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The prediction of yearly rain attenuation statistics at Q-band is made from Ka-band measurement for a temperate location, Vigo, Spain, using different frequency scaling models. The validity of the different frequency scaling models is tested for the present location by graphical comparison between measurement and prediction and also in terms of mean, standard deviation, and root mean square errors (RMSE). The Battesti model performs better compared to other existing frequency scaling models, RMSE is only 4.16% and 5.52% for the periods July 2016 to June 2017 and July 2017 to June 2018 respectively. The proposed new power law model increases the accuracy of the prediction for which the RMSE error is 1.09% and 2.17% less compared to the Battesti model for the periods July 2016 to June 2017 and July 2017 to June 2018, respectively. In predicting monthly statistics, the proposed model performs better compared to the Battesti model for all the months except December, January, and February. While predicting monthly statistics, for the proposed model, the maximum and minimum prediction errors are 18.50% and 0.39%, respectively. For the prediction of diurnal statistics, the proposed model performs better compared to the Battesti model with a very small prediction error, less than 4% for both days. The present study can be useful in the design and planning of satellite communication links in present or similar climatic regions for estimating rain attenuation at Q band or above, for which the experimental setup's cost is very high and requires a large receiver margin.

We develop a rapid and mild protocol to access sulfonimidoyl fluoride-[S(VI)] from sulfenamide-[S(II)] directly. The transformation occurs via the reaction of sulfenamide with NCS (N-chlorosuccinimide), water, and TBAF in acetonitrile. Water and TBAF act as the source for S═O bond formation and fluoride, respectively. The reaction takes a very short time (within 5 min). The drug molecules, such as Carbamazepine and Levetiracetam attached sulfonimidoyl fluorides are also achieved following this protocol. Furthermore, sulfonimidoyl fluoride is transformed into sulfonimidamide in the presence of AlCl3. To the best of our knowledge, it is the first report detailing the synthesis of sulfonimidoyl fluoride-[S(VI)] directly from S(II)-sulfenamide.

There is a growing demand for gas sensors with excellent efficiency, high flexibility, and low energy consumption due to the rapid development of smart electronic devices. Metal-oxide–semiconductor (MOS) nanostructures have been the preferred choice for advanced gas sensors over the last 30 years. However, MOS sensors suffer from drawbacks, such as low selectivity, high operating temperatures, high power consumption, and stability issues. To find the alternative way, this work focuses on the modeling and simulation of a low power gas sensor based on Au-loaded WS2/SnO2 heterostructure using the COMSOL Multiphysics platform. Under optimized conditions, the Au-loaded WS2/SnO2 heterostructure can detect carbon monoxide (CO) with high sensitivity even at a low concentration of 25 parts per billion (ppb) at room temperature (RT). Moreover, the sensor shows a wide detection range of 25 ppb–150 parts per million (ppm) under exposure of CO. The Au-loaded WS2/SnO2 heterostructure also exhibited high selectivity toward CO against a variety of interference gases, including methane (CH4), nitrogen dioxide (NO2), benzene (C6H6), sulfur dioxide (SO2), hydrogen sulfide (H2S), carbon dioxide (CO2), and ethanol (C2H6O). The obtained sensing performance can be attributed to the charge transfer mechanism in the WS2/SnO2 heterostructure along with the catalytic effect of Au. Thus, this research could be useful to fabricate real gas sensors for practical applications.

The LV AC microgrid, having DERs with BESS and Solar PV, generally suffers from power fluctuation. Moreover, the nonlinear and unbalanced loads cause undesirable negative sequence and harmonic currents, which disturb the power-sharing and voltage quality. These perturbations are adverse for both systems, i.e., grid-connected and islanded AC microgrids. Hence, the proposed inverter control scheme introduces a dual-mode, solo control system to reconfigure itself into voltage control or current control mode suitable for islanded or grid-connected operations. An adaptive virtual impedance-based advanced angle droop control is introduced to voltage-controlled inverters that consider the coupling between active and reactive power and source side power perturbation. Such a controller minimizes power-sharing error with quick power settling among DERs under various power dynamic conditions. However, an adaptive voltage compensator for current control inverters is introduced to minimize the voltage imbalance and harmonics within the permissible range. The proposed decentralized scheme brings adaptivity with unconstrained optimization-based selection criteria for virtual impedance and voltage function coefficients. In addition, it follows the eigenvalue concept for stability analysis of the inverter control system and selection of droop coefficients. The simulation is tested on a CIGRE LV testbed and experimentally validated on a single bus system.

In this work, we present a physical understanding and a robust surface potential coupling relationship essential to accurately capture the transconductance in body-contacted (BC) dynamically depleted silicon-on-insulator (DDSOI) MOSFETs for varied body biases. It is observed that the crossover of transconductance for varied body biases occurs before the peak transconductance is reached for devices operating particularly in the saturation region. This phenomenon is investigated in detail and attributed to partial-depletion-to-full-depletion transition in the silicon body that occurs before the peak transconductance is reached, in the saturation region of operation. The proposed coupling relationship effectively captures this behavior, ensuring symmetry of the overall model around ${V}_{\text {ds}} = 0$ V and correct harmonic characteristics in linear and saturation regions, which are critical for RF IC design. An enhanced mobility model with improved body bias dependency has also been proposed that helps in the accurate validation of transconductance. The model is validated with state-of-the-art industry hardware data from GlobalFoundries. The model has been integrated into our new industry standard symmetric BSIM-SOI compact model framework.

