Recent advances of decatungstate photocatalyst in HAT process.

The decatungstate anion (W10O324-) appears to exhibit especially interesting properties as a photocatalyst. Because of its unique photocatalytic properties, it is now recognised as a promising tool in organic chemistry. This study examines recent advances in decatungstate chemistry, primarily concerned with synthetic and, to some degree, mechanistic challenges. In this short review we have selected to give a number of illustrative examples that demonstrate the various applications of decatungstate in the hydrogen atom transfer (HAT) process.

Metal-free visible light mediated direct C-H amination of benzoxazole with secondary amines.

An efficient visible light mediated, eosin Y catalyzed direct C-H oxidative amination of benzoxazoles with secondary amines has been developed, which providing a straightforward, green, and environmentally benign access to a wide variety of substituted benzoxazole-2-amines under mild reaction conditions. The biological studies such as drug-likeness and molecular docking are also carried out on the molecule.

Mammalian cargo receptors for endoplasmic reticulum-to-Golgi transport: mechanisms and interactions.

Proteins that are destined to enter the secretory pathway are synthesized on the rough endoplasmic reticulum (ER) and then translocated into the ER lumen, where they undergo posttranslational modifications, folding, and assembly. After passing a quality control system, the cargo proteins are packaged into coat protein complex II (COPII) vesicles to exit the ER. In metazoans, most COPII subunits have multiple paralogs, enabling COPII vesicles the flexibility to transport a diverse range of cargo. The cytoplasmic domains of transmembrane proteins can interact with SEC24 subunits of COPII to enter the ER exit sites. Some transmembrane proteins may also act as cargo receptors that bind soluble secretory proteins within the ER lumen, enabling them to enter COPII vesicles. The cytoplasmic domains of cargo receptors also contain coat protein complex I binding motifs that allow for their cycling back to the ER after unloading their cargo in the ER-Golgi intermediate compartment and cis-Golgi. Once unloaded, the soluble cargo proteins continue maturation through the Golgi before reaching their final destinations. This review provides an overview of receptor-mediated transport of secretory proteins from the ER to the Golgi, with a focus on the current understanding of two mammalian cargo receptors: the LMAN1-MCFD2 complex and SURF4, and their roles in human health and disease.

A systematic approach for COVID-19 predictions and parameter estimation.

The world is currently facing a pandemic called COVID-19 which has drastically changed our human lifestyle, affecting it badly. The lifestyle and the thought processes of every individual have changed with the current situation. This situation was unpredictable, and it contains a lot of uncertainties. In this paper, the authors have attempted to predict and analyze the disease along with its related issues to determine the maximum number of infected people, the speed of spread, and most importantly, its evaluation using a model-based parameter estimation method. In this research the Susceptible-Infectious-Recovered model with different conditions has been used for the analysis of COVID-19. The effects of lockdown, the light switch method, and parameter variations like contact ratio and reproduction number are also analyzed. The authors have attempted to study and predict the lockdown effect, particularly in India in terms of infected and recovered numbers, which show substantial improvement. A disease-free endemic stability analysis using Lyapunov and LaSalle's method is presented, and novel methods such as the convalescent plasma method and the Who Acquires Infection From Whom method are also discussed, as they are considered to be useful in flattening the curve of COVID-19.

Multiscale Approach to Studying Biomolecular Interactions in Cellulose-Casein Adhesion.

