Supported-amine-catalyzed cascade synthesis of spiro-thiazolone-tetrahydrothiophenes: assessing HSA binding activity.

We have devised a supported-amine-catalyzed efficient synthesis of spiro-thiazolone-tetrahydrothiophenes via a sulfa-Michael/aldol cascade approach. The catalyst demonstrated sustained efficacy over 21 cycles. These derivatives were found to exhibit excellent binding abilities with purified human serum albumin as indicated by both in silico and in vitro-based experiments.

Promising ferroelectric and piezoelectric response of Cr-doped ZnO nanofiller-incorporated PVDF flexible and laminated nanocomposite system.

Cr3+-doped ZnO (CZ) nanoparticles are prepared using hydrothermal and co-precipitation techniques. The desired crystallographic phase of the nanoparticles is confirmed using X-ray diffraction study. Rod-shaped and spherical morphologies of CZ nanoparticles prepared using hydrothermal and co-precipitation techniques were confirmed through FESEM observation. Each type of nanoparticle was taken separately in PVDF to understand the characteristic properties, such as dielectric, piezoelectric, and ferroelectric properties of the resultant CZ-PVDF nanocomposite films. All the nanocomposite films comprising rod-shaped or spherical CZ nanoparticles show butterfly loops with a low leakage current density of 10-5 A m-2 at a maximum electric field of 100 kV m-2 under J-E measurement. These findings suggest that the polarization property of CZ-PVDF nanocomposite films can be obtained at a high external electric field without causing electric breakdown in the samples. Dielectric permittivity as a function of temperature increases with an increase in the loading percentage of both rod-shaped or spherical CZ nanofillers in PVDF. Polarization response also improves with an increase in the loading percentage of CZ nanofillers in PVDF. In particular, the rod-shaped CZ nanofillers in PVDF with a higher loading percentage (CZHP2) result in a maximum polarization of (10 ± 0.29) × 10-4 µC cm-2, remanent polarization of (2 ± 0.04) × 10-4 µC cm-2, and coercive field of (10 ± 0.1) kV cm-1 at a maximum electric field of 50 kV cm-1. The CZHP2 nanocomposite film has a piezoelectric coefficient (d33) of (25 ± 0.24) pC N-1 and a power density of 1278.90 W m-3. These results indicate that the nanocomposite films have potential application in piezoelectric energy harvesters, offering a possible solution to the energy issue faced by modern society.

Recyclable Polymer Supported DMAP Catalyzed Cascade Synthesis of α-Pyrones.

Polymer-supported catalysts have emerged as one of the sustainable and cost-effective alternatives in organic synthetic chemistry. We have developed the first polymer-supported DMAP catalyzed one-pot synthesis of diversely substituted α-pyrones. The cascade approach involves C5 conjugate addition of 5H-oxazol-4-ones to α,ß-unsaturated-ß-ketoesters followed by lactonization/elimination.

Chimeras in globally coupled oscillators: A review.

The surprising phenomenon of chimera in an ensemble of identical oscillators is no more strange behavior of network dynamics and reality. By this time, this symmetry breaking self-organized collective dynamics has been established in many networks, a ring of non-locally coupled oscillators, globally coupled networks, a three-dimensional network, and multi-layer networks. A variety of coupling and dynamical models in addition to the phase oscillators has been used for a successful observation of chimera patterns. Experimental verification has also been done using metronomes, pendula, chemical, and opto-electronic systems. The phenomenon has also been shown to appear in small networks, and hence, it is not size-dependent. We present here a brief review of the origin of chimera patterns restricting our discussions to networks of globally coupled identical oscillators only. The history of chimeras in globally coupled oscillators is older than what has been reported in nonlocally coupled phase oscillators much later. We elaborate the story of the origin of chimeras in globally coupled oscillators in a chronological order, within our limitations, and with brief descriptions of the significant contributions, including our personal experiences. We first introduce chimeras in non-locally coupled and other network configurations, in general, and then discuss about globally coupled networks in more detail.

