Biogenic Polymer-Based Fluorescent Assemblies: Versatile Platforms for Ultrasensitive ATP Detection and Enzyme Assay.

Here, we investigated the optical properties of biocompatible supramolecular assemblies formed through electrostatic interactions between anionic fluorescent dyes and biogenic polymers. The dynamic equilibrium between the monomeric form (fluorescent) and aggregates (nonfluorescent) of dye molecules is responsible for the stimuli-responsive behavior of these polymer composites, which can respond to changes in pH, temperature, and ionic strength. Furthermore, we employed supramolecular assemblies for the purpose of turn-on fluorescence sensing of adenosine triphosphate (ATP) at physiological pH. Notably, no interference was observed even in the presence of well-known competing analytes such as pyrophosphate. In addition to its outstanding selectivity, the present system can detect ATP at concentrations as low as 4.8 nM. The superior detection capabilities are achieved through multiple interactions with biogenic polymers, involving the adenine ring, ribose unit (through hydrogen bonding), and phosphate groups (via charge pairing) of ATP. Given the remarkable sensitivity to ATP, we have applied the present system for the detection of a dephosphorylating enzyme, alkaline phosphatase.

Comparative Analysis of the Hydrazine Interaction with Arylene Diimide Derivatives: Complementary Approach Using First Principles Calculation and Experimental Confirmation.

Suitable functional group-engineered π-conjugated aromatic dimides based on perylene (PDI) and naphthyl scaffolds (NDI) demonstrated excellent sensitivity toward different gaseous analytes. However, to date, no methodical analysis has been performed to rationalize molecular-level interactions in the context of optical transduction, which is essential for systematic performance optimization of NDI/PDI-based molecular sensors. Therefore, in this present work, NDI/PDI scaffolds have been designed with amino acid functional groups (alanine, ALA and glutamic acid, GLU) at the terminal positions, and we subsequently compared the efficacy of four different imide derivatives as model hosts for hydrazine adsorption. Specifically, the adsorption of hydrazine at different interaction sites has been thoroughly investigated using ab initio calculations, where the adsorption energy, charge transfer, and recovery time have been emphasized. Theoretical results exhibit that irrespective of host specification the COOH groups offer a primary interaction site for hydrazine through the hydrogen bonding interaction. The presence of more COOH groups and relatively stronger interaction with secondary edge oxygen ensure that GLU functional moieties are a superior choice over ALU for efficient hydrazine binding. The molecular energy spectrum analysis exhibits more favorable HOMO/LUMO gap variations after hydrazine interaction in the case of PDI derivatives irrespective to the nature of the amino acid residues. Therefore, by a combination of both factors, PDI-GLU has been identified as the most suitable host molecule for hydrazine among four derivatives. Finally, the key theoretical predictions has been later experimentally validated by analyzing UV-visible spectroscopy and NMR studies, wherein the mechanism of interaction has also been experimentally verified by EPR analysis and FT-IR studies.

Surfactant-induced alterations in optoelectronic properties of perylene diimide dyes: modulating sensing responses in the aqueous environment.

The compartmentalization effect of microheterogeneous systems, like surfactant aggregates, showcases altered optoelectronic properties of a perylene diimide-based chromogenic dye (PDI-Ala) compared to bulk water. The relatively hydrophobic microenvironment, poor hydration, and exceptionally large local concentration of dye molecules in the confined environment affect their interaction with target analytes. This realization intrigued us to investigate if micellization can modify the sensing properties (selectivity, sensitivity, response kinetics, output signal, etc.) of the encapsulated dye molecules in the aqueous medium. Response comparisons of PDI-Ala to the ionic analyte (Fe3+) and biomolecule (heparin) in aqueous and surfactant-bound states highlighted significant variations. Fe3+ interaction exhibited a "turn-off" fluorescence response in a water medium, while surfactant-bound conditions triggered "turn-on" fluorescence, enhancing selectivity at the micelle-water interface. Conversely, the native probe showed no interaction with heparin in water but displayed a turn-on fluorescence response in cetyltrimethylammonium bromide (CTAB) micelles, indicating the transformation of a silent molecule into a turn-on fluorescence sensor. This study underscores the influence of micellar environments on dye molecules, altering the sensing responses and selectivity toward analytes, crucial for applications in understanding cellular pathways and toxicity mechanisms.

