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Enhanced hydrogen evolution was pursued in this work. Rhodobacter sp. (Rb) and Rhodopseudomonas palustris (Rp), single or mixed were used to extract hydrogen molecules from Chlorella fusca biomass. To elevate their fermentable contents, Chlorella was grown at nitrogen and/or phosphorus deprivation. Besides, cellulase and/or macerozyme, Triton X100 or sonicated yeast were applied for further biohydrogen fermentation. Utilizing hydrolysates of mineral deprived Chlorella cultures, Rb exhibited relatively higher cumulative hydrogen (4200 ml L−1) than Rp (2500 ml L−1) while mixed cultures attained significantly higher levels (4700 ml L−1). Triton or enzymes significantly enhanced hydrogen evolution, with more effectiveness of macerozyme than cellulase. A novel use of sonicated yeast, as enzymes pool, induced the highest significant collective H2 (up to 47 times that of microalgal supernatant). Sonicated yeast induced a remarkable hydrolysis of algae, as inferred from increased reducing sugars. However, hydrogen evolution efficiency exhibited poor proportionality with reducing sugars, indicating fermentation of other metabolites.

Periodontitis is prevalent in half of the adult population and raises critical health concerns as it has been recently associated with an increased risk of cancer. While information about the topic remains somewhat scarce, a deeper understanding of the underlying mechanistic pathways promoting neoplasia in periodontitis patients is of fundamental importance. This manuscript presents the literature as well as a panel of tables and figures on the molecular mechanisms of Porphyromonas gingivalis and Fusobacterium nucleatum, two main oral pathogens in periodontitis pathology, involved in instigating tumorigenesis. We also present evidence for potential links between the RANKL–RANK signaling axis as well as circulating cytokines/leukocytes and carcinogenesis. Due to the nonconclusive data associating periodontitis and cancer reported in the case and cohort studies, we examine clinical trials relevant to the topic and summarize their outcome.

Light chain (AL) amyloidosis is characterized by deposition of immunoglobulin light chains (LC) as fibrils in target organs. Alongside the full-length protein, abundant LC fragments are always present in AL deposits. Herein, by combining gel-based and mass spectrometry analyses, we identified and compared the fragmentation sites of amyloid LCs from multiple organs of an AL λ amyloidosis patient (AL-55). The positions pinpointed here in kidney and subcutaneous fat, alongside those previously detected in heart of the same patient, were aligned and mapped on the LC's dimeric and fibrillar states. All tissues contain fragmented LCs along with the full-length protein; the fragment pattern is coincident across organs, although microheterogeneity exists. Multiple cleavage positions were detected; some are shared, whereas some are organ-specific, likely due to a complex of proteases. Cleavage sites are concentrated in "proteolysis-prone" regions, common to all tissues. Several proteolytic sites are not accessible on native dimers, while they are compatible with fibrils. Overall, data suggest that the heterogeneous ensemble of LC fragments originates in tissues, and is consistent with digestion of preformed fibrils, or with the hypothesis that initial proteolytic cleavage of the constant domain triggers the amyloidogenic potential of LCs, followed by subsequent proteolytic degradation. This work provides a unique set of molecular data on proteolysis from ex vivo amyloid, which allows discussing hypotheses on role and timing of proteolytic events occurring along amyloid formation and accumulation in AL patients.

In Industrial-Internet-of-Things (IIoT) applications, fog computing (FC) has soared as a means to improve the Quality of Services (QoSs) provided to users through cloud computing, which has become overwhelmed by the massive flow of data. Transmitting all these amounts of data to the cloud and coming back with a response can cause high latency and requires high network bandwidth. The availability of sustainable energy sources for FC servers is one of the difficulties that the service providers can face in IIoT applications. The most important factor contributing to energy consumption on fog servers is task scheduling. In this article, we suggest an energy-aware metaheuristic algorithm based on a Harris Hawks optimization algorithm based on a local search strategy (HHOLS) for task scheduling in FC (TSFC) to improve the QoSs provided to the users in IIoT applications. First, we describe the high virtualized layered FC model taking into account its heterogeneous architecture. The normalization and scaling phase aids the standard Harris hawks algorithm to solve the TSFC, which is discrete. Moreover, the swap mutation ameliorates the quality of the solutions due to its ability to balance the workloads among all virtual machines. For further improvements, a local search strategy is integrated with HHOLS. We compare HHOLS with other metaheuristics using various performance metrics, such as energy consumption, makespan, cost, flow time, and emission rate of carbon dioxide. The proposed algorithm gives superior results in comparison with other algorithms.

We would like to acknowledge King Abdullah University of Science and Technology for funding. We also acknowledge KAUST NMR core lab for their continuous help. We acknowledge as well the KAUST Imaging Core Lab, particularly Dr. Alessandro Genovese.

The emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag9(1,2-BDT)6]3– (1,2-BDT = 1,2-benzenedithiolate). The NC’s crystal structure reveals the self-assembly of two Ag square pyramids through preferential pyramidal vertex sharing of a single metallic Ag atom, while all other Ag atoms are incorporated in a motif with thiolate ligands, resulting in an elongated body-centered Ag9 skeleton. Steric hindrance and arrangement of the dithiolated ligands on the surface favor the formation of an anisotropic shape. Time-dependent density functional theory based calculations reproduce the experimental optical absorption features and identify the molecular orbitals responsible for the electronic transitions. Our findings will open new avenues for the design of novel single-digit metal NCs with directional self-assembled building blocks., An isomeric dithiol-based synthesis strategy is used to synthesize the smallest crystallized Ag nanocluster, [Ag9(1,2-BDT)6]3−. The single-digit cluster reveals novel bonding modes and building blocks, which include the self-assembly of two Ag square pyramids sharing a common vertex and six bidentate thiolate motifs.

