Nanoscale assembly of enantiomeric supramolecular gels driven by the nature of solvents.

Understanding the key parameters that control the self-assembly process is critical to predict self-assembly modes in multi-component systems, which will lead to the development of nanofibrous materials with tuneable properties. Enantiomeric amino acid-based low-molecular-weight gelators (LMWGs) were mixed in polar (polar protic) and aromatic apolar (aromatic) solvents and compared to their individual counterparts to probe the effect of solvent polarity on the self-assembly process. Scanning electron microscopy (SEM) reveals that xerogels of individual components display hollow needles in polar protic solvents, while chiral coils are observed in aromatic solvents. In contrast, the multi-component gel displays hollow needle morphologies in both solvents, indicating similar morphologies in polar protic solvents but an entirely different nanostructure for the individual gel networks in aromatic solvents. PXRD experiments performed on the dried gels showed that the nature of the solvents plays a vital role in the co-assembly process of multi-component gels. The self-assembly modes and the gel state structure of the gels are analysed by wide-angle X-ray diffraction (WAXS) and small-angle neutron diffraction (SANS), which reveals that the mixed gel undergoes different co-assembly modes depending on the nature of the solvent systems. This study shows that different co-assembly modes can be achieved for structurally similar components by varying the solvent polarity, demonstrating the importance of solvent choice in the self-assembly process of multi-component gels.

Metal Cross-Linked Supramolecular Gel Noodles: Structural Insights and Antibacterial Assessment.

Achieving precise control over gelator alignment and morphology is crucial for crafting tailored materials and supramolecular structures with distinct properties. We successfully aligned the self-assembled micelles formed by a functionalized dipeptide 2NapFF into long 1-D "gel noodles" by cross-linking with divalent metal chlorides. We identify the most effective cross-linker for alignment, enhancing mechanical stability, and imparting functional properties. Our study shows that Group 2 metal ions are particularly suited for creating mechanically robust yet flexible gel noodles because of their ionic and nondirectional bonding with carboxylate groups. In contrast, the covalent nature and high directional bonds of d-block metal ions with carboxylates tend to disrupt the self-assembly of 2NapFF. Furthermore, the 2NapFF-Cu noodles demonstrated selective antibacterial activity, indicating that the potent antibacterial property of the copper(II) ion is preserved within the cross-linked system. By merging insights into molecular alignment, gel extrusion processing, and integrating specific functionalities, we illustrate how the versatility of dipeptide-based gels can be utilized in creating next-generation soft materials.

Stimuli-Responsive Properties of Supramolecular Gels Based on Pyridyl-N-oxide Amides.

The nature of functional groups and their relative position and orientation play an important role in tuning the gelation properties of stimuli-responsive supramolecular gels. In this work, we synthesized and characterized mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)nicotinamide (L1-L3). The gelation properties of these N-oxide compounds were compared with the reported isomeric counterpart mono-/bis-pyridyl-N-oxide compounds of N-(4-pyridyl)isonicotinamide. Hydrogels obtained with L1 and L3 were thermally and mechanically more stable than the corresponding isomeric counterparts. The surface morphology of the xerogels of di-N-oxides (L3 and diNO) obtained from the water was studied using scanning electron microscopy (SEM), which revealed that the relative position of N-oxide moieties did not have a prominent effect on the gel morphology. The solid-state structural analysis was performed using single-crystal X-ray diffraction to understand the key mechanism in gel formation. The versatile nature of N-oxide moieties makes these gels highly responsive toward an external stimulus, and the stimuli-responsive behavior of the gels in water and aqueous mixtures was studied in the presence of various salts. We studied the effect of various salts on the gelation behavior of the hydrogels, and the results indicated that the salts could induce gelation in L1 and L3 below the minimum gelator concentration of the gelators. The mechanical properties were evaluated by rheological experiments, indicating that the modified compounds displayed enhanced gel strength in most cases. Interestingly, cadmium chloride formed supergelator at a very low concentration (0.7 wt% of L3), and robust hydrogels were obtained at higher concentrations of L3. These results show that the relative position of N-oxide moieties is crucial for the effective interaction of the gelator with salts/ions resulting in LMWGs with tunable properties.