AbstractThe present study tends to evaluate the possible potential of bio-active Morroniside (MOR), against alloxan (ALX)-induced genotoxicity and hyperglycaemia. In silicoprediction revealed the interaction of MOR with Poly (ADP-ribose) polymerase (PARP) protein which corroborated well with experimental in vitroL6 cell line and in vivomice models. Data revealed the efficacy of MOR in the selective activation of PARP protein and modulating other stress proteins NF-κB, and TNF-α to initiate protective potential against ALX-induced genotoxicity and hyperglycaemia. Further, the strong interaction of MOR with CT-DNA (calf thymus DNA) analyzed through CD spectroscopy, UV-Vis study and ITC data revealed the concerted action of bio-factors involved in inhibiting chromosomal aberration and micronucleus formation associated with DNA damage. Finally, MOR does not play any role in microbial growth inhibition which often occurs due to hyperglycemic dysbiosis. Thus, from the overall findings, we may conclude that MOR could be a potential drug candidate for the therapeutic management of induced-hyperglycaemia and genotoxicity.Communicated by Ramaswamy H. Sarma

Progress in machine learning has facilitated the development of potentials that offer both the accuracy of first-principles techniques and vast increases in the speed of evaluation. Recently, Δ-machine learning has been used to elevate the quality of a potential energy surface (PES) based on low-level, e.g., density functional theory (DFT) energies and gradients to close to the gold-standard coupled cluster level of accuracy. We have demonstrated the success of this approach for molecules, ranging in size from H3O+to 15-atom acetyl-acetone and tropolone. These were all done using the B3LYP functional. Here, we investigate the generality of this approach for the PBE, M06, M06-2X, and PBE0 + MBD functionals, using ethanol as the example molecule. Linear regression with permutationally invariant polynomials is used to fit both low-level and correction PESs. These PESs are employed for standard RMSE analysis for training and test data sets, and then general fidelity tests such as energetics of stationary points, normal-mode frequencies, and torsional potentials are examined. We achieve similar improvements in all cases. Interestingly, we obtained significant improvement over DFT gradients where coupled cluster gradients were not used to correct the low-level PES. Finally, we present some results for correcting a recent molecular mechanics force field for ethanol and comment on the possible generality of this approach.

The production and application of fluorescent carbon dots (CD) derived from different biomass sources and biowastes can help reduce costs and improve waste management. In this work, we synthesized fluorescent carbon nanoparticles from cellulose through a two-step process. The quantum yield of the obtained CDs was further increased upon reduction, and these CDs tend to aggregate in the presence of suitable surfactants. These aggregations were studied using different spectroscopic and microscopic techniques. The loading of doxorubicin hydrochloride in both aqueous and aqueous carboxymethyl cellulose solutions leads to the generation of white light emission. Further studies indicate that FRET and secondary inner filter effect (sIFE) may be responsible for this generation of white light. White light-emitting thin films have recently been used in various light-harvesting systems. Consequently, we used these CDs to produce an excellent white light-emitting carboxymethylcellulose film. This makes CDs more practical for use in light-emitting devices.

In recent years, an increase in the number of chronic kidney disease (CKD) cases has led to a global health burden majorly affecting underdeveloped and developing nations. A key biomarker for assessing the kidneys’ normal functioning is creatinine, which is filtered out from the blood by the kidney. Thus, timely and specific detection of creatinine becomes necessary for diagnosis and subsequent treatment of CKD. Hence, in this study, we have tried to develop a field-deployable, software-integrated immunosensor for the detection of creatinine in a serum sample. The immunosensor was developed by incorporating gold nanoparticles, boron doped MXene, polyaniline, and anticreatinine antibody using an appropriate bioconjugation reaction. The developed sensor was able to detect creatinine in a linear dynamic range of 10 nM to 0.1 M with a limit of detection of 1.72 (±0.07) nM. The sensor was integrated with an indigenously developed software named “CretCheck” which simplifies the process of data analysis. The software integrated personalized biosensing device was used to find the creatinine concentrations directly from the obtained analytical signals. The developed immunosensor with the integrated software can also be implemented directly in primary health care facilities for creatinine detection in the future.

The performance of six ruthenium catalysts and two iron catalysts were evaluated toward the acceptorless dehydrogenation of benzylamine. All catalysts shared the common structure [M(Cp/Cp*)(PR2NR’2)(MeCN)]PF6(M = Fe, Ru; Cp = cyclopentadienyl; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; PR2NR’2= 1,5-R′-3,7-R-1,5-diaza-3,7-diphosphacyclooctane) in which the PR2NR’2ligands contain a pendant tertiary amine that enables cooperative catalytic mechanisms. Catalytic activity and selectivity were evaluated to identify the optimal catalyst structural features. The iron catalyst [Fe(Cp)(PPh2NPh2)(MeCN)]PF6demonstrated near-exclusive selectivity for the acceptorless dehydrogenative coupled product, N-benzylidenebenzylamine. The absence of the hydrogen-borrowed (dibenzylamine) product indicates that this iron catalyst strongly favors dehydrogenation pathways over hydrogenation. This was confirmed through the control reactions. The performance of [Fe(Cp)(PPh2NPh2)(MeCN)]PF6was optimized, but the catalyst was ineffective toward a broader scope of substrates.

The implications of retained strain on in vitroand in vivodegradation behavior as well as cytocompatibility of the Mg–4Zn–0.5Ca–0.8Mn alloy is comprehensively studied. The retained strain is induced in homogenized specimens by hard-plate hot forging (HPHF) at a temperature (523 K) lower than the recrystallization temperature of the alloy. The retained strain generated during deformation process deteriorated the corrosion response of the deformed alloy as compared to its homogenized counterpart. The strained area of deformed specimen with high dislocation density promoted defect generation (oxygen vacancies) in the film and facilitated preferential migration of ions, consequently leading to formation of a nonuniform product film with low protectiveness. In addition to strain magnitude, the distribution of retained strain also influenced the product film properties in the deformed specimens. An even distribution of retained strain improved the uniformity of the product film to certain extent by providing greater film coverage, resulting in higher film resistance. After 24 h of immersion, the protectiveness of the film was further improved in this specimen due to annihilation of defects through homogeneous ionic migration, which led to the development of a uniform and stable film that restricted further ionic diffusion. The dissolution of Zn(OH)2into Zn2+ions was promoted at lower pH, resulting in enhanced antimicrobial activity in the specimen with the lowest degradation. Besides, the specimen with stable product film not only minimized the rate of further degradation but also served as an interface for new bone growth, as evident from in vivostudies.