The gap between supply and demand of propylene has become more and more evident, because of a large consumption of the downstream products derived from propylene. Propane dehydrogenation (PDH) constitutes an important alternative for the production of propylene, and thus considerable attention has been paid to the development of eco-friendly and cost-efficient catalysts for this process. Herein, we discover that the Sn-Beta zeolite with Lewis acid sites can activate the C-H bond, and exhibits high catalytic performance in the PDH. XRD, STEM, and XPS characterizations confirm that Sn species are incorporated into the zeolite framework, and H2-TPR suggests that there is a strong interaction between Sn species and zeolite framework. It is found that the Lewis acid is the active site for dehydrogenation reaction, and the Bronsted acid is responsible for cracking reaction. The dehydrogenation rate/cracking rate is positively proportional to the L/B ratio, and a high L/B ratio is beneficial for the propane dehydrogenation reaction. The Na-Sn-Beta-30 catalyst possessing the highest amount of Lewis acid but the lowest Bronsted/Lewis ratio, exhibits the best performance in the PDH, which delivers propane conversion of 40% and propylene selectivity of 92%. Most importantly, these Sn-Beta zeolites are extremely stable without any detectable deactivation under the harsh reaction condition for 72 h. Density functional theory calculations reveal that both Sn and adjacent O atom or OH group cooperatively act as the active sites. The PDH occurs through the direct reaction mechanism in which hydrogen molecule is produced by the direct coupling of H atom of primary C3H7 motif with the Bronsted proton in closed sites or the proton of water in open sites. It seems that open sites are more reactive than the closed ones, and the intrinsic enthalpy barriers are calculated to be 242 ~ 301 kJ/mol depending on the hydroxylation extents. These efficient Sn-Beta zeolites could provide a new possibility for the development of a new generation of PDH catalysts with a high stability for the production of propylene.

Worldwide NH3 production reached 0.18 Gton in 2019, and 1–2% of the global CO2 emissions are due to large-scale NH3 synthesis (1 billion tons of CO2 / year). A catalyst for ammonia synthesis has been obtained by pyrolysis of iron phthalocyanine (FePc) precursor under N2, followed by impregnation with alkali metals (Na, Li, K, and Cs) and H2 treatment. Characterization (XPS, XRD, HR-TEM, ICP-OES, TGA, CHNS analysis, and BET) revealed nano-sized core–shell structures formed during H2 treatment, with Fe in the core and promoters (“Cs2O” and “K2O”) with carbon on the shell. The alkali metals partially inhibit the methanation process of carbon. These Fe NPs were found to be very active and stable catalysts, as compared to the commercial iron-based catalyst KM1 (Haldor-Topsoe). Activities of promoted catalysts follow the order: K > Cs > Na ~ Li, with more than 6% of NH3 at 400 °C and 7 MPa, and contact time (WHSV) of 12000 ml g−1 h−1 with K. The apparent activation energy was found to be 31 kJ mol−1 and 34 kJ mol−1 for 3-K-FePc700 and 10-Cs-FePc700 suggesting the facile activation of N2 on the catalysts surface. DFT-based predicted atomic and electronic structures reveal a similarity in the partial charge distribution on surface Fe species with K or Cs. Surprisingly the main effect of alkali is related to the geometrical repartition of alkali, leading to a larger number of exposed iron atoms, active sites, in the case of K than Cs. The alkali (present as metal oxide) leaves at medium coverage of the surface some exposed Fe(0) for N2 non-dissociative chemisorption (end-on type). The free energy profile demonstrates that the thermodynamic stability of the reaction intermediates for nitrogen reduction reaction (NRR) increases with pressure indicating better feasibility of the reaction at higher pressures.

In this work, chitosan was used as powerful chelating agent and an excellent template for synthesis of metal oxide nanoparticles. Chitosan-Pb and Chitosan-Bi nanoparticles have been synthesized by incorporating PbO/BiO nanoparticles within the chitosan matrix using a simple solution cast method. Dielectric and optical properties of the nanocomposite film were studied. Moreover, the effect of temperature on the dielectric properties of the hybrid film was determined. The absorption and transmittance were measured for the prepared samples by using UV–Vis spectrophotometer. The optical parameters such as refractive index, absorption coefficient, energy band gap, dispersion energy, oscillation energy, and the skin or penetration depth for the chitosan-PbO/-BiO nanocomposite were obtained.

In this article, we offer a summary of a broad variety of colloidal drug delivery systems with a special emphasis on vesicular used in testing or theoretically useful as carrier systems for medicines or active biomolecules or as cell carriers with therapeutic use. They provide several significant details of the currently developed drug delivery systems for academic or clinical applications. This series of systems are commonly used due to outstanding drug tracking, continuous and regulated release behavior, improved drug molecules clogging performance, avoidance of product hydrolysis or enzymatic degradation, and therapeutic efficacy improvements. Such characteristics aid in the discovery of suitable carrier structures for the transmission of medicines, cells, and genes in various fields. Colloidal drug delivery systems play a significant role in drug delivery. In my opinion, all colloidal carriers present notable characteristics after application. These vesicles can deliver an active compound through the biological membranes via absorption, fusion, and to raise the quantity of permeated drugs compared with conventional formulations.

In this study, polymeric films based on chitosan (CS) doped with Lanthanum oxide nanoparticles at different weight percentages (5, 10, 15, and 20% La2O3/CS) were prepared using the simple solution cast transformation. The dielectric constant increases with increasing the La2O3 content, and this could be attributed to the induced defects, as a result more dipoles are produced in the polymer matrix. Also, the values of Z′ and Z″ increase with La contents. On other hand, we noticed that the plot of the normalized-imaginary electric modulus versus the frequency shows a clear peak at high frequency for all samples. This peak is associated with ionic conduction. The AC conductivity increased by increasing the La2O3 content. Furthermore, AC conductivity increases with frequency because the absorbed energy from the electric field can increase the number of charge carriers that are participating in the electric conduction. Moreover, the values of the universal exponents were larger than the unity and increase with increasing temperatures which means that the conduction process may be pertinent to reorientational (or localized) mechanism.

We report here the first step by step anchoring of a W(≡CtBu)(CH2tBu)3 complex on a highly crystalline and mesoporous MOF, namely Zr-NU-1000, using a Surface Organometallic Chemistry (SOMC) concept...

We would like to acknowledge King Abdullah University of Science and Technology for funding. We also acknowledge the NMR core lab for their continuous help.

