Step In Synthesis Research Articles

P‐d Orbital Hybridization in Ag‐based Electrocatalysts for Enhanced Nitrate‐to‐Ammonia Conversion

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate‐to‐ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p‐d orbital hybridization via doping p‐block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn‐doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5 ± 1.85 % for NH3 at ‐0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3 ± 14.1 mg h‐1 mgcat.‐1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere‐level current density of 1.1 A cm‐2 with an NH3 yield of 78.6 mg h‐1 cm‐2, during which NH3 can be further extracted to prepare struvite as high‐quality fertilizer. A mechanistic study reveals that a strong p‐d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate‐determining step for NH3 synthesis, which as a general principle, can be further extended to Bi‐ and In‐doped Ag catalysts. Moreover, when integrated into a Zn‐nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L‐1, high power density of 18.1 mW cm‐2, and continuous NH3 production.

Clinical and molecular study of patients with thyroid dyshormogenesis and variants in the thyroglobulin gene.

Defects in any thyroid hormone synthesis steps cause thyroid dyshormonogenesis (THD). THD due to thyroglobulin (TG) gene variants is a cause of congenital hypothyroidism (CH) with a wide clinical spectrum, ranging from mild to severe permanent hypothyroidism. We present high-throughput sequencing results of patients with TG variants. A CH high-throughput sequencing-panel of the main genes involved in the regulation of thyroid hormonogenesis was performed to identify those TG variants that may be related to patient THD phenotype. We identified 21 TG gene variants in 19 patients (11.8%) which could explain their phenotype. Ten of those (47.6%) were not previously described. CH was biochemically severe in these 19 patients. Eight of them were reevaluated after one month of discontinuing LT4 treatment and all had severe permanent hypothyroidism. We also identified another 16 patients who presented heterozygous TG variants, of whom, at reevaluation, five had mild permanent and only one had severe permanent hypothyroidisms. In this study, 10 novel and 11 previously reported variants in the TG gene have been identified that could explain the phenotype of 19 patients from non-consanguineous families from a large THD cohort. Although not all these TG gene variants can explain all the patients' THD phenotypes, some of them had severe or mild permanent hypothyroidism at reevaluation.

Noteworthy synthesis strategies and applications of metal-organic frameworks for the removal of emerging water pollutants from aqueous environment

17 global Sustainable Development Goals (SDGs) were established through the adoption of the 2030 Agenda for Sustainable Development by all United Nations members. Clean water and sanitation (SDG 6) and industry, innovation, and infrastructure (SDG 9) are the SDGs focus of this work. Of late, various new companies delivering metal-organic frameworks (MOFs) have blossomed and moved the field of adsorption utilizing MOFs to another stage. Inside this unique circumstance, this article aims to catch recent advancements in the field of MOFs and the utilizations of MOFs relate to the expulsion of arising contaminations that present huge difficulties to water quality because of their steadiness and possible damage to environments and human wellbeing. Customary water treatment techniques regularly neglect to eliminate these poisons, requiring the advancement of novel methodologies. This study overviews engineering techniques for controlling MOF characteristics for better flexibility, stability, and surface area. A current report on MOFs gathered new perspectives that are amicably discussed in emergent technologies and extreme applications towards environmental sectors. Various applications in many fields that exploit MOFs are being fostered, including gas storage, fluid separation, adsorbents, catalysis, medication delivery, and sensor utilizations. The surface area of a wide range of MOFs ranges from 103 to 104 m2/g, which exceeds the standard permeability of several material designs. MOFs with extremely durable porosity are more significant in their assortment and variety than other classes of porous materials. The work outlines the difficulties encountered in the synthesis steps and suggests ways to make use of MOFs' value in a variety of contexts. This caters to creating multivariate systems enclosed with numerous functionalities, leading to the synthesis of MOFs that offer a synergistic blend of in-built properties and exclusive applications. Additionally, the MOF-related future development opportunities and challenges are discussed.