Molecular crystals that can display stimuli-responsive behavior are a fascinating class of materials that can be used in various advanced technologies. However, designing and developing molecular crystal polymorphs that could respond differently to a single stimulus are still a challenging task. In this article, we report remarkably different photoresponses of the two polymorphs (DMA-αand DMA-β) of a simple donor–acceptor-type organic molecule (E)-3(4-(dimethylamino)phenyl)-2(4-(trifluoromethyl)phenyl)acrylonitrile (DMA). Upon 456 nm light irradiation, DMA-αcrystals undergo topochemical [2 + 2] cycloaddition reaction due to favorable stacking of C═C double bonds in the crystal lattice, while DMA-βcrystals exhibit E- to Z-isomerization reaction. Furthermore, the emission maxima (λmax,em) of both crystals shifted differently due to photoreaction. The origin of the distinct photoreactivities of two polymorphs could be rooted to different molecular packing and intermolecular interactions in the respective crystal lattices. Our work provides an effective strategy to tune the photoreactivity of organic crystalline materials and their potential applications in sensors, actuators, and other optoelectronic devices.

Unraveling the reaction pathway of photoinduced reactions poses a great challenge owing to its complexity. Recently, graph theory-based machine learning combined with nonadiabatic molecular dynamics (NAMD) has been applied to obtain the global reaction coordinate of the photoisomerization of azobenzene. However, NAMD simulations are computationally expensive as they require calculating the nonadiabatic coupling vectors at each time step. Here, we showed that ab initio molecular dynamics (AIMD) can be used as an alternative to NAMD by choosing an appropriate initial condition for the simulation. We applied our methodology to determine a plausible global reaction coordinate of retinal photoisomerization, which is essential for human vision. On rank-ordering the internal coordinates, based on the mutual information (MI) between the internal coordinates and the HOMO energy, NAMD and AIMD give a similar trend. Our results demonstrate that our AIMD-based machine learning protocol for retinal is 1.5 times faster than that of NAMD to study reaction coordinates.

The optoelectronic properties of polythiophene (PT) graft block copolymers are most important for fabricating optoelectronic devices, and recently, we reported a single-pot atom-transfer radical polymerization (ATRP) technique for preparation of PT graft block copolymers between thermoresponsive poly(diethylene glycol methyl ether methacrylate) (PDEGMEM) and pH-responsive poly(dimethyl amino ethyl methacrylate) (PDMAEMA) from the PT backbone via the “grafting from” strategy with an 11 mol % contamination. A “grafting onto” strategy has been opted to eliminate the contamination from the block copolymer where we synthesized poly(thiophene acetic acid) (P3TAA) followed by the coupling with PDEGMEM-b-PDMAEMA-Cl, PDMAEMA-b-PDEGMEM-Cl, and PDMAEMA-ran-PDEGMEM-Cl copolymers, produced separately by the ATRP technique. The polymers were characterized using 1H NMR, SEC, etc. TEM study exhibits mostly vesicular morphology and optical properties measured using UV–vis and photoluminescence spectroscopy showing pH dependent behavior. dc conductivity values indicate semiconducting nature in the order P2 > P3 > P1. The abrupt hike of P2 (∼80 times) in conductivity at pH 3 from that of previously prepared P2 copolymers formed by the grafting fromprocess is attributed to the absence of ∼11 mol % contamination. Conductivity decreases with increasing pH, due to coiling of the PT backbone in accordance with the blue shifts of λabspeaks. The current (I)–voltage (V) plots exhibit bimodal memory and organic mixed ionic and electronic conductivity. Higher current (3.3 mA for P2, pH 3) and electronic memory occur upon light irradiation than that of dark. Photoswitching property decreases with increase of pH, showing highest photocurrent gain of 8.05 for P2 at pH 3. Photocurrent gain follows the order P2 > P3 > P1 indicating P2 is the best to develop photoswitches in the P-series polymers. Fitting of growth and decay curves suggests that they are a two-stage process: photocurrent raises fast at the on state initially and then at a slower rate and similar at an off state. Impedance spectra suggest charge-transfer resistance and Warburg impedance values follow the order of P1 > P3 > P2, whereas capacitance value follows the opposite order.

This article proposes a novel method for detecting human mouth-neck activities using the nearfield effect of a single antenna used as the noninvasive sensor capable of capturing very complex and subtle variations of the surroundings. The time-varying signatures of reflection coefficient ( ${S}_{{11}}$ ) due to perturbed nearfield radiation reveal minute distinct characteristics gathered from the Flexible-RT/Duroid (F-RTD) antenna, which can pinpoint the distinct qualities and coexisting changes in radiation of these actions for various mouth-neck motions. The F-RTD antenna demonstrates good biocompatibility to electromagnetic absorption. The wavelet-based denoising of perturbed ${S}_{{11}}$ signatures is obtained using decomposition, elimination of coefficients, and reconstruction process. A deep learning (DL) model is used to extract deep features from 2-D time-frequency (TF) images generated by a Gaussian windowed Gabor wavelet transform (GWT) of the denoised signals. Two more pretrained benchmark models, namely, Squeeze-Net and Alex-Net, are used, and it is found that the proposed DL model produces the best outcome in every case. The antenna is placed in two distinct locations, on the neck and near the mouth. The neck mount is shown to be effective localization for detecting six different motions. The classification performance is analyzed ${S}_{{11}}$ magnitude and phase, as well as several sliding time windows. At the optimal sliding frame of 2.5 s, the accuracy (ACC), ${F}1$ score, sensitivity (SEN), and precision (PRC) metrics for neck mount are found to be 94.68%, 94.7%, 94.68%, and 94.72%, respectively. Similarly, the corresponding metrics for mouth mount are 90.88%, 90.45%, 90%, and 90.88%.