The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(≡Si–O−)Ti(−NMe2)3], which transforms into a three-membered metallacycle (called ...

The purpose of this investigation was to encapsulate carvedilol, a model beta-blocker antihypertensive into nano-spanlastics, followed by incorporation into 1% CMC wafer to afford a mucoadhesive buccal drug delivery system, targeting to sidestep the first-pass metabolism, improving the drug absorption and pharmacological effect, achieving non-invasive buccal delivery for treating hypertension. Carvedilol-loaded nano-spanlastics were rendered by ethanol injection technique, using 23 factorial design. The effect of formulation variables was investigated on nano-spanlastic characteristics. The optimal nano-spanlastic formulation (S2; containing 20% Brij 97) exhibited particle size (239.8 ± 5 nm), entrapment efficiency (98. 16 ± 1.44%), deformability index (8.74 ± 0.42 g), and the flux after 24 h (Jmax) (22.5 ± 0.25 (μg/cm2/h) with enhancement ratio 2.87 as well as excellent stability after storage. Permeation study verified the preeminence of the S2 formula. A confocal laser scanning microscope showed deep penetration of S2 through sheep buccal mucosa formula compared to rhodamine B solution. S2-based wafer showed acceptable characters (pH, swelling, drug content, residence time, and release rate). In vivo studies (pharmacodynamic study and biochemical evaluation) showed considerable improvement in blood pressure, the profile of the lipid, oxidant stress biomarkers, and cardiac markers. Histopathological studies revealed the superiority of S2 wafer in the protection of heart tissues over Carvid®. The results achieved indicate that nano-spanlastic-based wafer offers a promising improving trans-buccal carvedilol delivery system.

Hydrogen is a clean fuel widely used in fuel cells, engines, rockets and many other devices. The catalytic decomposition of methane (CDM) is a COx-free hydrogen production technology from which carbon nano materials (CNMs) can be generated as a high value-added byproduct for electrode, membranes and sensors. Recent work has focused on developing a low cost catalyst that could work without rapid deactivation by carbon deposition. In this review, the economic and environmental evaluation of CDM are compared with coal gasification, steam reforming of methane, and methanol steam reforming in terms of productivity, CO2 emissions, and H2 production and cost. CDM could be a favorable technology for on-site demand-driven hydrogen production on a small or medium industrial scale. This study covers the Fe-based, Ni-based, noble metal, and carbonaceous catalysts for the CDM process. Focusing on hydrogen (or carbon) yield and production cost, Fe-based catalysts are preferable for CDM. Although Ni-based catalysts showed a much higher hydrogen yield with 0.39 molH2/gcat./h than Fe-based catalysts with 0.22 molH2/gcat./h, the hydrogen cost of the former was estimated to be 100-fold higher ($0.89/$0.009). Further, the CDM performance on different types of reactors are detailed, whereas the molten-metal catalyst/reactor is suggested to be a promising route to commercialize CDM. Finally, the formation mechanism, characterization, and utilization of carbon byproducts with different morphologies and structures are described and analyzed. Versus other reviews, this review shows that cheap Fe-based catalysts (10 tons H2/1 ton iron ore) and novel molten-metal reactors (95% methane conversion) for CDM are feasible research directions for a fundamental understanding of CDM. The CNMs by CDM could be applied to the waste water purification, lubricating oils, and supercapacitors.

Duchenne muscular dystrophy (DMD) is a common and severe X-linked myopathy, characterized by muscle degeneration due to altered or absent dystrophin. DMD has no effective cure, and the underlying molecular mechanisms remain incompletely understood. The aim of this study is to investigate the metabolic changes in DMD using mass spectrometry-based imaging. Nine human muscle biopsies from DMD patients and nine muscle biopsies from control individuals were subjected to untargeted MSI using matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry. Both univariate and pattern recognition techniques have been used for data analysis. This study revealed significant changes in 34 keys metabolites. Seven metabolites were decreased in the Duchenne biopsies compared to control biopsies including adenosine triphosphate, and glycerophosphocholine. The other 27 metabolites were increased in the Duchenne biopsies, including sphingomyelin, phosphatidylcholines, phosphatidic acids and phosphatidylserines. Most of these dysregulated metabolites are tightly related to energy and phospholipid metabolism. This study revealed a deep metabolic remodelling in phospholipids and energy metabolism in DMD. This systems-based approach enabled exploring the metabolism in DMD in an unprecedented holistic and unbiased manner with hypothesis-free strategies.

Catalytic decomposition of methane (CDM) is a promising technology for producing COx-free hydrogen and nano-carbon, meanwhile it is a prospective substitute to steam reforming of methane for producing hydrogen. The produced hydrogen is refined and can be applied to the field of electronic, metallurgical, synthesis of fine organic chemicals and aerospace industries. However, the CDM for COx-free hydrogen production is still in its infancy. The urgent for industrial scale of CDM is more important than ever in the current situation of huge COx emission. This review studies CDM development on Ni-based, noble metal, carbon and Fe-based catalysts, especially over cheap Fe-based catalyst to indicate that CDM would be a promising feasible method for large hydrogen production at a moderate cheap price. Besides, the recent advances in the reaction mechanism and kinetic study over metal catalysts are outlined to indicate that the catalyst deactivation rate would become more quickly with increasing temperature than the CDM rate does. This review also evaluates the roles played by various parameters on CDM catalysts performance, such as metal loading effect, influences of supports, hydrogen reduction, methane reduction and methane/hydrogen carburization. Catalysts deactivation by carbon deposition is the prime challenge found in CDM process, as an interesting approach, a molten-metal reactor to continually remove the floated surface solid carbons is put forwarded in accordance to overcome the deactivation drawback. Moreover, particular CDM reactors using substituted heating sources such as plasma and solar are detailed illustrated in this review in addition to the common electrical heating reactors of fixed bed, fluidized bed reactors. The development of high efficiency catalysts and the optimization of reactors are necessary premises for the industrial-scale production of CDM.