Casein finds application as an eco-friendly adhesive for paper, wood, glass, etc. Casein being a protein can undergo conformational and microstructural changes during various processing steps involved in interfacial bonding. This study aims at understanding the multiscale contributions of these changes in casein to its adhesion to cellulose pressboards. Investigations spanning from molecular structure to macroscopic adhesion characteristics have been used in this work. The lap shear strength of casein bonded cellulose pressboards is found to increase with the increase in casein concentration. It was observed from Fourier transform infrared spectroscopy (FTIR) investigations along with microscopy and rheological studies that casein dispersions result in more α-helical conformations during the preconcentration process of casein dispersions. This results in increased hydrophobicity of the casein particles/aggregates, which in turn affects the wetting characteristics and the adhesion behavior. Casein compositions lacking α-helices were found to enhance the bonding strength of casein with cellulose. The present study shows that the adhesion between casein and microporous cellulose substrate has contributions at the multiscale originating from the polar-polar interactions of casein and cellulose molecules, conformational changes in the protein structure of casein during drying, microstructure of casein particles in the dispersion, and the microporous nature of the cellulose boards. These interactions at multiple scales can be tuned to suit different adhesive applications using casein.

Recent advances in using 4DPAIPN in photocatalytic transformations.

1,3-Dicyano-2,4,5,6-tetrakis(diphenylamino)-benzene (4DPAIPN), with diphenylamino as an electron donor and dicyanobenzene as an electron acceptor, is a typical donor-acceptor fluorophore. Due to its excellent redox window, good chemical stability and broad applicability, this fluorophore has emerged as a powerful and attractive metal-free organophotocatalyst. This review has highlighted the design, synthesis and application of 4DPAIPN photoredox catalysts as well as their exceptionally broad range of redox properties. This flourishing class of organophotocatalysts is expected to contribute to a great extent toward the advancement of synthetic methodologies and its adaptation to a large scale inventive implementation due to their flexibility.

Novel Small Molecule Growth Inhibitors of Xanthomonas spp. Causing Bacterial Spot of Tomato.

Bacterial spot (BS) of tomato, caused by Xanthomonas gardneri, X. perforans, X. vesicatoria, and X. euvesicatoria, is difficult to control because of the high prevalence of copper- and streptomycin-resistant strains and the lack of resistance cultivars and effective bactericides. The objective of this study was to identify novel growth inhibitors of BS-causing Xanthomonas (BS-X) species by using small molecules (SM; n = 4,182). Several SMs (X1, X2, X5, X9, X12, and X16) completely inhibited the growth of BS-X isolates (n = 68 X. gardneri, 55 X. perforans, 4 X. vesicatoria, and 32 X. euvesicatoria) at ≥12.5 µM by disrupting Xanthomonas cell integrity through weakening of the cell membrane and formation of pores. These SMs were also effective against biofilm-embedded, copper- and streptomycin-resistant Xanthomonas strains while having minimal impact on other plant pathogenic (n = 20) and beneficial bacteria (n = 12). Furthermore, these SMs displayed equivalent antimicrobial activity against BS-X in seeds and X. gardneri in seedlings compared with conventional control methods (copper sulfate and streptomycin) at similar concentrations while having no detectable toxicity to tomato tissues. SMs X2, X5, and X12 reduced X. gardneri, X. perforans, X. vesicatoria, and X. euvesicatoria populations in artificially infested seeds ≤3.4-log CFU/seed 1 day postinfection (dpi) compared with the infested untreated control (P ≤ 0.05). SMs X1, X2, X5, and X12 reduced disease severity ≤72% and engineered bioluminescent X. gardneri populations ≤3.0-log CFU/plant in infected seedlings at 7 dpi compared with the infected untreated control (P ≤ 0.05). Additional studies are needed to increase the applicability of these SMs for BS management in tomato production.

Contributions from microstructural changes to the rheological behavior of casein dispersions during drying.

In several applications, a protein such as casein in dispersion form undergoes multiple processing steps including drying. In this work, the rheological and microstructural features of casein dispersions concentrated by evaporation of the solvent (drying dispersions) were studied in comparison with those of equal concentrations of the as-prepared dispersions without drying. The molecular assembly of casein is affected by drying along with the conformational composition changes in the secondary structures such as α-helix, ß-sheets, turns and random structures of the protein. Modeling of the rheological data indicates that these changes also affect the packing of casein molecular assemblies and these molecular assemblies in alkaline dispersions can behave as soft deformable particles. During drying, casein dispersions show prominent shear thinning for concentrations higher than 20 wt% along with the prevalence of α-helices and ß-sheets. In comparison, the as-prepared dispersions show different microstructural features, and therefore different rheological responses. A detailed analysis shows that alkalinity changes during drying is the crucial factor controlling the microstructural changes of the soft casein particles and hence the rheology.