The current study examines the strength and transport properties of reclaimed asphalt pavement (RAP) inclusive pervious concrete (PC) pavement mixes containing various industrial and agricultural wastes such as silica fume (SF), fly ash (FA), and bagasse ash (BGA). Apart from a conventional PC mix (containing natural aggregates) and a 100% RAP inclusive PC mix, seven different mixes were developed by mixing 100% RAP aggregates with SF (5 and 10%), FA (10 and 15%), and BGA (5, 10, and 15%) as partial replacements for ordinary Portland cement. The above-mentioned PC pavement mixes were investigated for density, porosity, permeability, compressive strength, modulus of rupture, and abrasion resistance. The interconnected pore structure of conventional PC and RAP-PC pavement mixes was investigated using 2D image analysis and X-Ray microcomputed tomography. Based on the laboratory results, it can be stated that the inclusion of RAP significantly improves the transport properties of PC pavement mixes with increased porosity and permeability values. This was primarily due to a more interconnected pore matrix and lesser isolated voids in the RAP-PC pavement mix. The addition of SF could only improve the strength parameters (compressive strength and modulus of rupture) of the RAP-PC pavement mix. In contrast, BGA inclusion was observed to improve its transport properties (porosity and permeability). Furthermore, the inclusion of SF, FA, and BGA in a 100% RAP-PC mix improved abrasion resistance. When compared to the conventional PC pavement mix, incorporating RAP aggregates blended with SF, FA, and BGA can reduce the production cost of 1 m3PC by 30–61% and lower CO2emissions by 13–21%. However, considering the strength and transport property requirements of PC mixes, as well as the economic and environmental viability, the present investigation recommends using 5% SF, 10% FA, and 10% BGA in a 100% RAP-PC pavement mix.

AbstractHuman adenovirus (HADV) infection can pose a serious threat to children, leading to a variety of respiratory illnesses and other complications. Particularly, children with weak immune systems are vulnerable to severe adenovirus infections with high mortality. The main focus of this study is to propose new antiviral agents as lead HADV inhibitors for children. So, several antiviral agents used in children were subjected to finding new HADV inhibitors using important computational methods of molecular docking, molecular dynamics (MD) simulation, Molecular Mechanics Poisson-Boltzmann Surface Area (MM-PBSA) binding free energy calculations, density functional theory (DFT), and pharmacokinetic analysis. Molecular docking of standard cidofovir along with other ligands, suggested that sofosbuvir has the highest binding energy (−10.8 kcal/mol), followed by baloxavir marboxil (−10.36 kcal/mol). Further, the analysis of molecular interactions using MD simulation (100 ns) and MM-PBSA indicated that baloxavir marboxil has formed the most stable protein–ligand complex with HADV, followed by sofosbuvir. The binding free energies of baloxavir marboxil and sofosbuvir were found to be −61.724 kJ/mol and −48.123 kJ/mol, respectively. The DFT and drug-likeness properties of these compounds were also investigated. Overall, two antiviral agents, such as baloxavir marboxil, and sofosbuvir are suggested as lead repurposed candidates against HADV.Communicated by Ramaswamy H. Sarma

NNN-Bis(imino) pyridine-based pincer-Fe(II) complexes with an expected trigonal bipyramidal (TBP) geometry equilibrated to a rearranged ion pair of an octahedral dicationic Fe complex containing two bis(imino)pyridine ligands that are neutralized by a tetrahedral dianionic-[FeCl4]2–. Single-crystal X-ray diffraction (SCXRD), high-resolution mass spectrometry (HRMS), and UV–visible (UV–vis) studies suggested that the equilibrium was dictated by the sterics of the R group on the imine N, with the less-crowded groups tilting the equilibrium to the ion pair and the bulky ones favoring the TBP geometry. Electron paramagnetic resonance (EPR) and Evan’s magnetic moment measurements indicated that the complexes were paramagnetic with Fe(II) in a high-spin state. In solution, over a period of 7 days, these Fe(II) complexes oxidized to a mixture of low-spin and high-spin Fe(III) species. These pincer-Fe(II) were found to be highly active toward the transformation of biodiesel waste glycerol to value-added lactic acid (LA). Particularly, (Ph2NNN)FeCl2(0.1 mol %) gave 91% LA with a 99% selectivity at 140 °C using 1.2 equiv of NaOH. With 0.0001 mol % (Ph2NNN)FeCl2, very high turnovers (74% LA, 98% selectivity, 740 000 turnover number (TON) at 4405 turnovers per hour (TOs/h)) were obtained after 7 days. EPR indicated Fe(III) species to be the active catalyst, a few of which were detected by HRMS. Experiments with Hg are suggestive of the mostly homogeneous molecular nature of the catalyst with a minor contribution from heterogeneous Fe nanoparticles.

