Dalrympleashworth9753

has minimized the fitting error of the DMS and tested the completeness of the DMS. Some examples of our work on NH3, CO2, and SO2 are given to highlight the usefulness of the BTRHE strategy and to provide ideas on how to further improve its predictive power in the future. In particular, it is shown how successive refinement steps, once new high-resolution data are available, can lead to PESs that yield highly accurate transition energies to larger spectral regions. The importance of including nonadiabatic corrections to reduce the J-dependence of errors for H-containing molecules is shown with work on NH3. Another very important aspect of the BTRHE approach is the consistency across isotopologues, which allows for highly accurate line lists for any isotopologue once one is obtained for the main isotopologue (which has more high-resolution data available for refinement).Photobioelectrodes represent one of the examples where artificial materials are combined with biological entities to undertake semi-artificial photosynthesis. Here, an approach is described that uses reduced graphene oxide (rGO) as an electrode material. This classical 2D material is used to construct a three-dimensional structure by a template-based approach combined with a simple spin-coating process during preparation. Inspired by this novel material and photosystem I (PSI), a biophotovoltaic electrode is being designed and investigated. Both direct electron transfer to PSI and mediated electron transfer via cytochrome c from horse heart as redox protein can be confirmed. Electrode preparation and protein immobilization have been optimized. The performance can be upscaled by adjusting the thickness of the 3D electrode using different numbers of spin-coating steps during preparation. Thus, photocurrents up to ∼14 μA/cm2 are measured for 12 spin-coated layers of rGO corresponding to a turnover frequency of 30 e- PSI-1 s-1 and external quantum efficiency (EQE) of 0.07% at a thickness of about 15 μm. Operational stability has been analyzed for several days. Particularly, the performance at low illumination intensities is very promising (1.39 μA/cm2 at 0.1 mW/cm2 and -0.15 V vs Ag/AgCl; EQE 6.8%).Cyclodextrins (CDs), as pharmaceutical excipients with excellent biocompatibility, non-immunogenicity, and low toxicity in vivo, are widely used to carry drugs by forming inclusion complexes for improving the solubility and stability of drugs. However, the limited space of CDs' lipophilic central cavity affects the loading of many drugs, especially with larger molecules. In this study, β-CDs were modified by acetonization to improve the affinity for the chemotherapy drug doxorubicin (DOX), and doxorubicin-adsorbing acetalated β-CDs (Ac-CDDOX) self-assembled to nanoparticles, followed by coating with the amphiphilic zinc phthalocyanine photosensitizer ZnPc-(PEG)5 for antitumor therapy. The final product ZnPc-(PEG)5Ac-CDDOX was demonstrated to have excellent stability and pH-sensitive drug release characteristics. The cell viability and apoptosis assay showed synergistic cytotoxic effects of chemotherapy and phototherapy. The mechanism of cytotoxicity was analyzed in terms of intracellular reactive oxygen species, mitochondrial membrane potential, and subcellular localization. More importantly, in vivo experiments indicated that ZnPc-(PEG)5Ac-CDDOX possessed significant tumor targeting, prominent antitumor activity, and less side effects. Our strategy expands the application of CDs as drug carriers and provides new insights into the development of CD chemistry.Cells are powerful carriers that can help to improve the delivery of nanomedicines. One approach to use cells as carriers is to immobilize the nanoparticulate cargo on the cell surface. While a plethora of chemical conjugation strategies are available to bind nanoparticles to cell surfaces, only relatively little is known about the effects of particle size and cell type on the surface immobilization of nanoparticles. This study investigates the biotin-NeutrAvidin mediated immobilization of model polymer nanoparticles with sizes ranging from 40 nm to 1 μm on two different T cell lines, viz., human Jurkat cells as well as mouse SJL/PLP7 T cells, which are of potential interest for drug delivery across the blood-brain barrier. The nanoparticle cell surface immobilization and the particle surface concentration and distribution were analyzed by flow cytometry and confocal microscopy. The functional properties of nanoparticle-modified SJL/PLP7 T cells were assessed in an ICAM-1 binding assay as well as in a two-chamber setup in which the migration of the particle-modified T cells across an in vitro model of the blood-brain barrier was studied. The results of these experiments highlight the effects of particle size and cell line on the surface immobilization of nanoparticles on living cells.Ion transport is crucial for biological systems and membrane-based technologies from both fundamental and practical aspects. Unlike biological ion channels, realizing efficient ion sieving by using membranes with artificial ion channels remains an extremely challenging task. Inspired by biological ion channels with proper steric containment of target ions within affinitive binding sites along the selective filter, herein we design a system of biomimic two-dimensional (2D) ionic transport channels based on a graphene oxide (GO) membrane, where the ionic imidazole group tunes the appropriate physical confinement of 2D ionic transport channels to mimic the confined cavity structures of the biological selectivity filter, and the ionic sulfonic group creates a favorable chemical environment of 2D ionic transport channels to mimic the affinitive binding sites of the biological selectivity filter. As a result, the as-fabricated ionic GO membrane demonstrates an exceptional K+ transport rate of ∼1.36 mol m-2 h-1 and competitive K+/Mg2+ selectivity of ∼9.11, outperforming state-of-the-art counterparts. Moreover, the semiquantitative studies of ion transport through 2D ionic transport