The technical feasibility of synthetic natural gas production from biogenic source was evaluated under industrially relevant conditions. The biogas produced from anaerobic digestion in a waste water treatment plant was considered as renewable carbon dioxide source and renewable hydrogen was produced by alkaline electrolysis (37 kWhe) of tap water. In the present work, the catalytic methanation of biogas, partially upgraded biogas and carbon dioxide released by a membrane upgrading unit was performed through innovative micro-structured heat-exchange reactors. A 2-step methanation process, including gas pre-heating, catalytic reaction and water condensation was implemented. Experimentation revealed that, through this process strategy, the outlet gas mixture (CH4 ≥ 95%, H2 ≤ 5% and CO2 ≤ 2.5%) fulfils the requirements for gas grid injection. It was observed that most reaction occurred in the first reactor (T ≈ 400 °C), while the second reactor (T ≈ 300 °C) was necessary to assure a high methane content. The introduction of methane together with carbon dioxide was found to be positive, namely biogas or partially upgraded biogas instead of pure carbon dioxide. The methanation of biogas reduced the reaction hot-spots and increased the methane content at the outlet. Finally, a proper balance between injection requirements and costs was found at 4–5 bar (g).

We present a novel approach to produce gold nanoclusters (Au NCs) in the pores of mesoporous silica nanoparticles (MSNs) by sequential and controlled addition of metal ions and reducing agents. This impregnation technique was followed to confine Au NCs inside the pores of MSNs without adding external ligands or stabilizing agents. TEM images show a uniform distribution of monodisperse NCs with an average size of 1.37 ± 0.4 nm. Since the NCs are grown in situ in MSN pores, additional support and high temperature calcination are not required to use them as catalysts. The use of Au NC/MSNs as a catalyst for the epoxidation of styrene in the presence of tert-butyl hydroperoxide (TBHP) as a terminal oxidant resulted in an 88% conversion of styrene in 12 h with a 74% selectivity towards styrene epoxide. Our observations suggest that this remarkable catalytic performance is due to the small size of Au NCs and the strong interaction between gold and the MSNs. This catalytic conversion is environmentally friendly as it is solvent free. We believe our synthetic approach can be extended to other metal NCs offering a wide range of applications.

Alkylation of Ti(CH3)2Cl21 by MeLi gives the homoleptic Ti(CH3)42 for the first time in the absence of any coordinating solvent. The reaction of 2 with silica pretreated at 700 °C (SiO2–700) gives two inequivalent silica-supported Ti-methyl species 3. Complex 3 was characterized by IR, microanalysis (ICP-OES, CHNS, and gas quantification), and advanced solid-state NMR spectroscopy (1H, 13C, DQ, TQ, and HETCOR). The catalytic activity of the pre-catalyst 3 is investigated in low-temperature hydrogenolysis of propane and n-butane with TONs of 419 and 578, respectively.

The rapid spread of novel coronavirus pneumonia (COVID-19) has led to a dramatically increased mortality rate worldwide. Despite many efforts, the rapid development of an effective vaccine for this novel virus will take considerable time and relies on the identification of drug-target (DT) interactions utilizing commercially available medication to identify potential inhibitors. Motivated by this, we propose a new framework, called DeepH-DTA, for predicting DT binding affinities for heterogeneous drugs. We propose a heterogeneous graph attention (HGAT) model to learn topological information of compound molecules and bidirectional ConvLSTM layers for modeling spatio-sequential information in simplified molecular-input line-entry system (SMILES) sequences of drug data. For protein sequences, we propose a squeezed-excited dense convolutional network for learning hidden representations within amino acid sequences; while utilizing advanced embedding techniques for encoding both kinds of input sequences. The performance of DeepH-DTA is evaluated through extensive experiments against cutting-edge approaches utilising two public datasets (Davis, and KIBA) which comprise eclectic samples of the kinase protein family and the pertinent inhibitors. DeepH-DTA attains the highest Concordance Index (CI) of 0.924 and 0.927 and also achieved a mean square error (MSE) of 0.195 and 0.111 on the Davis and KIBA datasets respectively. Moreover, a study using FDA-approved drugs from the Drug Bank database is performed using DeepH-DTA to predict the affinity scores of drugs against SARS-CoV-2 amino acid sequences, and the results show that that the model can predict some of the SARS-Cov-2 inhibitors that have been recently approved in many clinical studies.

Highly efficient and very stable iron and/or cobalt-based catalysts for the ammonia synthesis reaction were synthesized by one-step pyrolysis of metal phthalocyanine precursors. The presence of alkaline earth or alkali metals is found to be essential for accelerating the reaction rate for the ammonia synthesis process. When promoted by alkali metals, the catalysts show a 3-fold increase in their catalytic performance (at 400 °C and 0.1–7 MPa) compared to a commercial benchmark iron-based catalyst, widely used for the Haber–Bosch process. TEM images reveal the local structure of the catalysts obtained upon pyrolysis of the metal phthalocyanine precursor, with metal nanoparticles (5–50 nm) confined in a nitrogen-doped carbon mesoporous matrix, where the alkali metal promoters are located on the top of the iron nanoparticles but also on the carbon support. Finally, kinetic analysis shows a lower activation energy for the Fe phthalocyanine-derived catalyst (42 kJ mol−1) versus 70 kJ mol−1 reported for the iron-benchmark catalyst. Furthermore, this kinetic analysis suggests that the rate-determining step shifts from nitrogen activation to NHx formation, which only few catalysts have achieved.

The metal complex (Zr(CH3)4(THF)2) has been fully synthesized, characterized and grafted onto partially dehydroxylated silica to give two surface species [([triple bond, length as m-dash]Si-O-)Zr(CH3)3(THF)2] (minor) and [([triple bond, length as m-dash]Si-O-)2Zr(CH3)2(THF)2] (major) which have been characterized by SS NMR, IR, and elemental analysis. These supported pre-catalysts exhibit the best conversion of CO2 to cyclic carbonates, as compared to the previously reported SOMC catalysts.