Eggshell membrane-based biomedical applications have recently received great attention for their wound-healing properties. However, there are limited studies on diabetic wound healing. In this regard, we devised four types of composite eggshell membrane mats with nanoscale coatings of bioactive glass/Zn/Co-doped bioactive glass (ESM + BAG, ESM + ZnBAG, ESM + CoBAG, and ESM + ZnCoBAG) as wound-dressing materials for chronic nonhealing diabetic wounds. A detailed study of the physicochemical properties of the mats was conducted. In vitro studies demonstrated cytocompatibility and viability of human dermal fibroblasts on all four types of mats. The cells also attached finely on the mats with the help of cellular extensions, as evident from scanning electron microscopy (SEM) and rhodamine-phalloidin and Hoechst 33342 staining of cellular components. Endowed with bioactive properties, these mats influenced all aspects of full-thickness skin wound healing in diabetic animal model studies. All of the mats, especially the ESM + ZnCoBAG mat, showed the earliest wound closure, effective renewal, and restructuring of the extracellular matrix in terms of an accurate and timely accumulation of collagen, elastin, and reticulin fibers. Hydroxyproline and sulfated glycosaminoglycans were significantly (p< 0.01, p< 0.05) higher in ESM-ZnCoBAG-treated wounds in comparison to ESM-BAG-treated wounds, which suggests that these newly developed mats have potential as an affordable diabetic wound care solution in biomedical research.

In an effort to break the single-cage 16-vertex supraicosahedral barrier, we have explored the reaction of [Cp*CoCl2], 1with [LiBH4·THF], followed by thermolysis with [BH3·SMe2] [Cp* = η5-C5Me5]. Although our objective to synthesize a high-nuclearity single-cage cluster was not achieved, we have isolated a 25-vertex macropolyhedral cluster [(Cp*Co)5Co2B18H17(CH3)S] (2). Cluster 2is an exceptional fused hourglass-shaped macropolyhedral cluster composing two icosahedral cores ([Co3B9] and [Co4B8]) and three tetrahedral cores [Co2B2]. Although the fusion in cluster 2is very complex, it follows Mingos fusion formalism, leading to an attractive hourglass-shaped cluster. Through subtle changes in reaction conditions, two new cobaltaborane clusters, nido-4,5,7-[(Cp*Co)3B7H11] (3) and nido-2,9-[(Cp*Co)2B8H12] (4), have been isolated. The observed core geometries of clusters 3and 4are similar to the parent deltahedra [B10H14] with (n+ 2) SEP (SEP = skeletal electron pair, n= no. of vertices). All the synthesized cobaltaboranes have been characterized in solution by ESI-mass, nuclear magnetic resonance spectroscopy, infrared spectroscopy and structurally solved by single-crystal X-ray diffraction analysis.

Bioengineered composite hydrogel platforms made of a supramolecular coassembly have recently garnered significant attention as promising biomaterial-based healthcare therapeutics. The mechanical durability of amyloids, in conjunction with the structured charged framework rendered by biologically abundant key ECM component glycosaminoglycan, enables us to design minimalistic customized biomaterial suited for stimuli responsive therapy. In this study, by harnessing the heparin sulfate-binding aptitude of amyloid fibrils, we have constructed a pH-responsive extracellular matrix (ECM) mimicking hydrogel matrix. This effective biocompatible platform comprising heparin sulfate-amyloid coassembled hydrogel embedded with polyphenol functionalized silver nanoparticles not only provide a native skin ECM-like conductive environment but also provide wound-microenvironment responsive on-demand superior antibacterial efficacy for effective diabetic wound healing. Interestingly, both the cytocompatibility and antibacterial properties of this bioinspired matrix can be fine-tuned by controlling the mutual ratio of heparin sulfate-amyloid and incubated silver nanoparticle components, respectively. The designed biomaterial platform exhibits notable effectiveness in the treatment of chronic hyperglycemic wounds infected with multidrug-resistant bacteria, because of the integration of pH-responsive release characteristics of the incubated functionalized AgNP and the antibacterial amyloid fibrils. In addition to this, the aforementioned assemblage shows exceptional hemocompatibility with significant antibiofilm and antioxidant characteristics. Histological evidence of the incised skin tissue sections indicates that the fabricated composite hydrogel is also effective in controlling pro-inflammatory cytokines such as IL6 and TNFα expressions at the wound vicinity with significant upregulation of angiogenesis markers like CD31 and α-SMA.

A mild and metal-free approach has been developed for 1,2-difunctionalization of aryne using sulfenamides as a nucleophile and a halogen source (CX4) as an electrophile to synthesize S-(o-halo)aryl sulfilimines. The late-stage functionalizations of halide handles via Suzuki–Miyaura and Buchwald–Hartwig reactions exhibit the synthetic utilities of the products. The chemoselectivity, regioselectivity, rapidity, and use of economical CCl4are the advantages of this protocol.

Polymer-metal hybrid nanocomposites have garnered significant attention in recent years due to their exceptional electrical and dielectric properties, which find applications in a wide range of industries, including electronics, energy storage, and advanced materials. This review article provides a comprehensive overview of the current state-of-the-art in the field of polymer-metal hybrid nanocomposites, with a particular focus on their electrical and dielectric properties. The first section of the review delves into the synthesis and fabrication techniques employed to create these nanocomposites, highlighting the importance of controlling the dispersion and distribution of metal nanoparticles within the polymer matrix. Various approaches, such as in-situ polymerization, melt mixing, and electrospinning, are discussed in detail, along with their respective advantages and limitations.The subsequent sections explore the influence of metal nanoparticles on the electrical conductivity and dielectric constant of the nanocomposites. The role of factors such as nanoparticle size, shape, and concentration in determining these properties is thoroughly examined. Moreover, the impact of metal surface modifications and the choice of polymer matrix on enhancing electrical and dielectric performance are also addressed. In addition to discussing fundamental aspects, this review highlights practical applications of polymer-metal hybrid nanocomposites in the development of high-performance capacitors, sensors, electromagnetic shielding materials, and flexible electronics. The potential for these materials to revolutionize various technological sectors is discussed, emphasizing their role in advancing miniaturization, energy efficiency, and durability. Furthermore, the review outlines current challenges and future prospects in the field, including the need for a deeper understanding of the underlying mechanisms governing electrical and dielectric behavior in these nanocomposites. Emerging trends such as the incorporation of 2D materials and the development of multifunctional hybrid systems are also explored, hinting at exciting avenues for further research and innovation. In conclusion, polymer-metal hybrid nanocomposites offer a promising platform for tailoring electrical and dielectric properties to meet the demands of modern technology. This review serves as a valuable resource for researchers, engineers, and scientists seeking to explore the potential of these materials and drive advancements in the field of electrical and dielectric engineering.