channels suggest that efficient ion sieving with the ionic GO membrane is achieved by the high diffusion and partition coefficients of hydrated monovalent ions, as well as the large energy barrier and limited potential gradient of hydrated divalent ions encountered.An absorbance-based colorimetric sensor array that is self-powered by an ion-selective electrode (ISE) in a short-circuited cell is presented. As the cell voltage is maintained at zero, the potential at the ISE serves as the power generator to directly transfer its power to a potential-dependent Prussian blue (PB) film in contact with an electrolyte solution in a separate detection compartment. This allows one to activate the color change of the PB film without the need for an external power supply. The potential of the PB detection element is optimized to change color between 50 and 250 mV (vs Ag/AgCl). Because the potential originates at the ISE, it is proportional to the ion activity in the sample in agreement with the Nernst equation. In this way, a higher cation activity in the sample generates a more positive potential, which enhances the PB absorbance that serves as the analytical signal. A self-powered optical sensor array coupled to poly(vinyl-chloride)-based pH electrodes based on two different ionophores is utilized here as a model. The measuring range is tuned chemically by varying the pH of the inner filling solution of each ISE, giving a measuring range from pH 2 to 10.5. As the optical sensor is driven by a potentiometric probe, the sensor output is independent of solution ionic strength. It is successfully applied for quantitative analysis in unmodified turbid/colored samples that included red wine, coke, coffee, baking soda, and antacid. The colorimetric output correlates well with the reference method, a calibrated pH electrode. Compared to earlier systems where the cell potential is dictated by an external power source, the PB film exhibits excellent reproducibility and a rapid response time of about 44 s.Iron is an essential micronutrient for the survival and virulence of the bacterial pathogen Pseudomonas aeruginosa. To overcome iron withholding and successfully colonize a host, P. aeruginosa uses a variety of mechanisms to acquire iron, including the secretion of high-affinity iron chelators (siderophores) or the uptake and utilization of heme. P. aeruginosa heme oxygenase (HemO) plays pivotal roles in heme sensing, uptake, and utilization and has emerged as a therapeutic target for the development of antipseudomonal agents. Using a high-throughput fluorescence quenching assay combined with minimum inhibitory concentration measurements, we screened the Selleck Bioactive collection of 2100 compounds and identified acitretin, a Food and Drug Administration-approved oral retinoid, as a potent and selective inhibitor of HemO. Acitretin binds to HemO with a KD value of 0.10 ± 0.02 μM and inhibits the growth of P. aeruginosa PAO1 with an IC50 of 70 ± 18 μg/mL. In addition, acitretin showed good selectivity for HemO, which uniquely generates BVIXβ/δ, over human heme oxygenase (hHO1) and other BVIXα-producing homologues such as the heme oxygenases from Neisseria meningitidis (nmHO) and Acinetobacter baumannii (abHO). The binding of acitretin within the HemO active site was confirmed by 1H-15N heteronuclear single-quantum coherence nuclear magnetic resonance, and molecular modeling provided further insight into potential interactions of acitretin with residues specific for orienting heme in the β/δ selective HemO. Moreover, at 20 μM, acitretin inhibited the enzymatic activity of HemO in P. aeruginosa cells by >60% and effectively blocked the ability of P. aeruginosa to sense and acquire heme as demonstrated in the β-galactosidase transcriptional reporter assay.In contrast to artificial molecules, natural photosensitizers have the benefit of excellent toxicity profiles and of life-compatible activating energy ranges. Flavins are such photosensitizers that were selected by nature in a plethora of light-triggered biochemical reactions. Flavin-rich nanoparticles could thus emerge as promising tools in photodynamic therapies and in active-targeting drug delivery. Self-assembled flavin-conjugated phospholipids improve the pharmacokinetics of natural flavins and, in the case of controlled morphologies, reduce photobleaching phenomena. The current article presents a proof of concept for the design of riboflavin-rich nanoparticles of tunable morphology from multilamellar patches to vesicular self-assemblies. Coarse-grained simulations of the self-assembling process revealed the key interactions governing the obtained nanomaterials and successfully guided the synthesis of new flavin-conjugates of predictable self-assembly. The obtained flavin-based liposomes had a 65 nm hydrodynamic diameter, were stable, and showed potential photosensitizer activity.Cyclodextrin (CD)-based host-guest interactions with adamantane (Ad) have demonstrated use for functionalizing living cells in vitro. The next step in this supramolecular functionalization approach is to explore the concept to deliver chemical cargo to living cells in vivo, e.g., inoculated bacteria, in order to study their dissemination. selleck chemicals llc We validated this concept in two rodent Staphylococcus aureus models. Bacteria (1 × 108 viable S. aureus) were inoculated by (1) intramuscular injection or (2) intrasplenic injection followed by dissemination throughout the liver. The bacteria were prefunctionalized with 99mTc-UBI29-41-Ad2 (primary vector), which allowed us to both determine the bacterial load and create an in vivo target for the secondary host-vector (24 h post-inoculation). The secondary vector, i.e., chemical cargo delivery system, made use of a 111In-Cy50.5CD9PIBMA39 polymer that was administered intravenously. Bacteria-specific cargo delivery as a result of vector complexation was evaluated by dual-isotope SPECT imaging and biodistribution studies (111In), and by fluorescence (Cy5); these evaluations were performed 4 h post-injection of the secondary vector.