Background and objective Cyanobacteria grown under abiotic stress affect on some metabolites that used as promising for foods and feeds biotechnology. Thus, the objective of the study was to evaluate the 3 local cyanobacteria isolates for production of foods and feeds under various concentration of phosphorus. Material and methods Cyanobacteria namely; Anabaena sp., Merismopedia tenuissima and Spirulina platensis were grown photoautotrophically in modified medium. The growth pattern in the medium containing various phosphorus concentrations were followed and harvested around 14 days. Results A decrease in phosphorus concentrations by 50% led to an increase in chlorophyll-a of M. tenuissima and S. platensis. The application of high concentration of phosphorus (+100%) to the culture of Anabaena sp. led to an increase in dry weight and growth rate by 0.382 mg mL-1 and 0.013 h-1, respectively. The deficiency of phosphorus concentrations led to a decrease in carbohydrate contents of Anabaena, Merismopedia and Spirulina with compared to the control culture. In general, the total lipid contents of Anabaena sp. and M. tenuissima were stimulated by phosphorus deficiency. The phosphorus-free media and increase in phosphorus concentration by 100% resulted in an increase in protein fractions such as soluble, insoluble, globulins, prolamines, glutelins and total protein content of Anabaena sp. The application of high concentration of phosphorus (+100%) to the culture of S. platensis led to an increase in total lipid contents in comparison to control. The highest phycobiliprotein contents of S. platensis were recorded at 50% phosphorus deficiency. Conclusion Cyanobacteria has a soft cell wall that makes it especially easy to digest and is additionally full of live active enzymes which further enhances metabolism and the efficient intake of nutrients.

Catalytic methane decomposition was investigated over 40 wt% Fe/Al2O3 catalyst in fluidized bed reactor (FLBR). After optimization of FLBR conditions in terms of catalyst bulk density, particle size, minimum fluidization velocity, and the catalyst bed height, the catalyst activity and stability tests were conducted by comparison with a fixed bed reactor (FBR). Although a similar stable methane conversion was obtained over both reactors, the pressure drop during 35 min operation of FBR was 9 times higher than that of FLBR, which indicated the possibility of continuous operation of methane decomposition process over FLBR. Further, the influence of the space velocity, feed dilution and regeneration on catalysts reactivity was studied in FLBR to conclude that a reaction condition of 12 L/gcat∙h, feed of 20%H2–80%CH4 and CO2-regeneration of deactivated catalysts may be favourable for operating methane decomposition in FLBR continually and effectively to provide stable hydrogen.

Plants have evolved the ability to derive the benzenoid moiety of the respiratory cofactor and antioxidant, ubiquinone (coenzyme Q), either from the β-oxidative metabolism of p-coumarate or from the peroxidative cleavage of kaempferol. Here, isotopic feeding assays, gene co-expression analysis and reverse genetics identified Arabidopsis 4-COUMARATE-COA LIGASE 8 (4-CL8; At5g38120) as a contributor to the β-oxidation of p-coumarate for ubiquinone biosynthesis. The enzyme is part of the same clade (V) of acyl-activating enzymes than At4g19010, a p-coumarate CoA ligase known to play a central role in the conversion of p-coumarate into 4-hydroxybenzoate. A 4-cl8 T-DNA knockout displayed a 20% decrease in ubiquinone content compared with wild-type plants, while 4-CL8 overexpression boosted ubiquinone content up to 150% of the control level. Similarly, the isotopic enrichment of ubiquinone's ring was decreased by 28% in the 4-cl8 knockout as compared with wild-type controls when Phe-[Ring-13C6] was fed to the plants. This metabolic blockage could be bypassed via the exogenous supply of 4-hydroxybenzoate, the product of p-coumarate β-oxidation. Arabidopsis 4-CL8 displays a canonical peroxisomal targeting sequence type 1, and confocal microscopy experiments using fused fluorescent reporters demonstrated that this enzyme is imported into peroxisomes. Time course feeding assays using Phe-[Ring-13C6] in a series of Arabidopsis single and double knockouts blocked in the β-oxidative metabolism of p-coumarate (4-cl8; at4g19010; at4g19010 × 4-cl8), flavonol biosynthesis (flavanone-3-hydroxylase), or both (at4g19010 × flavanone-3-hydroxylase) indicated that continuous high light treatments (500 µE m−2 s−1; 24 h) markedly stimulated the de novo biosynthesis of ubiquinone independently of kaempferol catabolism.

The relationship between total column ozone (TCO) and the development of a cyclonic system that occurred in the period from January 18 to January 25, 1981 has been studied using the ERA-Interim reanalysis database. It was found that TCO increases and decreases with the development and weakening of the cyclonic system. Also, a good correlation between TCO and the thickness of the layer was found between 1000-100 hPa and tropopause pressure. The study of daily variations in TCO based on the vertical distribution of the ozone mass mixing ratio (OMR) illustrate that with the beginning of the growth period there is a high decrease of the tropopause height, which was associated to high deepening of the cyclone and was accompanied by a significant vertical increase of OMR in the troposphere and stratosphere. The obvious significant increase of OMR starts at the stratospheric layer and is then transported to the tropospheric layer. The analysis of the time-height variation of the differences of OMR between the average of the domain containing the center of the cyclone at each level and the corresponding monthly average, illustrates that during the days of maximum deepening the positive values of OMR extend downwards to reach the 850 hPa level. The increase in positive values continues to be higher in the upper levels and reaches maximum values between 300-100 hPa and also between the 60-10 hPa layer. The characteristics of these changes of OMR concentrations from layer to layer are predominantly due to dynamical processes. Also, this was attributed to the effect of horizontal advection of ozone from a different neighboring region into the column, and by a vertical exchange of air between the high ozone at the stratosphere and low ozone at troposphere.

Selective hydroamination of terminal alkynes with primary aryl amines is catalyzed by an unprecedented well-defined silica-supported tantalum complex [(≡Si–O−)Ta(η1σ-NEtMe)2(=NtBu)]. A molecular-level characterization of the surface organometallic Ta species was done with the help of characterization techniques including in situ infrared, 1H and 13C solid-state NMR (including double and triple quanta sequencing), and X-ray absorption spectroscopies. These were complemented by the state-of-the-art DNP-SENS 15N characterization. Several catalytic intermediates have been isolated, in particular the 4-membered metallacycle ring intermediate resulting from the anti-Markovnikov addition of the alkyne to the surface tantalum imido. A mechanism is proposed that is on the isolation of all intermediates. A density functional theory (DFT) calculation has confirmed all the elementary steps and intermediates that were fully characterized.