Discerning toxic nerve gas agents via a distinguishable 'turn-on' fluorescence response: multi-stimuli responsive quinoline derivatives in action.

We have successfully synthesized quinoline derivatives that exhibit easy scalability and responsiveness to multiple stimuli. These derivatives are capable of forming self-assembled nanoscopic aggregates in an aqueous medium. Consequently, when placed in an aqueous environment, we observe dual fluorescence originating from both twisted intramolecular charge transfer and aggregation-induced emission. The introduction of nerve gas agents, such as diethyl chlorophosphate (DClP) or diethylcyanophosphate (DCNP), to the probe molecules facilitates the charge-transfer process, resulting in a red-shift in absorption maxima. Notably, when operating in fluorescence mode, both of these analytes produce distinct output signals, making them easily distinguishable. DCNP generates a blue fluorescence, while the addition of DClP yields cyan fluorescence. Our mechanistic investigation reveals that the initial step involves phosphorylation of the quinoline nitrogen end. However, in the case of DCNP, the released cyanide ion subsequently attacks the carbonyl carbon centre, forming a cyanohydrin derivative. The response to these target analytes appears to be influenced by the nucleophilicity of the quinoline nitrogen end and the electrophilic nature of the carbonyl unit.

Oxidized Bisindolyl-Based Amphiphilic Probe for Dual Mode Analysis of Heavy Metal Pollutants in Aqueous Medium.

The oxidized bisindolyl-based amphiphilic, chromogenic probe has been synthesized that can form nanoscopic aggregates in the aqueous medium. Along with solvent polarity and pH of the medium, it was observed that the addition of heavy metal pollutants, like Hg2+ can cause significant alteration in the charge transfer state. This resulted in the immediate change in the solution color from yellow to orange. Additionally, we could excite either the monomer species or the aggregates of the probe by choosing the proper excitation wavelength. Upon exciting at 390 nm, the compound exhibited a broad fluorescence spectrum with maxima at 450 nm, presumably due to twisted state charge transfer. On the contrary, the aggregated species (λex = 465 nm) displayed a comparatively weaker fluorescence band centered at 565 nm. Interestingly, the fluorescence intensity at the 450 nm band experience fluorescence quenching in the presence of Hg2+ ion, while the aggregate emission band remained unaffected. Finally, the present system was utilized for detection of mercury ions in natural water samples.

Antimicrobial peptide moricin induces ROS mediated caspase-dependent apoptosis in human triple-negative breast cancer via suppression of notch pathway.

BACKGROUND: Breast cancer is the world's most prevalent cancer among women. Microorganisms have been the richest source of antibiotics as well as anticancer drugs. Moricin peptides have shown antibacterial properties; however, the anticancer potential and mechanistic insights into moricin peptide-induced cancer cell death have not yet been explored. METHODS: An investigation through in silico analysis, analytical methods (Reverse Phase-High Performance Liquid Chromatography (RP-HPLC), mass spectroscopy (MS), circular dichroism (CD), and in vitro studies, has been carried out to delineate the mechanism(s) of moricin-induced cancer cell death. An in-silico analysis was performed to predict the anticancer potential of moricin in cancer cells using Anti CP and ACP servers based on a support vector machine (SVM). Molecular docking was performed to predict the binding interaction between moricin and peptide-related cancer signaling pathway(s) through the HawkDOCK web server. Further, in vitro anticancer activity of moricin was performed against MDA-MB-231 cells. RESULTS: In silico observation revealed that moricin is a potential anticancer peptide, and protein-protein docking showed a strong binding interaction between moricin and signaling proteins. CD showed a predominant helical structure of moricin, and the MS result determined the observed molecular weight of moricin is 4544 Da. An in vitro study showed that moricin exposure to MDA-MB-231 cells caused dose dependent inhibition of cell viability with a high generation of reactive oxygen species (ROS). Molecular study revealed that moricin exposure caused downregulation in the expression of Notch-1, NF-ƙB and Bcl2 proteins while upregulating p53, Bax, caspase 3, and caspase 9, which results in caspase-dependent cell death in MDA-MB-231 cells. CONCLUSIONS: In conclusion, this study reveals the anticancer potential and underlying mechanism of moricin peptide-induced cell death in triple negative cancer cells, which could be used in the development of an anticancer drug.