Microbial assemblage for solid waste bioremediation and valorization with an essence of bioengineering.

Environmental solid waste bioremediation is a method of treating contaminated solid waste that involves changing ecological conditions to foster the growth of a broad spectrum of microorganisms and the destruction of the target contaminants. A wide range of microorganisms creates metabolites that may break down and change solid waste-based pollution to various value-added molecules. Diverse bioremediation technologies, their limitations, and the procedure involve recycling solid waste materials from the environment. The existing environmental solid waste disposal services are insufficient and must be upgraded with more lucrative recovery, recycling, and reuse technologies to decrease the enormous expenditures in treatment procedures. Bioremediation of solid waste eliminates the toxic components. It restores the site with the advent of potential microbial communities towards solid waste valorization utilizing agriculture solid waste, organic food waste, plastic solid waste, and multiple industrial solid wastes.Bioengineering on diverse ranges of microbial regimes has accelerated to provide extra momentum toward solid waste recycling and valorization. This approach increases the activity of bioremediating microbes in the commercial development of waste treatment techniques and increases the cost-effective valuable product generation. This framework facilitates collaboration between solid waste and utilities. It can aid in establishing a long-term management strategy for recycling development with the advent of a broad spectrum of potential microbial assemblages, increasing solid waste contamination tolerance efficiency and solid waste degradability. The current literature survey extensively summarises solid waste remediation valorization using a broad spectrum of microbial assemblages with special emphasis on bioengineering-based acceleration. This approach is to attain sustainable environmental management and value-added biomolecule generation.

Single-Step Capture and Targeted Metabolomics of Alkyl-Quinolones in Outer Membrane Vesicles (OMVs) of Pseudomonas Aeruginosa.

Outer membrane vesicles (OMVs), also called as bacterial membrane vesicles (BMVs), are secreted by many Gram-negative bacterial pathogens. These nanoscale vesicles traffic discrete arrays of virulence factors that can often induce complex pathologies far from the infection sites. The OMVs of P. aeruginosa, often regarded as the gold standard of BMVs are known to traffic a battery of specific small MW alkyl-quinolones (AQs). These AQs function like primordial hormones by modulating intra-species and inter-species bacterial interactions. They can also perform cross-kingdom signaling with the human host and directly exacerbate pathogenesis. The discrete isotopic signatures of AQs enjoy potential in the mass spectrometry-based diagnosis P. aeruginosa infections. Matrix-free laser desorption/ionization mass spectrometry (LDI-MS) presents a robust, cost-effective platform to fit this demand. We describe a LDI-MS system using inert ceramic filters that performs dual role of single-step enrichment of OMVs and matrix-free ionization/identification of AQs in situ.

Transferring Micellar Changes to Bulk Properties via Tunable Self-Assembly and Hierarchical Ordering.

Hierarchical self-assembly is an effective means of preparing useful materials. However, control over assembly across length scales is a difficult challenge, often confounded by the perceived need to redesign the molecular building blocks when new material properties are needed. Here, we show that we can treat a simple dipeptide building block as a polyelectrolyte and use polymer physics approaches to explain the self-assembly over a wide concentration range. This allows us to determine how entangled the system is and therefore how it might be best processed, enabling us to prepare interesting analogues to threads and webs, as well as films that lose order on heating and "noodles" which change dimensions on heating, showing that we can transfer micellar-level changes to bulk properties all from a single building block.

Analysing the role of anions in the synthesis of catalytically active urea-based MOFs.