The bimetallic Pt-Sn catalysts are known to be the most efficient ones for propane dehydrogenation reaction; however, the synthesis of bimetallic Pt-Sn nanocluster (below 1 nm) with an alloy structure still remains a formidable challenge. An approach for the controllable synthesis of Pt-Sn nanocluster based on Surface Organometallic Chemistry on oxide concept is developed here, which involves two basic steps: the sequential grafting of Pt(COD)Me2 and HSnPh3 at the surface of dehydroxylated θ-Al2O leading to the formation of well-defined bimetallic surface compound consisting of [( AlO )Pt(COD)Me] and [( AlO )SnPh3] fragments, and the hydrogenolysis of this surface compound under a mild condition giving rise to the ultra-small bimetallic Pt-Sn cluster around 0.75 nm. The achieved Pt-Sn/θ-Al2O3 catalysts exhibit high activity, selectivity and stability in propane dehydrogenation to propylene.

Significance Oxidation and reduction steps in catalysis are always in series, and excellent activity can be achieved when they occur in close proximity. Photooxidation and photoreduction are generally separated and rarely in series. This work develops defect engineering at the metal–oxide interface to make photooxidation sites close to photoreduction sites. Taking solar hydrogen production from aqueous alcohols over Pt/ T i O 2 as an example, the proximity effect triggers unusual reactions and thus increases hydrogen yield per photon from 0.046 to 1.28. Our study provides a direction for the development of efficient photocatalysis.

Ubiquinone (Coenzyme Q) is a vital respiratory cofactor and liposoluble antioxidant. In plants, it is not known how the C-6 hydroxylation of demethoxyubiquinone, the penultimate step in ubiquinone biosynthesis, is catalyzed. The combination of cross-species gene network modeling along with mining of embryo-defective mutant databases of Arabidopsis thaliana identified the embryo lethal locus EMB2421 (At1g24340) as a top candidate for the missing plant demethoxyubiquinone hydroxylase. In marked contrast with prototypical eukaryotic demethoxyubiquinone hydroxylases, the catalytic mechanism of which depends on a carboxylate-bridged di-iron domain, At1g24340 is homologous to FAD-dependent oxidoreductases that instead use NAD(P)H as an electron donor. Complementation assays in Saccharomyces cerevisiae and Escherichia coli demonstrated that At1g24340 encodes a functional demethoxyubiquinone hydroxylase and that the enzyme displays strict specificity for the C-6 position of the benzoquinone ring. Laser-scanning confocal microscopy also showed that GFP-tagged At1g24340 is targeted to mitochondria. Silencing of At1g24340 resulted in 40 to 74% decrease in ubiquinone content and de novo ubiquinone biosynthesis. Consistent with the role of At1g24340 as a benzenoid ring modification enzyme, this metabolic blockage could not be bypassed by supplementation with 4-hydroxybenzoate, the immediate precursor of ubiquinone's ring. Unlike in yeast, in Arabidopsis overexpression of demethoxyubiquinone hydroxylase did not boost ubiquinone content. Phylogenetic reconstructions indicated that plant demethoxyubiquinone hydroxylase is most closely related to prokaryotic monooxygenases that act on halogenated aromatics and likely descends from an event of horizontal gene transfer between a green alga and a bacterium.

The aim of this work is to explore the ability and magnitude of the temperate cyanobacterium Dolichospermum flosaquae in MICP (microbially-induced calcium carbonate precipitation). Environmentally, MICP controls the availability of calcium, carbon and phosphorus in freshwater lakes and simultaneously controls carbon exchange with the atmosphere. Cultures of flosaquae were grown in BG11 medium containing 0, 1, 1.5, 2 and 4 mg Ca2+ L−1, as cardinal concentrations previously reported in freshwater lakes, in addition to a control culture (BG11 containing 13 mg Ca2+ L−1). Growth (cell number, chlorophyll a, and protein content) of D. flosaquae was generally reduced by elevating calcium concentrations of the different salts used (chloride, acetate, or citrate). D. flosaquae seems able to perform MICP as carbonate alkalinity was sharply induced up to its highest level (six times that of the control) at a citrate concentration of 4 mg Ca2+ L−1. Calcium carbonate was formed at a pre-precipitation stage as the minimum pH necessary for precipitation (8.7) has been scarcely approached under such conditions. MICP took place mostly relying on photosynthesis and respiration, but not on urease activity, as urea was not supplemented in the growth media. However, D. flosaquae exhibited strong urease specific activity in in vitro assays (four times that of the control at 4 mg Ca2+ citrate L−1). Residual calcium exhibited its lowest value at 4 mg Ca2+ citrate L−1, coinciding with the highest alkalinity level. Consumed calcium was increasing with chlorophyll a content, but not with increasing cell numbers. The experiments should be repeated in a future study, but in the presence of urea, to evaluate the full potential of calcium carbonate precipitation of D. flosaquae, its dynamics and impact on biogeochemical cycles of calcium, carbon and phosphorus in freshwater lakes.

Summary Dew water, mostly ignored until now, can provide clean freshwater resources, just by extracting the atmospheric vapor available in surrounding air. Inspired by silicon-based solar panels, the vapor can be harvested by a concept of water condensing panels. Efficient water harvesting requires not only a considerable yield but also a timely water removal from the surface since the very beginning of condensation to avoid the huge evaporation losses. This translates into strict surface properties, which are difficult to simultaneously realize. Herein, we study various functionalized silicon surfaces, including the so-called Black Silicon, which supports two droplet motion modes—out-of-plane jumping and in-plane sweeping, due to its unique surface morphology, synergistically leading to a pioneering combination of above two required characteristics. According to silicon material's scalability, the proposed silicon-based water panels would benefit from existing infrastructures toward dual functions of energy harvesting in daytime and water harvesting in nighttime., Graphical abstract, Highlights • Unusual condensation dynamics occur on the hierarchical Black Silicon metasurface • Near-zero water removal time and good water yield are simultaneously achieved • Great scalability and multifunctionality are accessible to the proposed water panel, Materials design; Materials property; Metamaterials; Surface