Sequence-Specific Relay Recognition of Multiple Anions: An Interplay between Proton Donors and Acceptors.

Ratiometric detection of analyte is highly deserving since the technique is free from background correction. This work reports the design and synthesis of a pyridine-end oligo p-phenylenevinylene (OPV) derivative, 1 and its application in ratiometric dual-mode (both colorimetric and fluorogenic) recognition of dual anions, bisulfate (LOD=12.5 ppb) followed by fluoride (LOD=18.2 ppb) by sequence-specific relay (SPR) technique. The colorless probe turns brown with addition of bisulfate and again becomes colorless with the sequential addition of fluoride ion. In addition to such naked-eye color change, interestingly the ratiometric spectroscopic signals are reversible and evidently, the probe is reusable for several cycles. Besides, in presence of bisulfate, the protonated probe molecules, owing to their larger amphiphilic characteristics, formed self-assembled nanostructures. In addition to colorimetric and fluorescent changes, 1 H NMR titration and systematic DFT study evidently establish the underneath proton transfer mechanisms. Such reusable OPV-based chemosensor particularly with the capability of naked-eye recognition of dual anions using the SPR technique is seminal and possibly the first report in the literature.

Hydrogel Nanocomposite Towards Optical Sensing of Spermine in Biomedical and Real-Life Food Samples and Remediation of Toxic Dyes from Wastewater.

Nanocomposites such as graphene oxide (GO) have been incorporated into hydrogels to enhance conventional hydrogels' properties and develop new functions. Unique and strong molecular interactions between GO and low molecular weight gelators allow the fabrication of various functional hydrogels suitable for different applications. In the present study, we report a stable and soft nanocomposite hydrogel comprising a pyrene-based chiral amphipath having an amino acid (l-phenylalanine) core with pendant oligo-oxyethylene hydrophilic chains and GO. The mechanical and viscoelastic properties of the nanocomposite hydrogel were thoroughly studied using various spectroscopic, microscopic, and mechanical techniques. Even without GO, native hydrogels could form a self-supported thermoreversible and thixotropic hydrogel composed of the fibrillar network. Unlike native hydrogels, the morphological investigation of nanocomposite gels shows the presence of cross-linked nanosheet-like structures. The combined effect of π-π stacking and H-bonding interactions is the driving force for the formation of such composite hydrogels. Moreover, the nanocomposite hydrogels possess significantly superior mechanical stiffness than the native hydrogels. Interestingly, the thixotropic properties observed with the parent gel were retained even in the presence of carbon nanomaterials (GO). The nanocomposite hydrogel could be employed in the optical sensing of a biogenic polyamine, spermine, resulting in a visible gel-to-sol transition. The superior electrostatic interaction between the GOs and spermine molecules might have led to the release of entrapped fluorogenic dyes from the hydrogel network and a turn-on emission response. The sensory system was employed to analyze spermine content in human urine samples and decomposed food items. A gel-coated paper strip was also developed for onsite detection of the spermine. The nanocomposite hydrogel was further utilized to remove toxic organic dyes such as methylene blue (MB) and rhodamine B (RhB) from the aqueous media. The nanocomposite hydrogel thus showed excellent dye removal capabilities and was also found to be recyclable. Calculations of different mechanical parameters suggest that the dye removal efficiency of the nanocomposite hydrogel was better for MB than for RhB.

Differential response for multiple ions: a smart probe to construct optically tunable molecular logic systems.

