The reaction mechanism of the reverse water–gas shift (RWGS) reaction was investigated using two commercial gold-based catalysts supported on Al2O3 and TiO2. The surface species formed during the ...reaction and reaction mechanisms were elucidated by transient and steady-state operando DRIFTS studies. It was revealed that RWGS reaction over Au/Al2O3 proceeds through the formation of formate intermediates that are reduced to CO. In the case of the Au/TiO2 catalyst, the reaction goes through a redox mechanism with the suggested formation of hydroxycarbonyl intermediates, which further decompose to CO and water. The Ti3+ species, the surface hydroxyls, and oxygen vacancies jointly participate. The absence of carbonyl species adsorbed on gold particles during the reaction for both catalysts indicates that the reaction pathway involving dissociative adsorption of CO2 on Au particles can be discarded. To complete the study, operando ultraviolet–visible spectroscopy was successfully applied to confirm the presence of Ti3+ and to understand the role of the oxygen vacancies of TiO2 support in activating CO2 and thus the subsequent RWGS reaction.
Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the ...carbon–boron bond into a carbon–X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row d-block transition metals have become increasingly widely used as catalysts for the formation of a carbon–boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon–boron bonds.
Nanoparticles (NPs) have been gaining prominence as delivery vehicles for modulating immune responses to improve treatments against cancer and autoimmune diseases, enhancing tissue regeneration ...capacity, and potentiating vaccination efficacy. Various engineering approaches have been extensively explored to control the NP physical and chemical properties including particle size, shape, surface charge, hydrophobicity, rigidity and surface targeting ligands to modulate immune responses. This review examines a specific set of physical and chemical characteristics of NPs that enable efficient delivery targeted to secondary lymphoid tissues, specifically the lymph nodes and immune cells. A critical analysis of the structure-property-function relationship will facilitate further efforts to engineer new NPs with unique functionalities, identify novel utilities, and improve the clinical translation of NP formulations for immunotherapy.
Display omitted
The huge burden of malaria in developing countries urgently demands the development of novel approaches to fight this deadly disease. Although engineered symbiotic bacteria have been shown to render ...mosquitoes resistant to the parasite, the challenge remains to effectively introduce such bacteria into mosquito populations. We describe a Serratia bacterium strain (AS1) isolated from Anopheles ovaries that stably colonizes the mosquito midgut, female ovaries, and male accessory glands and spreads rapidly throughout mosquito populations. Serratia AS1 was genetically engineered for secretion of anti-Plasmodium effector proteins, and the recombinant strains inhibit development of Plasmodium falciparum in mosquitoes.
Three-level Box-Behnken experimental design with three factors (pH, temperature and antibiotic initial concentration) combined with response surface methodology (RSM) was applied to study the removal ...of Metronidazole and Sulfamethoxazole by walnut shell based activated carbon. This methodology enabled to identify the effects of the different factors studied and their interactions in the response of each antibiotic. The relationship between the independent variable (sorption capacity) and the dependent variables (pH, temperature and antibiotic concentration) was adequately modelled by second-order polynomial equation. The pH factor exerted a significant but distinct influence on the removal efficiency of both antibiotics. The removal of Metronidazole is favoured by increasing pH values, with the maximum value obtained for pH 8 - upper limit of the study domain; while Sulfamethoxazole displays a maximum value around 5.5, with a decrease in the extent of adsorption as the pH increases. The best conditions, predicted by the model, for the removal of the antibiotic Sulfamethoxazole (106.9 mg/g) are obtained at a temperature of 30 °C, initial concentration of 40 mg/L and a pH value of 5.5. For the antibiotic Metronidazole, the highest removal value (127 mg/g) is expected to occur at the maximum levels attributed to each of the factors (pH = 8, Cin = 40 mg/L, T = 30 °C). The results of isotherm experiments (at 20 °C and pH 6) displayed a good agreement with the models predictions. The maximum sorption capacity, estimated by the Langmuir model, was 107.4 mg/g for Metronidazole and 93.5 mg/g for Sulfamethoxazole.