The synthesis of catalytically active metal-organic frameworks (MOFs) with copper(II) paddle-wheel clusters and urea-carboxylate linkers was achieved at room temperature in the presence of sulphate anions. The role of various anions in determining the MOF structure was analysed using X-ray diffraction. Structural analysis of the MOFs indicated that a two-fold interpenetrated rhombus grid (HI-101) was formed in the presence of sulphate anions, but a three-fold interpenetrated square grid network (HI-102) was obtained with nitrate and perchlorate anions. The experiment performed with various anions in the presence of sulphate anions also resulted in the formation of HI-101, indicating the selectivity of sulphate anions in the formation of the HI-101 framework. HI-101 proved to be an efficient catalyst for the cycloaddition of CO2 at room temperature, the oxidation of primary alcohols to aldehydes and the methanolysis of epoxides, but the other MOFs were not catalytically active. Thus, the size, charge and affinity of sulphate anions play an important role in generating a two-fold interpenetrated rhombus grid, which is crucial for catalytic reactions. This study shows that anion-templated synthesis could generate a versatile urea-based MOF catalyst for CO2 fixation and other reactions.

Resolution of Papilledema Following Ventriculoperitoneal Shunt or Endoscopic Third Ventriculostomy for Obstructive Hydrocephalus: A Pilot Study.

Background and Objectives: Ventriculoperitoneal Shunt (VPS) and Endoscopic Third Ventriculostomy (ETV) are both gold standard procedures to reduce intracranial pressure (ICP) in patients with obstructive hydrocephalus, which often results in papilledema. This comparative study was carried out at the Department of Neurosurgery of Dhaka Medical College and Hospital to compare the efficacy of VPS and ETV in the resolution of papilledema in 18 patients with obstructive hydrocephalus. Materials and Methods: The success of CSF diversion was evaluated by a decrease in retinal nerve fiber layer (RNFL) thickness by optical coherence tomography (OCT) and modified Frisen grading of papilledema at the same time. The statistical analyses were carried out by using paired sample t test and the Spearman's correlation coefficient test. The level of significance (p value) was set at <0.05. Results: After 7 days, both VPS and ETV were able to reduce RNFL thickness of both eyes with a p value = 0.016 (right eye) and 0.003 (left eye) in group A (VPS) and with a p value <0.001 (both eyes) in group B (ETV). Change of Frisen grading after CSF diversion was not satisfying for both the procedures with p value > 0.05. Further, the inter-group comparison between VPS and ETV showed no difference in decreasing RNFL thickness and modified Frisen grading (p value = 0.56). Conclusion: VPS and ETV procedures both appear very efficient in treating obstructive hydrocephalus, which in turn reduces papilledema in these patients. This paper is preliminary and requires further work.

Designing a single-mode anomalous dispersion silicon core fiber for temporal multiplet formation.

A highly nonlinear single-mode anomalous dispersion silicon core fiber (SCF) is suitably designed and optimized to generate a high repetition rate pulse train in the temporal domain from a single input pulse at a sufficiently shorter optimum length in comparison to silica-based standard fibers used for the same purpose. The large amount of Kerr-induced nonlinearity of a SCF is effectively utilized here such that input Gaussian pulses or pulse trains transform into a highly repetitive temporal multiplet. The effects of free-carrier generation-induced change in absorption and dispersion are included while studying the nonlinear pulse propagation through the SCF. To declare the generated pulse as a superior-graded triplet, a Q parameter, as a function of relative pulse parameters of the individual pulses of a triplet, is defined for the first time, to the best of our knowledge. Different pulse parameters are thoroughly optimized as well as the effect of external gain is examined from the perspective of requirement of shorter fiber length and development of quality triplets. Finally, the work is further extended for the formation of quadruplet pulses by the same type of SCF. It is to be mentioned here that such a methodical study for the generation of a temporal multiplet using a semiconductor core fiber has not been reported earlier.

Dynamical analysis of novel COVID-19 epidemic model with non-monotonic incidence function.

In this study, we developed and analyzed a mathematical model for explaining the transmission dynamics of COVID-19 in India. The proposed SI u I k R model is a modified version of the existing SIR model. Our model divides the infected class I of SIR model into two classes: I u (unknown infected class) and I k (known infected class). In addition, we consider R a recovered and reserved class, where susceptible people can hide them due to fear of the COVID-19 infection. Furthermore, a non-monotonic incidence function is deemed to incorporate the psychological effect of the novel coronavirus diseases on India's community. The epidemiological threshold parameter, namely the basic reproduction number, has been formulated and presented graphically. With this threshold parameter, the local and global stability analysis of the disease-free equilibrium and the endemic proportion equilibrium based on disease persistence have been analyzed. Lastly, numerical results of long-run prediction using MATLAB show that the fate of this situation is very harmful if people are not following the guidelines issued by the authority.