A rhodamine-based optical probe has been designed through a one-pot synthetic protocol involving phenanthroline as a binding motif. The compound showed a bright pink coloration specifically upon the addition of Cu2+ and Hg2+ ions. However, the appearance of bright red fluorescence was observed only in the presence of Hg2+. Considering both, we can detect and discriminate these two ions even at ppb level concentration. Furthermore, these in situ generated metal complexes were utilized for the selective recognition of CN- and I- ions. Pre-coated TLC plates were developed for rapid on-site detection of these toxic ions even in remote places. Finally, on a single molecular probe based on differential opto-chemical interactions with different ions (Cu2+, Hg2+, CN- and I-), we were able to design numerous trivial (OR, NOR) and non-trivial (INHIBIT, IMPLICATION, COMPLEMENT, TRANSFER, NOT-TRANSFER) logic gates. Most fascinatingly, we can switch the logic response from one type to another by simply tuning only the optical output channel.

Site-specific ammonia adsorption and transduction on a naphthalimide derivative molecule - a complementary analysis involving ab initio calculation and experimental verification.

Naphthalene diimide derivatives (NDIs) have exhibited significant potential for sensing applications owing to their excellent photo-stability, environmental stability, reasonable electronic conductivity, and ability to form nanostructures with diverse morphologies through self-assembly. However, no systematic analysis has been performed to rationalize molecular-level interactions between ammonia (NH3) and functionalized NDI probes, which is essential for systematic performance optimizations of NDI-based NH3 sensors. Therefore, this work proposes a phenylalanine-functionalized NDI derivative (NDI-PHE) as a model host for NH3 adsorption. Subsequent molecular interactions have been comprehensively studied following a complementary approach using ab initio calculation and experimental investigation. Specifically, NH3 adsorption at different atomic positions of NDI-PHE has been investigated using ab initio calculation, where the adsorption energy, charge transfer, and recovery time have been emphasized. The environmental stability of NDI-PHE and the underlying transduction mechanism during NH3 adsorption have been experimentally demonstrated to complement the theoretical analysis. The results exhibit that the presence of phenylalanine groups acts as an anchoring moiety and augments NH3 adsorption via hydrogen bonding and proton transfer interaction. Specifically, a highly stable room temperature adsorption of NH3 near a carboxylic phenylalanine group has been observed with a suitable recovery time at higher temperatures. NH3 adsorption results in electron transfer to the host molecule leading to the formation of stable radical anion species, which significantly modulated the frontal molecular orbitals of NDI-PHE, suggesting superior transduction for both electrochemical and optical detection.

Synthetic Supramolecular Host for D-(-)-Ribose: Ratiometric Fluorescence Response via Multivalent Lectin-Carbohydrate Interactions.

Easily synthesizable, carbazole-based organic nanoaggregates have been designed for selective detection of D-(-)-ribose at physiological pH. The addition of D-ribose results in a ratiometric change in fluorescence color from green to cyan (LOD: ∼12 µM). The mechanistic studies indicate the presence of multipoint noncovalent interactions, such as hydrogen bonding and CH⋅⋅⋅π interactions between D-ribose and acyl hydrazone and terminal pyridyl units of the probe molecule. However, such multipoint interactions dissociate the preformed self-assembled nanoclusters and induce change in optical response. The probe molecule was further exploited in analyzing D-ribose content in biological fluids (diluted human urine and blood serum) and oral supplements. The small standard deviation values (2-3.8 %) with nearly quantitative recovery (93.5-105.5 %) indicate the high accuracy of the presented method. Further, low-cost portable device based coated paper strips were designed for 'on-location' rapid, detection of D-ribose even at remote locations.

Monitoring Local pH of Membranous Aggregates via Ratiometric Color Changing Response.

