative to its genetic parent, including vraA, bba66, ospD and oms28 (bba74).
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