Automated full-field polarization-sensitive optical coherence tomography diagnostic systems for breast cancer.

Intraoperative delineation of breast cancer is a major challenge. An effective breast tissue screening technique may reduce the risk of re-excision during surgery by specifically identifying positive margins. In this study, a high-resolution automated full-field polarization-sensitive optical coherence tomography (FF-PS-OCT) system was developed to classify healthy and malignant human breast tissue from quantitative phase retardation information of the tissues in ex vivo. Twelve breast tissue samples [four healthy, eight malignant (cancerous)] were imaged with the FF-PS-OCT system and the different phase features were extracted from the acquired OCT images (106), based on the differences in the optical signatures of the healthy and malignant tissues. A linear support vector model classifier was trained using 75 images, with a sensitivity of 92.10% and specificity of 89.18% was achieved. Thirty-one images were used to test the model, with a sensitivity of 90.90% and specificity of 85.0% achieved.

Enhanced production of recombinant serratiopeptidase in Escherichia coli and its characterization as a potential biosimilar to native biotherapeutic counterpart.

BACKGROUND: Serratia marcescens, a Gram-negative nosocomial pathogen secretes a 50 kDa multi-domain zinc metalloprotease called serratiopeptidase. Broad substrate specificity of serratiopeptidase makes it suitable for detergent and food processing industries The protein shows potent anti-inflammatory, anti-edemic, analgesic, antibiofilm activity and sold as an individual or fixed-dose enteric-coated tablets combined with other drugs. Although controversial, serratiopeptidase as drug is used in the treatment of chronic sinusitis, carpal tunnel syndrome, sprains, torn ligaments, and postoperative inflammation. Since the native producer of serratiopeptidase is a pathogenic microorganism, the current production methods need to be replaced by alternative approaches. Heterologous expression of serratiopeptidase in E. coli was tried before but not found suitable due to the limited yield, and other expression related issues due to its inherent proteolytic activity such as cytotoxicity, cell death, no expression, minimal expression, or inactive protein accumulation. RESULTS: Recombinant expression of mature form serratiopeptidase in E. coli seems toxic and resulted in the failure of transformation and other expression related issues. Although E. coli C43(DE3) cells, express protein correctly, the yield was compromised severely. Optimization of protein expression process parameters such as nutrient composition, induction point, inducer concentration, post-induction duration, etc., caused significant enhancement in serratiopeptidase production (57.9 ± 0.73% of total cellular protein). Expressed protein formed insoluble, enzymatically inactive inclusion bodies, and gave 40-45 mg/l homogenous (> 98% purity) biologically active and conformationally similar serratiopeptidase to the commercial counterpart upon refolding and purification. CONCLUSION: Expression of mature serratiopeptidase in E. coli C43(DE3) cells eliminated the protein expression associated with toxicity issues. Further optimization of process parameters significantly enhanced the overexpression of protein resulting in the higher yield of pure and functionally active recombinant serratiopeptidase. The biological activity and conformational features of recombinant serratiopeptidase were very similar to the commercially available counterpart suggesting it-a potential biosimilar of therapeutic and industrial relevance.

Volumetric analysis of breast cancer tissues using machine learning and swept-source optical coherence tomography.