A series of oxidized di(indolyl)arylmethanes (DIAM) with polyaromatic signaling moieties have been designed for monitoring local pH at the interfacial region of surfactant aggregates, such as micelles and vesicles. The oxidized DIAMs show changes in solution color from red to yellow when incorporated in cationic surfactants (at pH 7.4) and yellow to reddish pink when exposed to negatively-charged surfactants (at pH 5.0). The changes in surface charge can influence the interfacial pH (distinct from bulk pH of the medium) of the surfactant aggregates. The mechanistic studies indicate that the red-shifted absorption maxima observed in the presence of anionic amphiphiles (acidic local pH) originated from the protonated species. On the contrary, maxima in the blue region, triggered by positively charged amphiphiles (basic local pH), is attributed to the zwitterionic species. Such prototropic equilibrium affects charge transfer states of the molecules along with their self-assembly properties. Thus, it is evident that probes can predict as well as quantify the local pH change using the pseudophase ion exchange formalism. Also, the probes can detect the presence of anionic amphiphiles even when bound to phospholipid membranes.

Transparent decision support for mechanical ventilation using visualization of clinical preferences.

BACKGROUND: Systems aiding in selecting the correct settings for mechanical ventilation should visualize patient information at an appropriate level of complexity, so as to reduce information overload and to make reasoning behind advice transparent. Metaphor graphics have been applied to this effect, but these have largely been used to display diagnostic and physiologic information, rather than the clinical decision at hand. This paper describes how the conflicting goals of mechanical ventilation can be visualized and applied in making decisions. Data from previous studies are analyzed to assess whether visual patterns exist which may be of use to the clinical decision maker. MATERIALS AND METHODS: The structure and screen visualizations of a commercial clinical decision support system (CDSS) are described, including the visualization of the conflicting goals of mechanical ventilation represented as a hexagon. Retrospective analysis is performed on 95 patients from 2 previous clinical studies applying the CDSS, to identify repeated patterns of hexagon symbols. RESULTS: Visual patterns were identified describing optimal ventilation, over and under ventilation and pressure support, and over oxygenation, with these patterns identified for both control and support modes of mechanical ventilation. Numerous clinical examples are presented for these patterns illustrating their potential interpretation at the bedside. CONCLUSIONS: Visual patterns can be identified which describe the trade-offs required in mechanical ventilation. These may have potential to reduce information overload and help in simple and rapid identification of sub-optimal settings.

Agents intervening against delirium in the intensive care unit trial-Protocol for a secondary Bayesian analysis.

BACKGROUND: Delirium is highly prevalent in the intensive care unit (ICU) and is associated with high morbidity and mortality. The antipsychotic haloperidol is the most frequently used agent to treat delirium although this is not supported by solid evidence. The agents intervening against delirium in the intensive care unit (AID-ICU) trial investigates the effects of haloperidol versus placebo for the treatment of delirium in adult ICU patients. METHODS: This protocol describes the secondary, pre-planned Bayesian analyses of the primary and secondary outcomes up to day 90 of the AID-ICU trial. We will use Bayesian linear regression models for all count outcomes and Bayesian logistic regression models for all dichotomous outcomes. We will adjust for stratification variables (site and delirium subtype) and use weakly informative priors supplemented with sensitivity analyses using sceptical priors. We will present results as absolute differences (mean differences and risk differences) and relative differences (ratios of means and relative risks). Posteriors will be summarised using median values as point estimates and percentile-based 95% credibility intervals. Probabilities of any benefit/harm, clinically important benefit/harm and clinically unimportant differences will be presented for all outcomes. DISCUSSION: The results of this secondary, pre-planned Bayesian analysis will complement the primary frequentist analysis of the AID-ICU trial and facilitate a nuanced and probabilistic interpretation of the trial results.

McS-Net: Multi-class Siamese network for severity of COVID-19 infection classification from lung CT scan slices.