The genus Simplicillium and Emericellopsis: A review of phytochemistry and pharmacology.

The demand for novel and improved medicine from biological sources to cater to the biopharmaceutical sector has increased significantly in recent years. Among the vast and miscellaneous microbial diversity, fungi provide a prolific source of structurally unique and biologically active secondary metabolites. Natural products obtained from fungi have reformed the era of biomedicine, providing effective drugs that have diverse healing potential. In this review, we focus on the isolation, chemical structure, and bioactivity of biomolecules that have been identified and studied for the first time. Further, we also explain in substantial detail that how the vast uninvestigated Emericellopsis and Simplicillium species may serve as a potential treasure trove of chemically diverse compounds.

Basin Transition and Alternative States: Role of Multi-species Herbivores-Induced Volatile in Plant-Insect Interactions.

A simple model on volatile organic compound (VOC)-mediated plant-insect interactions is proposed and examined here, when two different classes of herbivorous insects competing for a common resource (plant) in the presence of a specialist carnivorous enemy, which only predates one of the herbivore species. We, particularly, emphasize the impact of VOCs on plant's growth fitness. The system experiences several local and global bifurcations with emergent alternative states for variations in recruitment factors and predation rate. Basin transitions and basin of attractions have provided detail descriptions on the selectivity of the alternative states, when only one of the herbivore species can survive depending on the choice of initial population densities of the interacting species and how it provides a steady growth in plant. Additionally, our results support the concept of competitive exclusion principle in an indirect interspecific competition between the two herbivore types for the common resource, plant.

Effect of pH on the Hydrolytic Transformation of a New Mixture Formulation of Fomesafen and Quizalofop-ethyl in Water.

A hydrolytic transformation study was conducted in water of pH 4.0, 7.0 and 9.2 to evaluate the effect of pH on persistence of a new readymix formulation of fomesafen and quizalofop-ethyl. The water samples were fortified at 0.5 and 1 µg mL-1 levels and analysed at 0 (2 h), 1, 3, 7, 15, 30, 60, 90, 120, 150 days interval. Both the analytical methods were validated following SANTE guideline and found accurate based on average recovery of 80-100%, Relative standard deviation (RSD) < 20% and Coefficient of Determination (R2) 0.99. The dissipation of both the molecules was pH dependent and followed first order kinetics. Higher persistence of fomesafen was observed in alkaline pH as compared to neutral and acidic pH with half-life of 41.56-63.24 days, whereas higher stability of quizalofop-ethyl was observed in the water of acidic pH followed by neutral and alkaline pH with half-life of 1.26-8.09 days.

Treatment of tea industry wastewater using coagulation-spinning basket membrane ultrafiltration hybrid system.

The present study delivers the significant effects of the coagulation-spinning basket membrane ultrafiltration on the treatment of tea industry generated effluent. Response surface methodology (RSM) was applied to optimize the process parameters, namely, alum dosage (50-300 mg L-1), pH (4-10), stirring speed (10.47-62.83 rad s-1), and stirring time (30-180 min) during the pretreatment of effluent. Prior to final treatment, the spinning basket membrane filtration was performed to explore the permeate flux decline behavior at different parametric conditions such as, applied transmembrane pressure drop (TMP drop: 207-414 kPa), rotational speed (10.47, 31.41, 52.36 and 73.30 rad s-1) and membrane MWCOs (5-50 kDa). Artificial neural network (ANN) analysis helps to compare the theoretical flux decline behavior with the experimental data. Modified Hermia's models were used to identify the reversible and irreversible fouling as well as cake layer formation. The decrease of cake filtration model constant from 1.31 × 107 to 0.56 × 107 m-2 s indicates the minimization of concentration polarization by virtue of membrane basket rotational speed. The effects of various parameters on the permeate quality have also been verified. The maximum improvement of permeate clarity of 94.46% was observed when the membrane basket rotation was 52.36 rad s-1. With changing MWCO of 50 to 5 kDa, the removal of chemical oxygen demand has been increased from 87% to 96.70% at a rotation of 52.36 rad s-1.