The contribution of three-dimensional genome organization to physiological ageing is not well known. Here we show that large-scale chromatin reorganization distinguishes young and old bone marrow progenitor (pro-) B cells. These changes result in increased interactions at the compartment level and reduced interactions within topologically associated domains (TADs). The gene encoding Ebf1, a key B cell regulator, switches from compartment A to B with age. Genetically reducing Ebf1 recapitulates some features of old pro-B cells. TADs that are most reduced with age contain genes important for B cell development, including the immunoglobulin heavy chain (Igh) locus. Weaker intra-TAD interactions at Ighcorrelate with altered variable (V), diversity (D) and joining (J) gene recombination. Our observations implicate three-dimensional chromatin reorganization as a major driver of pro-B cell phenotypes that impair B lymphopoiesis with age.

Background: Highly sensitized pediatric patients awaiting heart transplantation experience longer wait times and thus higher waitlist mortality. Similarly, children less than 2 years of age have increased waitlist times and mortality when compared to their older peers. To improve the likelihood of successful transplantation in these patients, various strategies have been utilized, including peri-operative plasmapheresis. However, limited data exists comparing plasmapheresis techniques for antibody reduction. This study’s aim was to compare the in vitromagnitude of isohemagglutinin titers (IT) and human leukocyte antigen (HLA) antibody removal and the time required between membrane-based plasmapheresis (MP) and centrifuge-based plasmapheresis (CP) incorporated into the extracorporeal (EC) circuit. Methods: Two MP (Prismaflex) and two CP (Spectra Optia, Terumo BCT) circuits were incorporated into four separate EC circuits primed with high titer, highly sensitized type O donor whole blood. Assays were performed to determine baseline IT and anti-HLA antibodies and then at 30-minute increments until completion of the run (two plasma volume exchanges) at two hours. Results: There was a decrease in anti-A and anti-B IgM and IgG titers with both MP and CP. Mean anti-A and anti-B titer reduction was by 4.625 titers (93.7% change) and 4.375 titers (93.8% change) using MP and CP, respectively. At 2 h of apheresis, CP reduced 62.5% of all ITs to ≤ 1:4, while MP reduced 50% of ITs to ≤ 1:4. Additionally, reduction of anti-HLA class II antibody to mean fluorescence intensity (MFI) <3000 was achieved with both MP and CP. At 2 h of apheresis, CP reduced MFI by 2–3.5 fold and MP reduced MFI by 1.7–2.5 fold. Both demonstrated similar hemolytic and thrombotic profiles. Conclusions: In this in vitroplasmapheresis model of IT and anti-HLA antibody reduction, both MP and CP incorporated into the EC circuit can be used quickly and effectively to reduce circulating antibodies. While CP may have some greater efficiency, further study is necessary to verify this in vivo.

Bioluminescence is a fascinating natural phenomenon, wherein organisms produce light through specific biochemical reactions. Among these organisms, Renillaluciferase (RLuc) derived from the sea pansy Renilla reniformisis notable for its blue light emission and has potential applications in bioluminescent tagging. Our study focuses on RLuc8, a variant of RLuc with eight amino acid substitutions. Recent studies have shown that the luminescent emitter coelenteramide can adopt multiple protonation states, which may be influenced by nearby residues at the enzyme’s active site, demonstrating a complex interplay between protein structure and bioluminescence. Herein, using the quantum mechanical consistent force field method and the semimacroscopic protein dipole-Langevin dipole method with linear response approximation, we show that the phenolate state of coelenteramide in RLuc8 is the primary light-emitting species in agreement with experimental results. Our calculations also suggest that the proton transfer (PT) from neutral coelenteramide to Asp162 plays a crucial role in the bioluminescence process. Additionally, we reproduced the observed emission maximum for the amide anion in RLuc8-D120A and the pyrazine anion in the presence of a Na+counterion in RLuc8-D162A, suggesting that these are the primary emitters. Furthermore, our calculations on the neutral emitter in the engineered AncFT-D160A enzyme, structurally akin to RLuc8-D162A but with a considerably blue-shifted emission peak, aligned with the observed data, possibly explaining the variance in emission peaks. Overall, this study demonstrates an effective approach to investigate chromophores’ bimolecular states while incorporating the PT process in emission spectra calculations, contributing valuable insights for future studies of PT in photoproteins.

Amidst the present healthcare issues, diabetes is unique as an emerging class of affliction with chronicity in a majority of the population. To check and control its effects, there have been huge turnover and constant development of management strategies, and though a bigger part of the health care area is involved in achieving its control and the related issues such as the effect of diabetes on wound healing and care and many of the works have reached certain successful outcomes, still there is a huge lack in managing it, with maximum effect yet to be attained. Studying pathophysiology and involvement of various treatment options, such as tissue engineering, application of hydrogels, drug delivery methods, and enhancing angiogenesis, are at constantly developing stages either direct or indirect. In this review, we have gathered a wide field of information and different new therapeutic methods and targets for the scientific community, paving the way toward more settled ideas and research advances to cure diabetic wounds and manage their outcomes.