Making and Breaking of Gels: Stimuli-Responsive Properties of Bis(Pyridyl-N-oxide Urea) Gelators.

The structural modification of existing supramolecular architecture is an efficient strategy to design and synthesize supramolecular gels with tunable and predictable properties. In this work, we have modified bis(pyridyl urea) compounds with different linkers, namely hexylene and butylene, to their corresponding bis(pyridyl-N-oxide urea). The gelation properties of both the parent and the modified compounds were studied, and the results indicated that modification of the 3-pyridyl moieties to the corresponding 3-pyridyl-N-oxides induced hydrogelation. The stability of the parent and modified compounds were evaluated by sol-gel transition temperature (Tgel) and rheological measurements, and single-crystal X-ray diffraction was used to analyze the solid-state interactions of the gelators. The morphologies of the dried gels were analyzed by scanning electron microscopy (SEM), which revealed that the structural modification did not induce any prominent effect on the gel morphology. The stimuli-responsive behavior of these gels in the presence of salts in DMSO/water was evaluated by rheological experiments, which indicated that the modified compounds displayed enhanced gel strength in most cases. However, the gel network collapsed in the presence of the chloride salts of aluminum(III), zinc(II), copper(II), and cadmium(II). The mechanical strength of the parent gels decreased in the presence of salts, indicating that the structural modification resulted in robust gels in most cases. The modified compounds formed gels below minimum gel concentration in the presence of various salts, indicating salt-induced gelation. These results show the making and breaking ability of the gel network in the presence of external stimuli (salts), which explains the potential of using LMWGs based on N-oxide moieties as stimuli-responsive materials.

Enantioselective Gel Phase Synthesis of Metal-Organic Materials.

We report the asymmetric synthesis of homochiral metal-organic materials (MOMs) in chiral gels from achiral components. The enantioselectivity of MOMs depends on the chirality of the gel, whereas the synthesis performed in solution phase and achiral gels resulted in conglomerates.

A fractional order SITR mathematical model for forecasting of transmission of COVID-19 of India with lockdown effect.

In this paper, we consider a mathematical model to explain, understanding, and to forecast the outbreaks of COVID-19 in India. The model has four components leading to a system of fractional order differential equations incorporating the refuge concept to study the lockdown effect in controlling COVID-19 spread in India. We investigate the model using the concept of Caputo fractional-order derivative. The goal of this model is to estimate the number of total infected, active cases, deaths, as well as recoveries from COVID-19 to control or minimize the above issues in India. The existence, uniqueness, non-negativity, and boundedness of the solutions are established. In addition, the local and global asymptotic stability of the equilibrium points of the fractional-order system and the basic reproduction number are studied for understanding and prediction of the transmission of COVID-19 in India. The next step is to carry out sensitivity analysis to find out which parameter is the most dominant to affect the disease's endemicity. The results reveal that the parameters η , µ and ρ are the most dominant sensitivity indices towards the basic reproductive number. A numerical illustration is presented via computer simulations using MATLAB to show a realistic point of view.

Role of N-Oxide Moieties in Tuning Supramolecular Gel-State Properties.

The role of specific interactions in the self-assembly process of low molecular weight gelators (LMWGs) was studied by altering the nonbonding interactions responsible for gel formation via structural modification of the gelator/nongelator. This was achieved by modifying pyridyl moieties of bis(pyridyl) urea-based hydrogelator (4-BPU) and the isomer (3-BPU) to pyridyl N-oxide compounds (L1 and L2, respectively). The modification of the functional groups resulted in the tuning of the gelation properties of the parent gelator, which induced/enhanced the gelation properties. The modified compounds displayed better mechanical and thermal stabilities and the introduction of the N-oxide moieties had a prominent effect on the morphologies of the gel network, which was evident from the scanning electron microscopy (SEM) images. The effect of various interactions due to the introduction of N-oxide moieties in the gel network formation was analyzed by comparing the solid-state interactions of the compounds using single crystal X-ray diffraction and computational studies, which were correlated with the enhanced gelation properties. This study shows the importance of specific nonbonding interactions and the spatial arrangement of the functional groups in the supramolecular gel network formation.