Effect of pH on the Transformation of a New Readymix Formulation of the Herbicides Bispyribac Sodium and Metamifop in Water.

A laboratory experiment was conducted to investigate the effect of pH on the persistence and the dissipation of the new readymix formulation of bispyribac sodium and metamifop. The experiment was conducted in water of three different pH viz. 4.0, 7.0 and 9.2. The spiking level of both the compounds in water was 1.0 and 2.0 µg/mL. The residues were extracted by a simple, quick and reliable method and quantified by liquid chromatography tandem mass spectrometry (LC-MS/MS). The method was justified based on the recovery study, which was > 85%. The dissipation of both compounds followed first order kinetics. The half-life values ranged between 19.86-36.29 and 9.92-19.69 days for bispyribac sodium and metamifop, respectively. The pH of water has a prominent effect on degradation of both the compounds. The rate of dissipation of both the compounds was highest in water of acidic pH followed by neutral and alkaline pH.

A self-assembled clavanin A-coated amniotic membrane scaffold for the prevention of biofilm formation by ocular surface fungal pathogens.

Amniotic membrane (AM) is frequently used in ophthalmologic surgery for rapid ocular surface reconstruction. Sometimes it may create a major problem with associated infections after biofilm formation over the membrane. To overcome this problem, AM was coated with the antimicrobial peptide clavanin A. The antifungal activity of clavanin A in the native and self-assembled form was determined against the common ocular surface pathogens Candida albicans, Aspergillus fumigatus, Alternaria sp. and Fusarium sp. Biofilm formation over the coated surface was significantly reduced in comparison with the uncoated membrane. The coated membrane revealed effectiveness in terms of biocompatibility, cell attachment colonization when tested in non-cancerous 3T3 and human embryonic kidney (HEK)-293 cell lines. Clavanin A-coated AM also exhibited excellent physical, morphological and antifungal characteristics, indicating potential applicability for ocular surface infection control.

Multicluster oscillation death and chimeralike states in globally coupled Josephson Junctions.

We observe the multiclustered oscillation death and chimeralike states in an array of Josephson junctions under a combination of self-repulsive and cross-attractive mean-field interaction when each isolated junction is in a bistable state, a coexisting fixed point and an oscillatory state. We locate the parameter landscape of the multiclustered oscillation death and chimeralike states. Alternatively, a purely repulsive mean-field interaction in an array of all oscillatory junctions produces chimeralike states with signatures of metastability in the incoherent subpopulation of junctions.

Electrosynthesis of Highly Functionalized Quinolines through Radical Annulation-Polar Addition Cascade.

Synthesis of diversely functionalized quinoline-2-carboxylates is illustrated through electrochemical cross-dehydrogenative coupling between N-aryl glycinates and methylenecyclopropanes. An extensive range of distinct functionalities is well-compatible under these transition-metal- and oxidant-free mild electrochemical conditions, contributing to a broad substrate scope and practical applicability. Cyclic voltammetric measurements and control experiments suggested a formal [4 + 2] cycloaddition involving radical intermediates, followed by a cyclopropyl ring opening through nucleophilic polar addition, consecutively fabricating C-C and C-N bonds.

Kaajal fights against eye pathogens and is safe for eye make-up: a reinvestigation of an ancient practice.

The present report includes a scientific view of the traditional use of 'Kaajal' from the leaf of Euphorbia neriifolia, an Indian spurge tree locally called the 'Monosha' plant. A thorough analysis of the material demonstrates that it contains carbon nanoparticles having two uniform sizes of 2-3 nm and 35-45 nm. Further study revealed that Kaajal has antimicrobial properties against eye pathogens and is biocompatible for cosmetic use.

Candida fermentati: a rare yeast involved in fungal keratitis.