In breast cancer, 20%-30% of cases require a second surgery because of incomplete excision of malignant tissues. Therefore, to avoid the risk of recurrence, accurate detection of the cancer margin by the clinician or surgeons needs some assistance. In this paper, an automated volumetric analysis of normal and breast cancer tissue is done by a machine learning algorithm to separate them into two classes. The proposed method is based on a support-vector-machine-based classifier by dissociating 10 features extracted from the A-line, texture, and phase map by the swept-source optical coherence tomographic intensity and phase images. A set of 88 freshly excised breast tissue [44 normal and 44 cancers (invasive ductal carcinoma tissues)] samples from 22 patients was used in our study. The algorithm successfully classifies the cancerous tissue with sensitivity, specificity, and accuracy of 91.56%, 93.86%, and 92.71% respectively. The present computational technique is fast, simple, and sensitive, and extracts features from the whole volume of the tissue, which does not require any special tissue preparation nor an expert to analyze the breast cancer as required in histopathology. Diagnosis of breast cancer by extracting quantitative features from optical coherence tomographic images could be a potentially powerful method for cancer detection and would be a valuable tool for a fine-needle-guided biopsy.

Overview: Nucleation of clathrate hydrates.

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Simple Isocratic HPLC Method for Determination of Enantiomeric Impurity in Besifloxacin Hydrochloride.

Besifloxacin is a unique chiral broad-spectrum flouroquinolone used in the treatment of bacterial conjunctivitis. R-form of besifloxacin hydrochloride shows higher antibacterial activity as compared to the S-isomer. Therefore, it is necessary to establish chiral purity. To establish chiral purity a high-performance liquid chromatography (HPLC) method for determination of R-besifloxacin and S-besifloxacin (BES impurity A) was developed and validated for in-process quality control and stability studies. The analytical performance parameters such as linearity, precision, accuracy, specificity, limit of detection (LOD), and lower limit of quantification (LOQ) were determined according to International Council for Harmonization ICH Q2(R1) guidelines. HPLC separation was achieved on Chiralpak AD-H (250 x 4.6 mm, 5 µm) column using n-heptane: ethanol: ethylenediamine: acetic acid (800:200:0.5:0.5) (v/v/v/v) as the mobile phase in an isocratic elution. The eluents were monitored by UV/Visible detector at 290 nm. The resolution between S-isomer and besifloxacin hydrochloride was more than 2.0. Based on a signal-to-noise ratio of 3 and 10 the LOD of besifloxacin was 0.30 µg/mL, while the LOQ was 0.90 µg/mL. The calibration curves were linear in the range of 0.9-7.5 µg/mL. Precision of the method was established within the acceptable range. The method was suitable for the quality control enantiomeric impurity in besifloxacin hydrochloride. Chirality 28:628-632, 2016. © 2016 Wiley Periodicals, Inc.

Correction: Visible-light acridinium-based organophotoredox catalysis in late-stage synthetic applications.

[This corrects the article DOI: 10.1039/D3RA01364B.].

Calcium-induced structural transitions are central to the folding, function, and processing of serratiopeptidase zymogen into mature form.

Serratia marcescens is an emerging health-threatening, gram-negative opportunistic pathogen associated with a wide variety of localized and life-threatening systemic infections. One of the most crucial virulence factors produced by S. marcescens is serratiopeptidase, a 50.2-kDa repeats-in-toxin (RTX) family broad-specificity zinc metalloprotease. RTX family proteins are functionally diverse exoproteins of gram-negative bacteria that exhibit calcium-dependent structural dynamicity and are secreted through a common type-1 secretion system (T1SS) machinery. To evaluate the impact of various divalent ligands on the folding and maturation of serratiopeptidase zymogen, the protein was purified and a series of structural and functional investigations were undertaken. The results indicate that calcium binding to the C-terminal RTX domain acts as a folding switch, triggering a disordered-to-ordered transition in the enzyme's conformation. Further, the auto-processing of the 16-amino acid N-terminal pro-peptide results in the maturation of the enzyme. The binding of calcium ions to serratiopeptidase causes a highly cooperative conformational transition in its structure, which is essential for the enzyme's activation and maturation. This conformational change is accompanied by an increase in solubility and enzymatic activity. For efficient secretion and to minimize intracellular toxicity, the enzyme needs to be in an unfolded extended form. The calcium-rich extracellular environment favors the folding and processing of zymogen into mature serratiopeptidase, i.e., the holo-form required by S. marcescens to establish infections and survive in different environmental niches.