Tuning Gel State Properties of Supramolecular Gels by Functional Group Modification.

The factors affecting the self-assembly process in low molecular weight gelators (LMWGs) were investigated by tuning the gelation properties of a well-known gelator N-(4-pyridyl)isonicotinamide (4PINA). The N-H∙∙∙N interactions responsible for gel formation in 4PINA were disrupted by altering the functional groups of 4PINA, which was achieved by modifying pyridyl moieties of the gelator to pyridyl N-oxides. We synthesized two mono-N-oxides (INO and PNO) and a di-N-oxide (diNO) and the gelation studies revealed selective gelation of diNO in water, but the two mono-N-oxides formed crystals. The mechanical strength and thermal stabilities of the gelators were evaluated by rheology and transition temperature (Tgel) experiments, respectively, and the analysis of the gel strength indicated that diNO formed weak gels compared to 4PINA. The SEM image of diNO xerogels showed fibrous microcrystalline networks compared to the efficient fibrous morphology in 4PINA. Single-crystal X-ray analysis of diNO gelator revealed that a hydrogen-bonded dimer interacts with adjacent dimers via C-H∙∙∙O interactions. The non-gelator with similar dimers interacted via C-H∙∙∙N interaction, which indicates the importance of specific non-bonding interactions in the formation of the gel network. The solvated forms of mono-N-oxides support the fact that these compounds prefer crystalline state rather than gelation due to the increased hydrophilic interactions. The reduced gelation ability (minimum gel concentration (MGC)) and thermal strength of diNO may be attributed to the weak intermolecular C-H∙∙∙O interaction compared to the strong and unidirectional N-H∙∙∙N interactions in 4PINA.

Quantitation of Neurotoxic Metabolites of the Kynurenine Pathway by Laser Desorption Ionization Mass Spectrometry (LDI-MS).

The metabolites of the mammalian kynurenine (KYN) pathway are generated from a branch of tryptophan metabolic pathway. The latter generates 3-hydroxykynurenine (3-HK), kynurenic acid (KYNA), quinolinic acid (QUIN), and picolinic acid (PIC) which are all strongly neuroactive, often with dramatically contrasting functional outcomes. Whereas KYNA and PIC are neuroprotective, 3-HK and QUIN are potently neurotoxic and attributed in major neurodegenerative diseases like schizophrenia, Alzheimer's disease, Huntington's disease, bipolar disorder, and depression. It is increasingly evident that the ratio(s) between the neurotoxic and neuroprotective metabolites may help predict the manifestations of disease vs. health. Therefore high-throughput platforms for determining the relative levels of these kynurenine metabolites in biofluids offer considerable potential. Current analytical tools for studying KYN pathway include assays of branching enzymes, PCR, immunoanalysis, and LCMS. None of these offer high-throughput, cost-effective analyses suited for clinical or drug-screening applications. In this report a laser desorption ionization mass spectrometry (LDI-MS) method is described using SBA-15 mesoporous silica. The system allows fast, high-resolution quantitation of neurotoxic kynurenines using targeted metabolomics on conventional MALDI platforms.

Assays for Intracellular Cyclic Adenosine Monophosphate (cAMP) and Lysosomal Acidification.