Polythiophene (PT) is an important conducting polymer for its outstanding optoelectronic properties. Here, we delineate the self-assembly-driven optoelectronic properties of PT-peptide and PT-polymer conjugates, taking examples from recent literature reports. PT-peptide conjugates made by both covalent and noncovalent approaches are discussed. Poly(3-thiophene acetic acid) (P3TAA) covalently coupled with Gly-Gly-His tripeptide, C-protected and deprotected tripeptide H2N-F-F-V-OMe, etc. exhibits self-assembly-driven absorbance, fluorescence, photocurrent, and electronic properties. Noncovalent PT-peptide conjugates produced via ionic, H-bonding, and p-stacking interactions show tunable morphology and optoelectronic properties by varying the composition of a component. PT conjugated with Alzheimer’s disease peptide (KLVFFAE, Aß16–22) shows enhanced photocatalytic water splitting, cationic PT(CPT-I)-perylene bisimide-appended dipeptide (PBI-DY), and anionic PT-perylene diimide-appended cationic peptide (PBI-NH3+) conjugates and exhibits self-assembly-driven enhanced photoswitching and organic mixed electronic and ionic conductivity (OMEIC) properties. In the PT-polymer conjugates, self-assembly-driven optoelectronic properties of covalently produced PT-random copolymers, PT-block copolymers, PT-graft-random copolymers, and PT-graft-block copolymer conjugates are discussed. The HOMO–LUMO levels of hyperbranched polymers are optimized to obtain better power conversion efficiency (PCE) in the bulk heterojunction (BHJ) solar cell than in linear polymers, and P3TAA-ran-P3HT (43 mol % P3TAA) conjugated with MAPbI3perovskite exhibits higher PCE (10%) than that with only P3TAA hole-transporting material. In the ampholytic polythiophene (APT), on increasing pH, the morphology changes from the vesicle to fibrillar network for the dethreading of the PT chain, resulting in a red shift of the absorbance peak, an enormous increase in PL intensity, lowering of the charge transfer resistance, and an induction of Warburg impedance for the release of quencher I–ions. The PT-g-(PDMAEMA-co-PGLU-HEM) graft copolymer self-assembles with Con-A lectin, causing fluorescence quenching, and acts as a sensor for Con-A with a LOD of 57 mg/L. Varying sequences of the block copolymer containing pH-responsive PDMAEMA and temperature-responsive PDEGMEM grafted to the PT backbone shows different self-assembly, optical, electronic, and photocurrent properties depending on the proximity and preponderance of the block sequence on the PT backbone.

In this work, we have used the standard symmetric key block cipher data encryption algorithm RC5(32,16,8) for the encryption of digital greyscale images. For this, we have only considered the nonzero elements of the sparse matrix of the images which have been generated using the sparse representation technique. The security strength of the proposed technique is verified through different quality parameters, e.g.information entropy, correlation coefficients, NPCR, UACI, and NIST test. Our proposed algorithm achieved the maximum information entropy value of 7.9977 for the cameraman image and nearly zero correlation coefficient values establish the robustness of the cryptosystem. The highest NPCR and UACI values obtained in our work are 99.6916 and 33.9605, which are closer to the maximum theoretical values. The proposed technique is also compared with some of the contemporary works to validate the credibility of our proposed algorithm.

We report a depolymerization strategy to nearly quantitatively regenerate isocyanates from thermoplastic and thermoset polyurethanes (PUs) and then resynthesize PUs using the recovered isocyanates. To date, chemical/advanced recycling of PUs has focused primarily on the recovery of polyols and diamines under comparatively harsh conditions (e.g.,high pressure and temperature), and the recovery of isocyanates has been difficult. Our approach leverages an organoboron Lewis acid to depolymerize PUs directly to isocyanates under mild conditions (e.g.,∼80 °C in toluene) without the need for phosgene or other harsh reagents, and we show that both laboratory-synthesized and commercially sourced PUs can be depolymerized. Furthermore, we demonstrate the utility of the recovered isocyanate in the production of second-generation PUs with thermal properties and molecular weights similar to those of the virgin PUs. Overall, this route uniquely provides an opportunity for circularity in PU materials and can add significant value to end-of-life PU products.

The formic acid–ammonia dimer is an important example of a hydrogen-bonded complex in which a double proton transfer can occur. Its microwave spectrum has recently been reported and rotational constants and quadrupole coupling constants were determined. Calculated estimates of the double-well barrier and the internal barriers to rotation were also reported. Here, we report a full-dimensional potential energy surface (PES) for this complex, using two closely related Δ-machine learning methods to bring it to the CCSD(T) level of accuracy. The PES dissociates smoothly and accurately. Using a 2d quantum model the ground vibrational-state tunneling splitting is estimated to be less than 10–4cm–1. The dipole moment along the intrinsic reaction coordinate is calculated along with a Mullikan charge analysis and supports the mildly ionic character of the minimum and strongly ionic character at the double-well barrier.

Individuals with serum antibodies to citrullinated protein antigens (ACPA), rheumatoid factor, and symptoms, such as inflammatory joint pain, are at high risk of developing rheumatoid arthritis. In the arthritis prevention in the pre-clinical phase of rheumatoid arthritis with abatacept (APIPPRA) trial, we aimed to evaluate the feasibility, efficacy, and acceptability of treating high risk individuals with the T-cell co-stimulation modulator abatacept.