Worldwide COVID-19 is a highly infectious and rapidly spreading disease in almost all age groups. The Computed Tomography (CT) scans of lungs are found to be accurate for the timely diagnosis of COVID-19 infection. In the proposed work, a deep learning-based P-shot N-ways Siamese network along with prototypical nearest neighbor classifiers is implemented for the classification of COVID-19 infection from lung CT scan slices. For this, a Siamese network with an identical sub-network (weight sharing) is used for image classification with a limited dataset for each class. The feature vectors are obtained from the pre-trained sub-networks having weight sharing. The performance of the proposed methodology is evaluated on the benchmark MosMed dataset having categories zero (healthy control) and numerous COVID-19 infections. The proposed methodology is evaluated on (a) chest CT scans provided by medical hospitals in Moscow, Russia for 1110 patients, and (b) case study of low-dose CT scans of 42 patients provided by Avtaran healthcare in India. The deep learning-based Siamese network (15-shot 5-ways) obtained an accuracy of 98.07%, the sensitivity of 95.66%, specificity of 98.83%, and F1-score of 95.10%. The proposed work outperforms the COVID-19 infection severity classification with limited scans availability for numerous infection categories.

Dynamic Polymer Free Volume Monitored by Single-Molecule Spectroscopy of a Dual Fluorescent Flapping Dopant.

Single-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled real-time nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short- and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state. The observed spectral jumps were statistically analyzed to reveal the dynamics of the molecular environment. The analysis together with MD and QM/MM calculations show that the excited-state planarization of the flapping probe occurs only when sufficiently large polymer free volume of more than, at least, 280 Å3 is available close to the molecule, and that such free volume lasts for an average of 1.2 s.

Imidazole-Functionalized Y-Shaped Push-Pull Dye for Nerve Agent Sensing as well as a Catalyst for Their Detoxification.

A Y-shaped push-pull dye (1) with N,N-dimethylanilino donors and a benzonitrile acceptor connected via an imidazole-based π-conjugated spacer was designed. It showed a dark yellow color in solution due to facile intramolecular charge-transfer interaction, but no fluorescence was detected, presumably due to the photo-induced electron transfer effect of the imidazole moiety. However, addition of nerve agents such as diethyl chlorophosphate (DCP, sarin mimic) and diethyl cyanophosphate (DCNP, Tabun mimic) resulted in a blue-colored fluorescence with fading of the native dark yellow color. Mechanistic studies indicated nucleophilic attack of imidazole at the phosphorus of DCP or DCNP, leading to the formation of a phosphorylated intermediate, which undergoes time-dependent hydrolysis (∼24 h) in aqueous medium. This process recovers the free probe (enzyme-like behavior) and releases a less-toxic organophosphate compound as the byproduct. The phosphorylated derivative of 1, formed during such interaction, shows a different electronic behavior, which reduces the extent of charge-transfer interaction as well as nonradiative decay and supports emissive properties. Considering the high sensitivity of 1 towards DCP and DCNP with LOD 35 and 42 ppb, we prepared easy test strips for on-site vapor-phase detection of nerve agents.

Deep transfer learning-based automated detection of COVID-19 from lung CT scan slices.

Lung abnormality is one of the common diseases in humans of all age group and this disease may arise due to various reasons. Recently, the lung infection due to SARS-CoV-2 has affected a larger human community globally, and due to its rapidity, the World-Health-Organisation (WHO) declared it as pandemic disease. The COVID-19 disease has adverse effects on the respiratory system, and the infection severity can be detected using a chosen imaging modality. In the proposed research work; the COVID-19 is detected using transfer learning from CT scan images decomposed to three-level using stationary wavelet. A three-phase detection model is proposed to improve the detection accuracy and the procedures are as follows; Phase1- data augmentation using stationary wavelets, Phase2- COVID-19 detection using pre-trained CNN model and Phase3- abnormality localization in CT scan images. This work has considered the well known pre-trained architectures, such as ResNet18, ResNet50, ResNet101, and SqueezeNet for the experimental evaluation. In this work, 70% of images are considered to train the network and 30% images are considered to validate the network. The performance of the considered architectures is evaluated by computing the common performance measures. The result of the experimental evaluation confirms that the ResNet18 pre-trained transfer learning-based model offered better classification accuracy (training = 99.82%, validation = 97.32%, and testing = 99.4%) on the considered image dataset compared with the alternatives.