Novel applications of photobiocatalysts in chemical transformations.

Photocatalysis has proven to be an effective approach for the production of reactive intermediates under moderate reaction conditions. The possibility for the green synthesis of high-value compounds using the synergy of photocatalysis and biocatalysis, benefiting from the selectivity of enzymes and the reactivity of photocatalysts, has drawn growing interest. Mechanistic investigations, substrate analyses, and photobiocatalytic chemical transformations will all be incorporated in this review. We seek to shed light on upcoming synthetic opportunities in the field by precisely describing mechanistically unique techniques in photobiocatalytic chemistry.

Light-driven photocatalysis as an effective tool for degradation of antibiotics.

Antibiotic contamination has become a severe issue and a dangerous concern to the environment because of large release of antibiotic effluent into terrestrial and aquatic ecosystems. To try and solve these issues, a plethora of research on antibiotic withdrawal has been carried out. Recently photocatalysis has received tremendous attention due to its ability to remove antibiotics from aqueous solutions in a cost-effective and environmentally friendly manner with few drawbacks compared to traditional photocatalysts. Considerable attention has been focused on developing advanced visible light-driven photocatalysts in order to address these problems. This review provides an overview of recent developments in the field of photocatalytic degradation of antibiotics, including the doping of metals and non-metals into ultraviolet light-driven photocatalysts, the formation of new semiconductor photocatalysts, the advancement of heterojunction photocatalysts, and the building of surface plasmon resonance-enhanced photocatalytic systems.

Development of an intelligent full-field polarization sensitive optical coherence tomography for breast cancer classification.

Biopsy is the gold standard for cancer detection, however the surge in breast cancer cases has made manual haematoxylin and eosin stained histopathological image examination difficult. Automatic cancer diagnosis is vital for a healthy life. It allows fast diagnosis without specific skills. This research proposes an intelligent full-field polarization-sensitive optical coherence tomography (FF-PS-OCT) system for ex-vivo breast classification using ensemble model corroborated by technique for order preference by similarity to ideal solution (TOPSIS). 220 samples image were scanned using the FF-PS-OCT to extract the phase information. The multilevel ensemble classifier has 94.8% precision, 92.5% recall, 93.7% F-score and 82.3% Mathews correlation coefficient on the testing dataset. The developed ensemble model corroborated by TOPSIS, outperforms the single model in terms of performance metrics. The initial results indicate that the rapid, non-contact and label-free FF-PS-OCT imaging modality using birefringent information is beneficial for making interventional decisions by clinicians.

Visible-light acridinium-based organophotoredox catalysis in late-stage synthetic applications.

The field of photoredox catalysis has been transformed by the use of organic photocatalysts, which give access to re-activities that were previously only possible with transition-metal photocatalysts. Recent advancements in the use of an acridinium photocatalyst in organic synthesis are covered in this review. Both the late-stage functionalization of biorelevant molecules and the activation of inert chemical bonds are explored, with an emphasis on their mechanistic features.

Recent advances in visible-light graphitic carbon nitride (g-C3N4) photocatalysts for chemical transformations.

Graphitic carbon nitride (g-C3N4) has emerged as a new research hotspot, attracting broad interdisciplinary attention in the form of metal-free and visible-light-responsive photocatalysts in the field of solar energy conversion and environmental remediation. These photocatalysts have evolved as attractive candidates due to their non-toxicity, chemical stability, efficient light absorption capacity in the visible and near-infrared regions, and adaptability as a platform for the fabrication of hybrid materials. This review mainly describes the latest advances in g-C3N4 photocatalysts for chemical transformations. In addition, the typical applications of g-C3N4-based photocatalysts involving organic transformation reactions are discussed (synthesis of heterocycles, hydrosulfonylation, hydration, oxygenation, arylation, coupling reactions, etc.).