Direct design of ground-state probabilistic logic using many-body interactions for probabilistic computing

In this work, an innovative design model aimed at enhancing the efficacy of ground-state probabilistic logic with a binary energy landscape (GSPL-BEL) is presented. This model enables the direct conversion of conventional CMOS-based logic circuits into corresponding probabilistic graphical representations based on a given truth table. Compared to the conventional approach of solving the configuration of Ising model-basic probabilistic gates through linear programming, our model directly provides configuration parameters with embedded many-body interactions. For larger-scale probabilistic logic circuits, the GSPL-BEL model can fully utilize the dimensions of many-body interactions, achieving minimal node overhead while ensuring the simplest binary energy landscape and circumventing additional logic synthesis steps. To validate its effectiveness, hardware implementations of probabilistic logic gates were conducted. Probabilistic bits were introduced as Ising cells, and cascaded conventional XNOR gates along with passive resistor networks were precisely designed to realize many-body interactions. HSPICE circuit simulation results demonstrate that the probabilistic logic circuits designed based on this model can successfully operate in free, forward, and reverse modes, exhibiting the simplest binary probability distributions. For a 2-bit × 2-bit integer factorizer involving many-body interactions, compared to the logic synthesis approach, the GSPL-BEL model significantly reduces the number of consumed nodes, the solution space (in the free-run mode), and the number of energy levels from 12, 4096, and 9–8, 256, and 2, respectively. Our findings demonstrate the significant potential of the GSPL-BEL model in optimizing the structure and performance of probabilistic logic circuits, offering a new robust tool for the design and implementation of future probabilistic computing systems.

Extended MOF-74-Type Variant with an Azine Linkage: Efficient Direct Air Capture and One-Pot Synthesis.

Direct air capture (DAC) shows considerable promise for the effective removal of CO2; however, materials applicable to DAC are lacking. Among metal-organic framework (MOF) adsorbents, diamine-Mg2(dobpdc) (dobpdc4- = 4,4-dioxidobiphenyl-3,3'-dicarboxylate) effectively removes low-pressure CO2, but the synthesis of the organic ligand requires high temperature, high pressure, and a toxic solvent. Besides, it is necessary to isolate the ligand for utilization in the synthesis of the framework. In this study, we synthesized a new variant of extended MOF-74-type frameworks, M2(hob) (M = Mg2+, Co2+, Ni2+, and Zn2+; hob4- = 5,5'-(hydrazine-1,2-diylidenebis(methanylylidene))bis(2-oxidobenzoate)), constructed from an azine-bonded organic ligand obtained through a facile condensation reaction at room temperature. Functionalization of Mg2(hob) with N-methylethylenediamine, N-ethylethylenediamine, and N,N'-dimethylethylenediamine (mmen) enables strong interactions with low-pressure CO2, resulting in top-tier adsorption capacities of 2.60, 2.49, and 2.91 mmol g-1 at 400 ppm of CO2, respectively. Under humid conditions, the CO2 capacity was higher than under dry conditions due to the presence of water molecules that aid in the formation of bicarbonate species. A composite material combining mmen-Mg2(hob) and polyvinylidene fluoride, a hydrophobic polymer, retained its excellent adsorption performance even after 7 days of exposure to 40% relative humidity. In addition, the one-pot synthesis of Mg2(hob) from a mixture of the corresponding monomers is achieved without separate ligand synthesis steps; thus, this framework is suitable for facile large-scale production. This work underscores that the newly synthesized Mg2(hob) and its composites demonstrate significant potential for DAC applications.