Purpose: Carvedilol (CRV) is a non-selective beta-blocker used for hypertension treatment, angina pectoris, and heart failure. Oral administration of CRV showed poor bioavailability (25%), which may be due to exposure to the first-pass metabolism. Buccal delivery was used to boost its bioavailability.Methods: In this study carboxymethylcellulose/hydroxypropyl cellulose (CMC/HPC) composite buccal sponge enriched with CRV bilosomes was developed. Bilosomes were prepared using the thin-film hydration-sonication technique by applying a 32 -factorial design.Results: BL9 possessed the highest desirability value (0.861) and therefore, it was chosen as an optimal bilosomes. It exhibited a spherical shape with 217.2 nm, 87.13% entrapment efficiency, and a sustained release of CRV up to 24h. Consecutively, BL9 was incorporated in a CMC/HPC gel and lyophilized for 24 h to obtain a CMC-HPCL9 bilosomal sponge to enhance CRV buccal delivery. Morphological analysis of the prepared sponge with improved swelling showed a porosity of 67.58 percent. The in vivo assessment of rats indicates that the CMC-HPC/BL9 sponge enhances systolic/diastolic blood pressure, lipid profiles, oxidative stress biomarkers, and heart biomarkers with improved heart tissue quality.Conclusion: These results strongly encourage the use of this novel CMC-HPC/BL9 composite buccal sponge for the management of hypertension.

Aims/hypothesis Inflammation has a major role in diabetic kidney disease. We thus investigated the role of the IL-8-CXCR1/2 axis in favoring kidney damage in diabetes. Methods Urinary IL-8 levels were measured in 1247 patients of the Joslin Kidney Study in type 2 diabetes (T2D). The expression of IL-8 and of its membrane receptors CXCR1/CXCR2 was quantified in kidney tissues in patients with T2D and in controls. The effect of CXCR1/2 blockade on diabetic kidney disease was evaluated in db/db mice. Results IL-8 urinary levels were increased in patients with T2D and diabetic kidney disease, with the highest urinary IL-8 levels found in the patients with the largest decline in glomerular filtration rate, with an increased albumin/creatine ratio and the worst renal outcome. Moreover, glomerular IL-8 renal expression was increased in patients with T2D, as compared to controls. High glucose elicits abundant IL-8 secretion in cultured human immortalized podocytes in vitro. Finally, in diabetic db/db mice and in podocytes in vitro, CXCR1/2 blockade mitigated albuminuria, reduced mesangial expansion, decreased podocyte apoptosis and reduced DNA damage. Conclusions/interpretation The IL-8- CXCR1/2 axis may have a role in diabetic kidney disease by inducing podocyte damage. Indeed, targeting the IL-8-CXCR1/2 axis may reduce the burden of diabetic kidney disease.

[EN] The abietane-type diterpenoids are significant bioactive compounds exhibiting a varied range of pharmacological properties. In this study, the first synthesis and biological investigation of the new abietane-diterpenoid (+)-4-epi-liquiditerpenoid acid (8a) together with several of its analogs are reported. The compounds were generated from the readily available methyl callitrisate (7), which was obtained from callitrisic acid present in Moroccan Sandarac resin. A biological evaluation was conducted to determine the effects of the different functional groups present in these molecules, providing basic structure-activity relationship (SAR) elements. In particular, the ferruginol and sugiol analogs compounds 10-16 were characterized by the presence of a phenol moiety, higher oxidization states at C-7 (ketone), and the hydroxyl, methyl ester or free carboxylic acid at C19. The biological profiling of these compounds was investigated against a panel of six human solid tumor cell lines (HBL-100, A549, HeLa, T-47D, SW1573 and WiDr), four parasitic Leishmania species (L. donovani, L. infantum, L. guyanensis and L. amazonensis) and two malaria strains (3D7 and K1). Furthermore, the capacity of the compounds to modulate gamma-aminobutyric acid type A (GABA(A)) receptors (alpha(1)beta(2)gamma(2s)) is also described. A comparison of the biological results with those previously reported of the corresponding C18-functionalized analogs was conducted., This research was funded by Spanish National Research Council: 201680I008; Austrian Science Fund: FWF W 1232; American Lebanese Syrian Associated Charities. Santander Bank. Spanish Ministry of Science: PGC2018-094503-B-C22 and "The APC was funded by MDPI".

International audience; This paper deals with the preparation and the characterization of four new ionic liquids resulting from the pairing of various polyoxotungstates or polyoxomolybdates with the cation trihexyltetradecylphosphonium. The physical properties measured by different techniques evidence that the viscosity and the rheological behaviors of such POM-based ionic liquids, POM-ILs, strongly depend on the nature of the POM, especially its charge. Playing on the nature of the POM, we can indeed obtain Newtonian liquids or some much more viscous materials exhibiting characteristics of resins or pseudo-plastics. In a second part of this study, the potentialities of using such materials both as solvent and catalyst for the oxidation of a series of alcohols are presented as proof of concept. This part highlights great differences in strength and selectivity as a function of the POM-IL used. Furthermore, a very simple way to recycle the catalyst is also presented.

Hydrogen delivered at hydrogen refuelling station must be compliant with requirements stated in different standards which require specialized sampling device and personnel to operate it. Currently, different strategies are implemented in different parts of the world and these strategies have already been used to perform 100s of hydrogen fuel sampling in USA, EU and Japan. However, these strategies have never been compared on a large systematic study. The purpose of this paper is to describe and compare the different strategies for sampling hydrogen at the nozzle and summarize the key aspects of all the existing hydrogen fuel sampling including discussion on material compatibility with the impurities that must be assessed. This review highlights the fact it is currently difficult to evaluate the impact or the difference these strategies would have on the hydrogen fuel quality assessment. Therefore, comparative sampling studies are required to evaluate the equivalence between the different sampling strategies. This is the first step to support the standardization of hydrogen fuel sampling and to identify future research and development area for hydrogen fuel sampling.