Background The Ministry of Health and Wellness of Jamaica has endorsed the use of pre-exposure prophylaxis (PrEP) as an HIV prevention strategy; however, PrEP was not included in the national HIV prevention program in 2021.Methods A cross-sectional online study involving physicians in Jamaica was conducted in 2021 to describe PrEP awareness, beliefs, attitudes, and practices. The study also assessed individual and social factors associated with discussing PrEP with patients and willingness to prescribe PrEP.Findings The mean age and standard deviation (SD) of the 69 physicians who completed the survey were 45.5 ± 13.6 years. Most of the participants (80%) reported that they were somewhat familiar with PrEP. PrEP attitude and perceived comfort in prescribing PrEP were moderate among participating physicians, with a mean and SD of 3.9 ± 0.8 and 3.6 ± 0.9 respectively. Six percent of physicians reported that they had prescribed PrEP and 17% had discussed PrEP with their patients in the past year. However, most (90%) reported that they were willing to prescribe PrEP after being informed about it. In the unadjusted model, identifying as Christian (compared to non-Christian) and reporting stronger homophobic beliefs were associated with reduced odds of discussing PrEP with patients. In the multivariable model, only homophobia remained statistically significant (OR, 0.24; 95% CI: 0.07–0.63).Conclusion The findings suggest that physicians in Jamacia may be willing to prescribe PrEP; however, homophobia is a barrier to discussions, underscoring the need for the Ministry of Health and Wellness to recognize the role that homophobia plays in the national HIV program to further reduce HIV incidence in Jamaica.

Photoionized and electronically excited ethylene C2H4+can undergo H-loss, H2-loss, and ethylene–ethylidene isomerization, where the latter entails a hydrogen migration. Recent pioneering experiments with few-femtosecond extreme ultraviolet pulses and complementary theoretical studies have shed light on the photodynamics of this prototypical organic cation. However, no theoretical investigation based on dynamics simulations reported to date has described the mechanisms and time scales of dissociation and isomerization. Herein, we simulate the coupled electron–nuclear dynamics of ethylene following vertical ionization and electronic excitation to its four lowest-lying cationic states. The electronic structure is treated at the CASSCF level, with an active space large enough to describe bond breaking and formation. The simulations indicate that dissociation and isomerization take place mainly on the cationic ground state and allow the probing of previous hypotheses concerning the correlation between the photochemical outcome and the traversed conical intersections. The results, moreover, support the long-standing view that H2-loss may occur from the ethylidene form. However, the ethylene–ethylidene isomerization time predicted by the simulations is considerably longer than those previously inferred from indirect experimental measurements.

Green synthesis of nanoparticles (NPs) is superior to conventional physical and chemical methods and increasingly becoming the preferred mode of synthesis nowadays. We report a method for phytosynthesis of ZnO NPs and their characterization for plausible diverse applications. ZnO NPs was synthesized using an extract of the leaves of Tagetes erectaL. (marigold), with optimum synthesis at a ratio of 1:150 for the leaf extract and salt solution (v/v), 150 mM zinc acetate at 85 °C and pH 6. The NPs were characterized using UV–vis spectrophotometer, FESEM, EDX, FT-IR, XRD, AFM, XPS, and ζ potential techniques. The band gap energy of the NPs was 3.44 eV. The IR spectrum confirmed the involvement of different phenolic and aromatic components of the plant extract as capping agents. The mean size of the NPs was ∼25 nm, using XRD and AFM techniques. The SEM image showed that the NPs were elongate with a rough surface. The EDX profile confirmed the purity of the preparation. UV–vis spectrophotometry and ζ potential data showed the NPs to be stable. SDS-PAGE of Saccharomyces cerevisiaecells exposed to 200 and 400 μg/mL NPs showed that expression levels of a few proteins were affected. The effect of the NPs on some microbes analyzed using agar well diffusion assay showed its antimicrobial potency indicating its potential use as an antimicrobial agent, especially against Gram-positive bacteria.

Measurement of pH in living cells is a great and decisive factor for providing an early and accurate diagnosis factor. Along with this, the multimodal transverse and longitudinal relaxivity enhancement potentiality over single modality within a single platform in the magnetic resonance imaging (MRI) field is a very challenging issue for diagnostic purposes in the biomedical field of application. Therefore, this work aims to design a versatile platform by fabricating a novel nanoprobe through holmium- and manganese-ion doping in carbon quantum dots (Ho–Mn–CQDs), which can show nearly neutral intracellular pH sensing and MRI imaging at the same time. These manufactured Ho–Mn–CQDs acted as excellent pH sensors in the near-neutral range (4.01–8.01) with the linearity between 6.01 and 8.01, which could be useful for the intracellular pH-sensing capability. An innumerable number of carboxyl and amino groups are present on the surface of the prepared nanoprobe, making it an excellent candidate for pH sensing through fluorescence intensity quenching phenomena. Cellular uptake and cell viability experiments were also executed to affirm the intracellular accepting ability of Ho–Mn–CQDs. Furthermore, with this pH-sensing quality, these Ho–Mn–CQDs are also capable of acting as T1–T2 dual modal imaging contrast agents in comparison with pristine Ho-doped and Mn-doped CQDs. The Ho–Mn–CQDs showed an increment of r1 and r2 relaxivity values simultaneously compared with only the negative contrast agent, holmium in holmium-doped CQDs, and the positive contrast agent, manganese in manganese-doped CQDs. The above-mentioned observations elucidate that its tiny size, excitation dependence of fluorescence behavior, low cytotoxicity, and dual modal contrast imaging capability make it an ideal candidate for pH monitoring in the near-neutral range and also as a dual modal MRI imaging contrast enhancement nanoprobe at the same time.

We report a full dimensional ab initio potential energy surface for NaCl–H2based on precise fitting of a large data set of CCSD(T)/aug-cc-pVTZ energies. A major goal of this fit is to describe the very long-range interaction accurately. This is done in this instance via the dipole–quadrupole interaction. The NaCl dipole and the H2quadrupole are available through previous works over a large range of internuclear distances. We use these to obtain exact effect charges on each atom. Diffusion Monte Carlo calculations are done for the ground vibrational state using the new potential.

To date, no studies have identified an optimal metric to match donor-recipient (D-R) pairs in pediatric heart transplantation (HT).