One step synthesis network supersaturation α phase through electron beam bombardment

Solid solution strengthening is a highly effective approach for enhancing the surface strength of Mg alloys. However, the realization of solid solution of Al in Mg remains a significant obstacle. Thus, a novel environmentally friendly technique for continuous electron beam bombardment is proposed to break through this bottleneck. The results revealed that a significant quantity of Al dissolved into the α-Mg phase, forming a reticulated supersaturated solid solution. Furthermore, the supersaturated α-Mg serves as an effective barrier and promotes notable microstructural refinement benefited from its enriched grain boundaries, contributing to a remarkable enhancement in their corrosion performance, an order of magnitude decrease. Additionally, AZ91D wear was reduced from 1.0 mg to 0.5 mg. Modified Mg alloy exhibited a noteworthy decrease of 50 % in wear when compared to its initial condition. This study provided insight into the development of efficient modification of Mg alloys by electron beam scanning.

Green-prepared high-performance electromagnetic wave absorption Ni6W6C/Co2O3@C composites and related broadband absorption device

In recent years, the synthesis of absorbing materials using green and environmentally friendly natural raw materials have become a research topic, but green and environmentally friendly materials with both high performance and simple synthesis steps still need to be developed. In this work, glucose and metal organic framework (MOF) were used to prepare composite materials with strong absorbing ability and low cost. We chose glucose, which is convenient to purchase on the market, as the raw material and constructed MOF derivatives with carbon shell skeleton nanostructures through a simple method of hydrothermal and annealing. Compared to the raw materials of traditional absorbing materials, glucose has environmentally friendly, low-cost and green characteristics. We characterized the microstructure and morphology of the material. In addition, we also analyzed the material composition and absorption mechanism of Ni6W6C/Co2O3@C. We have found from the theoretical analysis and simulation results of transmission lines that the minimum reflection loss (RLmin) value of Ni6W6C/Co2O3@C material at 5.43 GHz and 4.76 mm is −56.68 dB. And the effective absorption bandwidth (EAB) at 2.04 mm can reach 7.12 GHz. We load the best sample to the honeycomb structure, a broadband microwave absorber was designed for simulation. The results show that the broadband microwave absorber can achieve an average electromagnetic wave (EMW) loss of more than 99 % in the 0.3–16.04 GHz frequency band (RL value is less than −20 dB), and an average EMW loss of more than 90 % in the 16.04–18 GHz frequency band (RL value less than −10 dB). The composite structure of glucose and MOF derivatives enhances the dielectric loss of the material and enriches various EMW loss mechanisms. Finally, a green, environmental-friendly, high-performance absorbing material with a simple synthesis method is prepared. These results provide insights into the research on EMW absorption of composite materials and new methods for referring.

How to Manufacture a Drug API? A Simple Scheme from synthesis to analysis

Simply, production of a drug needs two main steps; the first step is the chemical synthesis, and the second one is the pharmaceutical analysis. At the first step, the desired drug must be synthesized via the lowest possible production cost. The synthesis scheme must be designed to proceed the reaction with the highest yield, cheapest solvents, and mildest possible conditions. It should also be user friendly (for operators of the production unit), as fast as possible, with lower steps leading to a highly pure active pharmaceutical ingredient (API). The pharmaceutical analysis step contains a series of the main analytical tests such as instrumental (HPLC, GC, XRD, and …), as well as physicochemical ones (like solubility, ash, heavy metals, …). These tests determine the quality of an API for being applied in the finish line formulation of a drug. In the present paper, we have simply described the two main steps for manufacturing a drug API which contains the synthesis step as well as the pharmaceutical analytical part. Also, some key notes for drug synthesis step will be presented.

Structural, Mössbauer and magnetic study of (Mn0.2Co0.2Ni0.2Cu0.2X0.2)Fe2O4 (X=Fe, Mg) spinel high-entropy oxides fabricated via reactive flash sintering

Herein, it is reported the concomitant synthesis and sintering in a single step of (Mn0.2Co0.2Ni0.2Cu0.2X0.2)Fe2O4 (X=Fe, Mg), a spinel-structured high-entropy oxides, by the reactive flash sintering technique. A single phase, identified with a spinel crystal structure Fd3̅m, was obtained in just 30 min at a furnace temperature of 1173 K. The structural and magnetic properties of the prepared compounds were assessed by the combined use of various techniques, aiming to understand the correlations between functional properties and crystal structure. Characteristic features of the Mössbauer spectra prove the existence of different nonequivalent Fe environments . Both compositions display soft magnetic behavior, characterized by low coercive fields and saturation magnetization reached at low fields. Thus, the substitution of nonmagnetic Mg2+ for magnetic Fe2+ results in a decrease in magnetic parameters due to the weakening of the super-exchange interaction among the magnetic moments.