PURPOSE: The aim of this study was to report a rare case of fungal keratitis from Eastern India. METHODS: This is a case report. RESULTS: A 52-year-old man with a history of minor trauma presented with a total corneal ulcer and hypopyon in the left eye. Microbiologic examination of corneal scrapings showed yeast cells in direct smear and typical yeast colonies on multiple solid agar media. Identification of the organism isolated in the culture was performed using the D1/D2 region of the large subunit (LSU 28S rDNA)-based molecular technique. Polymerase chain reaction amplified a band with a sequence that was 100% homologous with that of Candida fermentati. The organism was susceptible to amphotericin B and anidulafungin and demonstrated resistance to voriconazole, itraconazole, and fluconazole. Therapeutic keratoplasty was performed, followed by the recurrence of the infection in the graft, which was controlled with topical and intracameral amphotericin B. At the end of 3 months, the affected eye had developed phthisis bulbi. CONCLUSIONS: This is the first report of isolation of C. fermentati, a species closely related to Candida guilliermondii, from keratitis. Molecular diagnostic techniques are helpful in the accurate identification of this organism, which is clinically important in view of an antifungal susceptibility pattern that differs from that of other yeasts and for selection of appropriate therapy.

Schizophyllum commune: a new organism in eye infection.

PURPOSE: We report a case of mycotic keratitis caused by a rare fungus Schizophyllum commune. METHODS: Clinical examination, slit-lamp examination, and microbiological evaluation of the corneal ulcer were done, and its treatment outcome was studied. The fungal etiology was established by conventional microbiological techniques, polymerase chain reaction and speciation by DNA sequencing. RESULTS: Corneal scraping showed the presence of fungal filaments. The fungus was identified as S. commune based on DNA sequence analysis of the internal transcribed spacer region. The organism was susceptible to amphotericin B and voriconazole and demonstrated resistance to anidulafungin, itraconazole, and fluconazole. Therapeutic keratoplasty was performed but there was recurrence of the infection in the graft, which was controlled with topical voriconazole and intracameral amphotericin B. At the end of 3 months, the affected eye had developed phthisis bulbi. CONCLUSION: The best of our knowledge, this is the first reported case of keratitis caused by the rare fungus S. commune. Management of these cases is difficult, and surgical procedures may be needed.

Structural-and-dynamical similarity predicts compensatory brain areas driving the post-lesion functional recovery mechanism.

The focal lesion alters the excitation-inhibition (E-I) balance and healthy functional connectivity patterns, which may recover over time. One possible mechanism for the brain to counter the insult is global reshaping functional connectivity alterations. However, the operational principles by which this can be achieved remain unknown. We propose a novel equivalence principle based on structural and dynamic similarity analysis to predict whether specific compensatory areas initiate lost E-I regulation after lesion. We hypothesize that similar structural areas (SSAs) and dynamically similar areas (DSAs) corresponding to a lesioned site are the crucial dynamical units to restore lost homeostatic balance within the surviving cortical brain regions. SSAs and DSAs are independent measures, one based on structural similarity properties measured by Jaccard Index and the other based on post-lesion recovery time. We unravel the relationship between SSA and DSA by simulating a whole brain mean field model deployed on top of a virtually lesioned structural connectome from human neuroimaging data to characterize global brain dynamics and functional connectivity at the level of individual subjects. Our results suggest that wiring proximity and similarity are the 2 major guiding principles of compensation-related utilization of hemisphere in the post-lesion functional connectivity re-organization process.

Contrarian role of phase and phase velocity coupling in synchrony of second-order phase oscillators.

Positive phase coupling plays an attractive role in inducing in-phase synchrony in an ensemble of phase oscillators. Positive coupling involving both amplitude and phase continues to be attractive, leading to complete synchrony in identical oscillators (limit cycle or chaotic) or phase coherence in oscillators with heterogeneity of parameters. In contrast, purely positive phase velocity coupling may originate a repulsive effect on pendulumlike oscillators (with rotational motion) to bring them into a state of diametrically opposite phases or a splay state. Negative phase velocity coupling is necessary to induce synchrony or coherence in the general sense. The contrarian roles of phase coupling and phase velocity coupling on the synchrony of networks of second-order phase oscillators have been explored here. We explain our proposition using networks of two model systems, a second-order phase oscillator representing the pendulum or the superconducting Josephson junction dynamics, and a voltage-controlled oscillations in neurons model. Numerical as well as semianalytical approaches are used to confirm our results.