Cyclic adenosine monophosphate (3',5'-cAMP) is a multifunctional second messenger which controls extremely diverse and physiologically important biochemical pathways. Among its myriad roles, 3',5'-cAMP functions as an intracellular regulator of lysosomal pH, which is essential for the activity of acidic lysosomal enzymes. Defects in lysosomal acidification are attributed to many diseases like macular degeneration, Parkinson's, Alzheimer's, and cystic fibrosis. Strategic re-acidification of defective lysosomes by pharmacological increase of intracellular cAMP offers exciting therapeutic potential in these diseases. Modular assays for accurate assessment of intracellular cAMP and lysosomal pH are a critical component of this research. We describe label-free targeted metabolomics for quantitating intracellular cAMP and integrated assays for measuring lysosomal pH. These hybrid assays offer fast, unbiased information on intracellular cAMP concentrations and lysosomal pH that can be applied to many cell types and putative drug screening strategies.

Enhanced Mechanical and Thermal Strength in Mixed-Enantiomers-Based Supramolecular Gel.

Mixing supramolecular gels based on enantiomers leads to re-arrangement of gel fibers at the molecular level, which results in more favorable packing and tunable properties. Bis(urea) compounds tagged with a phenylalanine methyl ester in racemic and enantiopure forms were synthesized. Both enantiopure and racemate compounds formed gels in a wide range of solvents and the racemate (1-rac) formed a stronger gel network compared with the enantiomers. The gel (1R+1S) obtained by mixing equimolar amount of enantiomers (1R and 1S) showed enhanced mechanical and thermal stability compared to enantiomers and racemate gels. The preservation of chirality in these compounds was analyzed by circular dichroism and optical rotation measurements. Analysis of the scanning electron microscopy (SEM) and atomic force microscopy (AFM) images revealed that the network in the mixed gel is a combination of enantiomers and racemate fibers, which was further supported by solid-state NMR. The analysis of the packing in xerogels by solid-state NMR spectra and the existence of twisted-tape morphology in SEM and AFM images confirmed the presence of both self-sorted and co-assembled fibers in mixed gel. The enhanced thermal and mechanical strength may be attributed to the enhanced intermolecular forces between the racemate and the enantiomer and the combination of both self-sorted and co-assembled enantiomers in the mixed gel.

Prospective use of a normally dispersive step-index chalcogenide fiber in nonlinear pulse reshaping.

In this work, several normally dispersive highly nonlinear chalcogenide optical fibers (NDHNCFs) with a step-index profile have been designed and optimized in view of efficient parabolic pulse (PP) generation. A typical NDHNCF is selected such that the group velocity dispersion is highest among them and the corresponding nonlinearity is also very high. The input pulse parameters are optimized to find the lowest possible optimum length (Lopt) of the fiber where the linearly chirped PP is obtained. Further, it is found that for a shorter input pulse width, PP can be generated at a sufficiently smaller length of the NDHNCF with a slight compromise for its misfit parameter. A detailed analysis of the effect of pre-chirping helps to identify the suitable amount of initial chirp for different chalcogenide fibers with a choice of input pulse parameters. Although no improvement in PP generation is found for normal and initially chirped hyperbolic secant pulses, a highly efficient triangular pulse is achieved for a particular value of input pulse energy and the initial chirp parameter. Finally, the comparative study substantiates that our optimized NDHNCF is capable enough to generate quality PP at a length almost 70% shorter than a standard silica-based fiber.

Degradation and Stability of Polymeric High-Voltage Insulators and Prediction of Their Service Life through Environmental and Accelerated Aging Processes.

Polymeric composite insulators consisting of core fiber reinforced polymer insulators covered with polydimethylsiloxane (PDMS) housing are now replacing conventional ceramic insulators especially for high-outdoor power transmission lines due to some specific advantages. Unlike ceramics, polymers have relatively shorter life. Outdoor insulators experience different electrical, mechanical, chemical, and thermal stresses during service. The long-term service performance of these insulators and their service life estimation is an important issue, but it is complicated and time-consuming. The objective of the present investigation is to check the rate of property deterioration during service and to find the approximate lifetime. Working insulators with different ages were collected from service, and the changes in mechanical and electrical properties and hydrophobicity of the PDMS cover against aging time were measured. The service life estimated from the change in mechanical properties and surface hydrophobicity (using MATLAB software) was compared with the service life of a new compound subjected to accelerated aging tests. Prediction of service life is helpful for replacement of aged insulators from service to avoid interruption in power transmission.