Allosteric Effects of EF-G Domain I Mutations Inducing Ribosome Frameshifting Revealed by Multiplexed Force Spectroscopy.

Ribosome translocation catalyzed by elongation factor G (EF-G) is a critical step in protein synthesis where the ribosome typically moves along the mRNA by three nucleotides at each step. To investigate the mechanism of EF-G catalysis, it is essential to precisely resolve the ribosome motion at both ends of the mRNA, which, to our best knowledge, is only achieved with the magnetic-based force spectroscopy developed by our groups. Here, we introduce a novel multiplexed force spectroscopy technique that, for the first time, offers single-nucleotide resolution for multiple samples. This technique combines multiple acoustic force generators with the smallest atomic magnetometer designed for biological research. Utilizing this technique, we demonstrate that mutating EF-G at the GTP binding pocket results in the ribosome moving only two nucleotides on both ends of the mRNA, thereby compromising ribosome translocation. This finding suggests a direct link between GTP hydrolysis and ribosome translocation. Our results not only provide mechanistic insights into the role of GTP binding pocket but also illuminate how allosteric mutations can manipulate translocation. We anticipate broader applications of our technique in the ribosome field, leveraging its high efficiency and single-nucleotide resolution.

Synthesis and anticancer evaluation of new lupane triterpenoid derivatives containing various substituent at the 2 or 3 position

Betulonic acid benzyl ester 1 has been subjected to a series of structural modifications for the purpose of new triterpenoid synthesis and evaluating for anticancer activity. The one-pot two step synthesis of 2α-(aminomethyl)betulinic acid benzyl ester derivatives 3a–f (yield 46–69 %) was achieved by the Mannich reaction of compound 1 with methyleneiminium salts, generated in situ from N,N-disubstituted bis(amino)methanes 2a–f by the action of acetyl chloride in dichloromethane, and subsequent reduction of aminomethylation products with sodium borohydride. Minor 2β-(aminomethyl) triterpenoids 4c,d,f were also isolated (yield 6–15 %). We found, that the stereoselective reaction of triterpenoid 1 with acetylides, generated at –78 °C from alkynes in the presence of n-BuLi, has been useful and noteworthy as the key step in providing of new alkyne substituted triterpenoids – benzyl 3-alkynyl-3-deoxy-2(3),20(29)-lupadiene-28-oates or 3-deoxy-2(3)-dehydro-28-oxoallobetulin derivative. The new compounds were examined for anticancer activity against the human cell lines (MTT assay). All tested derivatives were non-toxic on human fibroblasts. The 3‐(phenylethynyl)lupa-2(3),20(29)-diene 9 showed selective cytotoxicity on cervical cancer cell lines. Tumor cells death trigged by the most active compound 4f resulted from apoptotic processes. These data make the series of synthesized 2 or 3 substituted lupane derivatives as promising compounds with anticancer potential.

One step synthesis of novel Cu3N/Cu2O/C3N4/Cu composite and their photocatalytic reduction activities

Copper nitride/cuprous oxide/carbon nitride/copper (Cu3N/Cu2O/C3N4/Cu) composite material was synthesized by one step thermal decomposition of copper-melamine complexes under N2 atmosphere. The as-synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS). The XRD analysis showed the mix phase of Cu3N, Cu2O, C3N4 and Cu. The photocatalytic activities of Cu3N/Cu2O/C3N4/Cu composite photocatalysts were evaluated by testing the photoreduction of chromium (VI) under UV–visible light irradiation. The results indicated that the synthesized samples are attractive photocatalysts for reduction of chromium (VI) under UV light irradiation. The photoreduction efficiencies of Cu3N/Cu2O/C3N4/Cu composite at 550 °C with TEOA induced by UV light within 120 min were 92.03 % caused by charge diffusion at the Cu3N/Cu2O/C3N4/Cu interface. The results indicated that the synthesized samples are attractive photocatalysts for reduction of chromium (VI) under UV light irradiation.