A new SEAIRD pandemic prediction model with clinical and epidemiological data analysis on COVID-19 outbreak.

Measuring the spread of disease during a pandemic is critically important for accurately and promptly applying various lockdown strategies, so to prevent the collapse of the medical system. The latest pandemic of COVID-19 that hits the world death tolls and economy loss very hard, is more complex and contagious than its precedent diseases. The complexity comes mostly from the emergence of asymptomatic patients and relapse of the recovered patients which were not commonly seen during SARS outbreaks. These new characteristics pertaining to COVID-19 were only discovered lately, adding a level of uncertainty to the traditional SEIR models. The contribution of this paper is that for the COVID-19 epidemic, which is infectious in both the incubation period and the onset period, we use neural networks to learn from the actual data of the epidemic to obtain optimal parameters, thereby establishing a nonlinear, self-adaptive dynamic coefficient infectious disease prediction model. On the basis of prediction, we considered control measures and simulated the effects of different control measures and different strengths of the control measures. The epidemic control is predicted as a continuous change process, and the epidemic development and control are integrated to simulate and forecast. Decision-making departments make optimal choices. The improved model is applied to simulate the COVID-19 epidemic in the United States, and by comparing the prediction results with the traditional SEIR model, SEAIRD model and adaptive SEAIRD model, it is found that the adaptive SEAIRD model's prediction results of the U.S. COVID-19 epidemic data are in good agreement with the actual epidemic curve. For example, from the prediction effect of these 3 different models on accumulative confirmed cases, in terms of goodness of fit, adaptive SEAIRD model (0.99997) ≈ SEAIRD model (0.98548) > Classical SEIR model (0.66837); in terms of error value: adaptive SEAIRD model (198.6563) < < SEAIRD model(4739.8577) < < Classical SEIR model (22,652.796); The objective of this contribution is mainly on extending the current spread prediction model. It incorporates extra compartments accounting for the new features of COVID-19, and fine-tunes the new model with neural network, in a bid of achieving a higher level of prediction accuracy. Based on the SEIR model of disease transmission, an adaptive model called SEAIRD with internal source and isolation intervention is proposed. It simulates the effects of the changing behaviour of the SARS-CoV-2 in U.S. Neural network is applied to achieve a better fit in SEAIRD. Unlike the SEIR model, the adaptive SEAIRD model embraces multi-group dynamics which lead to different evolutionary trends during the epidemic. Through the risk assessment indicators of the adaptive SEAIRD model, it is convenient to measure the severity of the epidemic situation for consideration of different preventive measures. Future scenarios are projected from the trends of various indicators by running the adaptive SEAIRD model.

A two-component charge transfer hydrogel with excellent sensitivity towards the microenvironment: a responsive platform for biogenic thiols.

A two-component charge transfer (CT) hydrogel has been derived from a supramolecular heteroassembly of a pyrene amino acid conjugate (PyHisOH, donor) with a 4-chloro-7-nitrobenzofurazan (NBD-Ox, acceptor) derivative in aqueous medium. The mechanical stiffness, as well as the thermal stability of the CT hydrogels largely depend on the relative ratios of donor and acceptor units as well as on their overall concentration. Moreover, the gel-to-sol transition is found to be susceptible to various external stimuli such as heat, pH, metal ions, etc. Circular dichroism and morphological investigation reveal the formation of left-handed helical fibers in the CT gel network. XRD studies show the lamellar packing of the interactive units in the 3D network of the CT hydrogel. The determination of different rheological parameters confirms the viscoelastic as well as the thixotropic nature of the CT gel. Furthermore, the CT gel is employed for turn-on sensing of biogenic thiols, cyan fluorescence was observed with cysteine/homocysteine, while blue fluorescence with glutathione. Nucleophilic attack at the NBD moiety leads to the formation of thermodynamically stable amino-linked derivatives for cysteine or homocysteine and kinetically controlled thiol-linked adduct for glutathione. Thus, the current system presents a unique opportunity, where a CT hydrogel sample is involved for discriminating biogenic thiols via specific chemodosimetric interactions.