Display omitted
•Walnut shell based activated carbon was tested for adsorption of two antibiotics.•The role of pH and temperature, on the removal, was studied by a Box-Behnken design.•The pH had the highest effect on Metronidazole (MNZ) removal.•The temperature had the greatest influence on Sulfamethoxazole (SMX) removal.•Langmuir maximum sorption capacities of 107.4 mg/g for MNZ and 93.5 mg/g for SMX
Bladder cancer - the tenth most frequent cancer worldwide - has a heterogeneous natural history and clinical behaviour. The predominant histological subtype, urothelial bladder carcinoma, is ...characterized by high recurrence rates, progression and both primary and acquired resistance to platinum-based therapy, which impose a considerable economic burden on health-care systems and have substantial effects on the quality of life and the overall outcomes of patients with bladder cancer. The incidence of urothelial tumours is increasing owing to population growth and ageing, so novel therapeutic options are vital. Based on work by The Cancer Genome Atlas project, which has identified targetable vulnerabilities in bladder cancer, immune checkpoint inhibitors (ICIs) have arisen as an effective alternative for managing advanced disease. However, although ICIs have shown durable responses in a subset of patients with bladder cancer, the overall response rate is only ~15-25%, which increases the demand for biomarkers of response and therapeutic strategies that can overcome resistance to ICIs. In ICI non-responders, cancer cells use effective mechanisms to evade immune cell antitumour activity; the overlapping Warburg effect machinery of cancer and immune cells is a putative determinant of the immunosuppressive phenotype in bladder cancer. This energetic interplay between tumour and immune cells leads to metabolic competition in the tumour ecosystem, limiting nutrient availability and leading to microenvironmental acidosis, which hinders immune cell function. Thus, molecular hallmarks of cancer cell metabolism are potential therapeutic targets, not only to eliminate malignant cells but also to boost the efficacy of immunotherapy. In this sense, integrating the targeting of tumour metabolism into immunotherapy design seems a rational approach to improve the therapeutic efficacy of ICIs.
Accelerating growth and global expansion of antimicrobial resistance has deepened the need for discovery of novel antimicrobial agents. Antimicrobial peptides have clear advantages over conventional ...antibiotics which include slower emergence of resistance, broad-spectrum antibiofilm activity, and the ability to favourably modulate the host immune response. Broad bacterial susceptibility to antimicrobial peptides offers an additional tool to expand knowledge about the evolution of antimicrobial resistance. Structural and functional limitations, combined with a stricter regulatory environment, have hampered the clinical translation of antimicrobial peptides as potential therapeutic agents. Existing computational and experimental tools attempt to ease the preclinical and clinical development of antimicrobial peptides as novel therapeutics. This Review identifies the benefits, challenges, and opportunities of using antimicrobial peptides against multidrug-resistant pathogens, highlights advances in the deployment of novel promising antimicrobial peptides, and underlines the needs and priorities in designing focused development strategies taking into account the most advanced tools available.
In real food, starch is usually forming part of a matrix with lipids and proteins. However, research on this ternary system and interactions between such food components has been scarce so far. The ...control of food microstructure is crucial to determine the product properties, including sensorial and nutritionals ones. This paper reviews the microstructural principles of interactions between starch, lipids, and proteins in foods as well as their effect on postprandial glycemic response, considering human intrinsic differences on postprandial glycemic responses. Several lines of research support the hypothesis that foods without rapidly digestible starch will not mandatorily generate the lowest postprandial glycemic response, highlighting that the full understanding of food microstructure, which modulates starch digestion, plays a key role on food design from a nutritional viewpoint.
As optical fibers revolutionize the way data is carried in telecommunications, the same is happening in the world of sensing. Fiber-optic sensors (FOS) rely on the principle of changing the ...properties of light that propagate in the fiber due to the effect of a specific physical or chemical parameter. We demonstrate the potentialities of this sensing concept to assess pressure in biomedical and biomechanical applications. FOSs are introduced after an overview of conventional sensors that are being used in the field. Pointing out their limitations, particularly as minimally invasive sensors, is also the starting point to argue FOSs are an alternative or a substitution technology. Even so, this technology will be more or less effective depending on the efforts to present more affordable turnkey solutions and peer-reviewed papers reporting in vivo experiments and clinical trials.
Covering: up to the end of 2017 The roles played by Rieske non-heme iron-dependent oxygenases in natural product biosynthesis are reviewed, with particular focus on experimentally characterised ...examples. Enzymes belonging to this class are known to catalyse a range of transformations, including oxidative carbocyclisation, N-oxygenation, C-hydroxylation and C-C desaturation. Examples of such enzymes that have yet to be experimentally investigated are also briefly described and their likely functions are discussed.
PDF