Correct Nucleotide Selection Is Confined at the Binding Site of Polymerase Enzymes.

DNA polymerases (Pols) add incoming nucleotides (deoxyribonucleoside triphosphate (dNTPs)) to growing DNA strands, a crucial step for DNA synthesis. The insertion of correct (vs incorrect) nucleotides relates to Pols' fidelity, which defines Pols' ability to faithfully replicate DNA strands in a template-dependent manner. We and others have demonstrated that reactant alignment and correct base pairing at the Pols catalytic site are crucial structural features to fidelity. Here, we first used equilibrium molecular simulations to demonstrate that the local dynamics at the protein-DNA interface in the proximity of the catalytic site is different when correct vs incorrect dNTPs are bound to polymerase β (Pol β). Formation and dynamic stability of specific interatomic interactions around the incoming nucleotide influence the overall binding site architecture. This explains why certain Pols' mutants can affect the local catalytic environment and influence the selection of correct vs incorrect nucleotides. In particular, this is here demonstrated by analyzing the interaction network formed by the residue R283, whose mutant R283A has an experimentally measured lower capacity of differentiating correct (G:dCTP) vs incorrect (G:dATP) base pairing in Pol β. We also used alchemical free-energy calculations to quantify the G:dCTP →G:dATP transformation in Pol β wild-type and mutant R283A. These results correlate well with the experimental trend, thus corroborating our mechanistic insights. Sequence and structural comparisons with other Pols from the same family suggest that these findings may also be valid in similar enzymes.

Upscaling and Risk Evaluation of the Synthesis of the 3,5-Diamino-1H-Pyrazole, Disperazol.

This paper presents the work performed to transition a lab-scale synthesis (1 g) to a large-scale (400 g) synthesis of the 3-5-diamino-1H-Pyrazole Disperazol, a new pharmaceutical for treatment of antibiotic-resistant Pseudomonas aeruginosa biofilm infections. The potentially hazardous diazotisation step in the lab-scale synthesis was transformed to a safe and easy-to-handle flow chemistry step. Additionally, the paper presents an OSHA-recommended safety assessment of active compound E, as performed by Fauske and Associates, LLC, Burr Ridge, IL, USA.

Update on heme biosynthesis, tissue-specific regulation, heme transport, relation to iron metabolism and cellular energy.

Heme is a primordial macrocycle upon which most aerobic life on Earth depends. It is essential to the survival and health of nearly all cells, functioning as a prosthetic group for oxygen-carrying proteins and enzymes involved in oxidation/reduction and electron transport reactions. Heme is essential for the function of numerous hemoproteins and has numerous other roles in the biochemistry of life. In mammals, heme is synthesised from glycine, succinyl-CoA, and ferrous iron in a series of eight steps. The first and normally rate-controlling step is catalysed by 5-aminolevulinate synthase (ALAS), which has two forms: ALAS1 is the housekeeping form with highly variable expression, depending upon the supply of the end-product heme, which acts to repress its activity; ALAS2 is the erythroid form, which is regulated chiefly by the adequacy of iron for erythroid haemoglobin synthesis. Abnormalities in the several enzymes of the heme synthetic pathway, most of which are inherited partial enzyme deficiencies, give rise to rare diseases called porphyrias. The existence and role of heme importers and exporters in mammals have been debated. Recent evidence established the presence of heme transporters. Such transporters are important for the transfer of heme from mitochondria, where the penultimate and ultimate steps of heme synthesis occur, and for the transfer of heme from cytoplasm to other cellular organelles. Several chaperones of heme and iron are known and important for cell health. Heme and iron, although promoters of oxidative stress and potentially toxic, are essential cofactors for cellular energy production and oxygenation.