Despite much progress in improving graft outcome during cardiac transplantation, chronic allograft vasculopathy (CAV) remains an impediment to long‐term graft survival. MicroRNAs (miRNAs) emerged as regulators of the immune response. Here, we aimed to examine the miRNA network involved in CAV. miRNA profiling of heart samples obtained from a murine model of CAV and from cardiac‐transplanted patients with CAV demonstrated that miR‐21 was most significantly expressed and was primarily localized to macrophages. Interestingly, macrophage depletion with clodronate did not significantly prolong allograft survival in mice, while conditional deletion of miR‐21 in macrophages or the use of a specific miR‐21 antagomir resulted in indefinite cardiac allograft survival and abrogated CAV. The immunophenotype, secretome, ability to phagocytose, migration, and antigen presentation of macrophages were unaffected by miR‐21 targeting, while macrophage metabolism was reprogrammed, with a shift toward oxidative phosphorylation in naïve macrophages and with an inhibition of glycolysis in pro‐inflammatory macrophages. The aforementioned effects resulted in an increase in M2‐like macrophages, which could be reverted by the addition of L‐arginine. RNA‐seq analysis confirmed alterations in arginase‐associated pathways associated with miR‐21 antagonism. In conclusion, miR‐21 is overexpressed in murine and human CAV, and its targeting delays CAV onset by reprogramming macrophages metabolism., The authors show that, after heart transplantation, microRNA‐21 is overexpressed in chronic allograft vasculopathy (CAV), that pharmacological and genetic modulation of microRNA‐21 mitigated CAV, and that microRNA‐21 antagonism abrogated CAV by reprogramming macrophage metabolism.

All over the world, societies are facing rapidly aging populations combined with a growing number of patients suffering from Alzheimer’s disease (AD). One focus in pharmaceutical research to address this issue is on the reduction of the longer amyloid-β (Aβ) fragments in the brain by modulation of γ-secretase, a membrane-bound protease. R-Flurbiprofen (tarenflurbil) was studied in this regard but failed to show significant improvement in AD patients in a phase 3 clinical trial. This was mainly attributed to its low ability to cross the blood–brain barrier (BBB). Here, we present the synthesis and in vitro evaluation of a racemic meta-carborane analogue of flurbiprofen. By introducing the carborane moiety, the hydrophobicity could be shifted into a more favourable range for the penetration of the blood–brain barrier, evident by a logD7.4 value of 2.0. Furthermore, our analogue retained γ-secretase modulator activity in comparison to racemic flurbiprofen in a cell-based assay. These findings demonstrate the potential of carboranes as phenyl mimetics also in AD research.

A dramatic rise in the prevalence of nonalcoholic fatty liver (NAFL) has been observed over the last few decades and it is now considered to be the most common liver disorder worldwide [1]. NAFL is characterized by excessive fat accumulation in the liver that is not associated with high alcohol consumption and NAFL can progress to more severe stages of liver disease. Importantly, even if no further progression of liver disease occurs, NAFL per se is also very strongly associated with metabolic diseases such as cardiovascular disease and type II diabetes [2–4]. Excessive fat accumulation in the liver is thought to be the result of an imbalance between lipid storage (due to increased delivery and synthesis), and disposal (Fig. ​(Fig.1).1). It is now well established that fat that is stored in the liver (in hepatocytes) originates from three main sources: first, direct fat storage from a meal; second, de novo synthesis of fatty acids (FAs) from glucose, fructose or amino acids (de novo lipogenesis; DNL); third, from uptake of plasma non-esterified FAs (NEFA) mainly derived from adipose tissue lipolysis (Fig. ​(Fig.1).1). Knowledge on the contribution of each of these pathways to liver fat content in humans is sparse [5,6], in part because appropriate techniques are lacking. Gaining a better understanding of the mechanisms, which contribute to hepatic fat accumulation is crucial to the development of effective treatment strategies for NAFL and its associated metabolic disturbances. Here, we discuss the techniques available to study storage pathways contributing to NAFL and review recent nutritional studies using these techniques to investigate whether these pathways can be modulated by diet. Open in a separate window FIGURE 1 Overview of liver fat storage and disposal pathways. Storage pathways include direct fat storage from a meal, de novo lipogenesis from carbohydrates and adipose tissue derived non-esterified fatty acid uptake. Liver lipid disposal pathways are mitochondrial fatty acid oxidation and ketogenesis after initial s-oxidation (acetyl-CoA disposal), and triglyceride incorporation into VLDL-particles to be secreted into the circulation.

The reactions between Tretinoin (Tret) and Isotretinoin (Itret) isomers with Iodine were thoroughly investigated under different conditions and solid products under proper conditions were prepared. Separation and identification of the formed products approved the stoichiometry (1:1). These newly prepared solid products were separated, washed, crystallized and structurally investigated and identified. Structures of the newly synthesized retinoid-iodine derivative products were carefully investigated in this research. Their structures were characterized, elucidated and analyzed by using the mass spectrometry (MS), Fourier Transform Infra-Red (FT-IR), 1H-NMR, thermal analyses (TA) and X- Ray Fluorescence (XRF). Then the results of the newly prepared compounds were compared with that of parent isomers analyses. Therefore; the proposed general formulae of the newly prepared compounds were found to be C20H27IO2. The biological activities of the newly obtained products in comparison with the parent isomers are thoroughly investigated against different kinds of bacteria and fungi.

In this paper, we explore the far-field radiative thermal rectification potential of common materials such as metals,ceramics and doped semi-conductors using radiative and thermo-radiative properties extracted from literature. Seventeen different materials are considered. The rectification coefficient is then calculated for 136 pairs of materials; each pair can be used for the two terminals of a radiative thermal diode. A thermal bias of 200 K is considered. The choice of materials and thermal bias value are only bound by data availability in literature. Obtained results, highlight new candidate materials for far-field radiative thermal rectification. They also highlight materials where thermal rectification is not negligible and should be considered with care in heat transfer calculations when considering systems subject to a comparable thermal bias and where these materials are used. Among the materials studied, undoped Indium Arsenide (InAs) shows great promise to be employed for thermal rectification, with a thermal rectification ratio reaching 96.35% in combination with other materials. Obtained results pave the way for an optimized design of thermal radiation control and management devices such as thermal diodes.