Mediator-free electrochemical trifluoromethylation: a cascade approach for the synthesis of trifluoromethylated isoxazolines.

The developed methodology describes an environmentally benign protocol for electro-oxidative CF3-radical generation, followed by cascade cyclization fabricating an isoxazoline scaffold from a ß,γ-unsaturated oxime. Consecutive C-O and C-C bond formations were achieved through this method featuring mild, robust, and scalable reaction conditions and broad substrate scope. Mechanistic studies revealed the necessity of anodic oxidation for the cascade process. Further conversion of the isoxazoline afforded other valuable derivatives.

Nanoscale borosilicate bioactive glass for regenerative therapy of full-thickness skin defects in rabbit animal model.

Bioactive glass (BG) occupies a significant position in the field of hard and soft tissue regeneration. Different processing techniques and formulas have been introduced to expand their regenerative, angiogenic, and antibacterial properties. In the present study, a new formula of bborosilicate bioactive glass nanofibers was prepared and tested for its wound-healing efficacy in a rabbit animal model. The glass formula ((1-2) mol% of B2O3 (68-69) mol% of SiO2, and (29-30) mol% of CaO) was prepared primarily by the sol-gel technique followed by the electrospinning technique. The material was characterized for its ultrastructure using scanning electron microscopy, chemical composition using FTIR, and its dynamic in vitro biodegradability using ICP-AES. Twelve rabbits were subjected to surgical induction of full-thickness skin defects using a 1 cm2 custom-made stainlessteel skin punch. The bioactive glass nanofibers were used as a grafting material in 6 experimental rabbits, while the defects in the remaining rabbits were considered as the negative control samples. All defects were assessed clinically for the decrease in wound size and clinical signs of healing and histologically for angiogenesis, collagen density, inflammatory response, cell recruitment, epithelial lining, and appendages at 1,2 and 3 weeks following the intervention. Structural analysis of the glass fibers confirmed their nano-size which ranged from 150 to 700 nm. Moreover, the chemical analysis confirmed the presence of SiO2 and B2O3 groups within the structure of the nanofibers. Additionally, dynamic biodegradation analysis confirmed the rapid degradation of the material starting from the first 24 h and rapid leaching of calcium, silicon, and boron ions confirming its bioactivity. The wound healing study of the nanofibrous scaffold confirmed its ability to accelerate wound healing and the closure rate in healthy rabbits. Histological analysis of the defects confirmed the angiogenic, regenerative and antibacterial ability of the material throughout the study period. The results unveil the powerful therapeutic properties of the formed nanofibers and open a new gate for more experimental and clinical applications.

ROAD: The Road Event Awareness Dataset for Autonomous Driving.

Humans drive in a holistic fashion which entails, in particular, understanding dynamic road events and their evolution. Injecting these capabilities in autonomous vehicles can thus take situational awareness and decision making closer to human-level performance. To this purpose, we introduce the ROad event Awareness Dataset (ROAD) for Autonomous Driving, to our knowledge the first of its kind. ROAD is designed to test an autonomous vehicle's ability to detect road events, defined as triplets composed by an active agent, the action(s) it performs and the corresponding scene locations. ROAD comprises videos originally from the Oxford RobotCar Dataset, annotated with bounding boxes showing the location in the image plane of each road event. We benchmark various detection tasks, proposing as a baseline a new incremental algorithm for online road event awareness termed 3D-RetinaNet. We also report the performance on the ROAD tasks of Slowfast and YOLOv5 detectors, as well as that of the winners of the ICCV2021 ROAD challenge, which highlight the challenges faced by situation awareness in autonomous driving. ROAD is designed to allow scholars to investigate exciting tasks such as complex (road) activity detection, future event anticipation and continual learning. The dataset is available at https://github.com/gurkirt/road-dataset; the baseline can be found at https://github.com/gurkirt/3D-RetinaNet.