Overexpression of oHIOMT results in various morphological, anatomical, physiological and molecular changes in switchgrass.

Melatonin (N-acetyl-5-methoxytryptamine) is a molecule implicated in multiple biological functions, but exerts contrasting effects on plants owing to concentration differences. Hydroxyindole O-methyltransferase (HIOMT), which catalyzes the last step of melatonin synthesis, plays a crucial role in this context. Transgenic switchgrass overexpressing oHIOMT with different melatonin levels displayed distinct morphological changes in a concentration-dependent manner. In this study, we divided the transgenic switchgrass into two groups: melatonin-moderate transgenic (MMT) plants and melatonin-rich transgenic (MRT) plants. To determine the concentration-dependent effect of melatonin on switchgrass growth and stress resistance, we conducted comparative morphological, physiological, omics and molecular analyses between MMT, MRT and wild-type (WT) plants. We found that oHIOMT overexpression, with moderate melatonin levels, was crucial in regulating switchgrass growth through changes in cell size rather than cell number. Moderate levels of melatonin were vital in regulating carbon fixation, stomatal development and chlorophyll metabolism. Regarding salt tolerance, melatonin with moderate levels activated numerous defense (e.g. morphological characteristics, anatomical structure, antioxidant enzymatic properties, non-enzymatic capacity and Na+/K+ homeostasis). Additionally, moderate levels of oHIOMT overexpression were sufficient to increase lignin content and alter monolignol compositions with an increase in the S/G lignin ratio. Taken together, oHIOMT overexpression in switchgrass with different melatonin levels resulted in morphological, anatomical, physiological and molecular changes in a concentration-dependent manner, which characterized by stimulation at low doses and inhibition at high doses. Our study presents new ideas and clues for further research on the mechanisms of the concentration-dependent effect of melatonin.

Human Gonads Do Not Contribute to the Circulating Pool of 11-Oxygenated Androgens.

Androstenedione (A4) and testosterone (T) are produced by both the adrenal glands and the gonads. The adrenal enzyme 11β-hydroxylase (CYP11B1) executes the final step in cortisol synthesis; CYP11B1 also uses A4 and T as substrates, generating 11-hydroxyandrostenedione and 11-hydroxytestosterone, respectively. It has been suggested that CYP11B1 is expressed in the gonads, yet the circulating levels of all 11-oxygenated androgens (11-oxyandrogens) are similar in males and females of reproductive ages, despite enormous differences in T. To assess the gonadal contribution to the circulating pool of 11-oxyandrogens. We used liquid chromatography-tandem mass spectrometry to measure 13 steroids, including traditional and 11-oxyandrogens in: (I) paired gonadal and peripheral vein blood samples obtained during gonadal venograms from 11 patients (7 women), median age 37 (range 31-51 years); and (II) 17 women, median age 57 (range 41-81 years) before and after bilateral salpingo-oophorectomy (BSO). We also compared CYP11B1, 17α-hydroxylase/17,20-lyase (CYP17A1), and 3β-hydroxysteroid dehydrogenase type 2 (HSD3B2) mRNA expression in adrenal, ovarian, and testicular tissue. A4, T, estradiol, estrone, progesterone, 17α- and 16α-hydroxyprogesterone were all higher in gonadal veins vs. periphery (p < 0.05 for all), while four 11-oxyandrogens were similar between matched gonadal and peripheral vein samples. Equally, in women who underwent BSO, A4 (median [interquartile range]: 59.7 [47.7-67.6] ng/dL vs. 32.7 [27.4-47.8] ng/dL, p < 0.001) and T (24.1 [16.4-32.3] vs.15.5 [13.7-19.0] ng/dL, p < 0.001) declined, while 11-oxyandrogens remained stable. Gonadal tissue displayed negligible CYP11B1 mRNA. Despite producing substantial amounts of A4 and T, human gonads are not relevant sources of 11-oxyandrogens.

An economic, accessible and stable sulphated cyclodextrin polymer as selector for efficiently separating chiral drugs in HPLC

In this study, sulfopropyl ether β-cyclodextrin polymer (SPE-β-CDP) with simple synthesis steps using cheap reagents was large-scalely prepared. Characterization results showed the average sulfonic group substitution in each β-CD molecule was about 7.261, and there were 195.87 μmol/g β-CD units in polymer. It was low viscosity and produced a little effect on column pressure. It was used as chiral selectors first time to add into mobile phase to separate 13 chiral drugs in HPLC. After investigation, results showed buffer pH, chiral additive concentration, organic phase proportion in mobile phase and flow rate could affect chiral separation. High separation ability of SPE-β-CDP was proved through baseline separation of 12 drugs which attributed to the homogeneity of SPE-β-CDP in sulfonic acid group substitution degree and position. The resolutions of salbutamol, bisoprolol, chlorpheniramine, propranolol and metoprolol could be even up to 7.47–19.02, which were significantly better than that of some references. Separations of 4 chiral drugs were even better than that of CE. Compared with monomer, SPE-β-CDP showed better chiral separation ability. SPE-β-CDP could be used in both of C8 and C18 columns. It was stable in batches and showed good recyclability and reusability. These provided a new strategy for chiral separation.

Experimental investigation of fracture mechanism in organically modified silica-based coating applied on austenitic stainless steel AISI 904L under monotonic and very high cycle fatigue loading

Surface morphology significantly influences the fatigue life of the metallic materials. Therefore, improving surface performance is important for economic and safety applications. Silica-based coatings are anticipated to protect the metallic materials under synergistic operating conditions, such as fatigue and corrosion. However, pure inorganic silica-based coatings are brittle and fail to protect metallic materials. The properties of the sol–gel coatings can be determined by optimizing synthesis factors, such as synthesis steps, precursors, solvents, and catalysts. Organically modified silica-based sol–gel coatings were synthesized using 3-glycidoxypropyl trimethoxysilane and 3-aminopropyltriethoxysilane as precursors, with ethanol as the solvent. The resulting coating was named EtOH. This coating was applied on the surface of stable austenitic stainless steel AISI 904L with the dip coating method. The fracture behavior of the coating during monotonic loading has been studied by interrupted tensile tests at different load steps and examined closely with scanning electron microscopy. On the other hand, very high cycle fatigue experiments were conducted using an ultrasonic fatigue testing system at load frequency of 20 kHz on coated specimens to investigate the fracture behavior of the coating during cyclic loading. Three different kinds of fracture due to stress relaxation in the coating and at its interface with substrate were observed in monotonic loading. The same kinds of stress relaxation were observed in cyclic loading with the difference being that the range of experienced elongation in cyclic tests was significantly smaller. Therefore, the fracture in cyclic loading were concentrated in the vicinity of macro crack. The application of organically modified coatings could suppress the persistent slip bands and result in increased fatigue life for coated specimens.

Total Synthesis and Bioactivity Profile of (+)-Ieodomycins A and B and their Stereoisomers.

Herein, we report the first- and second-generation syntheses of (+)-ieodomycins A and B and their stereoisomers via the late-stage elaboration of their conjugated E-diene side chains. Key steps for successful synthesis included Keck asymmetric allylation to introduce a hydroxyl group at the C5 position, consecutive Wipf's carboalumination modification, iodination, Sharpless asymmetric dihydroxylation, one-carbon homologation via cyanation, Mukaiyama lactonization, and Stille cross-coupling to form the conjugated E-diene moiety. Further, the preliminary in vitro bioactivity profile against various disease-related molecular targets and cell lines was investigated. Results indicated that compounds 30b and 30c, diastereoisomers of (+)-ieodomycin B (2), serve as α-glucosidase inhibitors, while compounds 30b and 30d inhibit the angiotensin-converting enzyme.