A novel GO hoisted SnO2-BiOBr bifunctional catalyst for the remediation of organic dyes under illumination by visible light and electrocatalytic water splitting.

It is imperative to develop affordable multi-functional catalysts based on transition metals for various applications, such as dye degradation or the production of green energy. For the first time, we propose a simple chemical bath method to create a SnO2-BiOBr-rGO heterojunction with remarkable photocatalytic and electrocatalytic activities. After introducing graphene oxide (GO) into the SnO2-BiOBr nanocomposite, the charge separation, electron mobility, surface area, and electrochemical properties were significantly improved. The X-ray diffraction results show the successful integration of GO into the SnO2-BiOBr nanocomposite. Systematic material characterization by scanning and transmission electron microscopy showed that the photocatalysts are composed of uniformly distributed SnO2 nanoparticles (∼11 nm) on the regular nanosheets of BiOBr (∼94 nm) and rGO. The SnO2-BiOBr-rGO photocatalyst has outstanding photocatalytic activity when it comes to reducing a variety of organic dyes like rhodamine B (RhB) and methylene blue (MB). Within 90 minutes of visible light illumination, degradation of a maximum of 99% for MB and 99.8% for RhB was noted. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance was also tested for the ternary nanocomposite, and significantly lower overpotential values of 0.34 and -0.11 V (vs. RHE) at 10 mA cm-2 were observed for the OER and HER, respectively. Furthermore, the Tafel slope values are 34 and 39 mV dec-1 for the OER and HER, respectively. The catalytic degradation of dyes with visible light and efficient OER and HER performance offer this work a broad spectrum of potential applications.

Analyzing of L-tryptophan thermodynamics and its solubility in aqueous acetonitrile blends at diverse temperatures.

This paper delves into an investigation of the solubility characteristics of L-tryptophan within binary solvent systems containing aqueous acetonitrile. The primary emphasis of the study revolves around assessments based on mole fractions. The study utilizes these solubility values to assess thermodynamic constraints, including solution entropies and solution transfer free energetics. The calculated thermodynamic energies are correlated with interaction parameters, including Gibbs free energies and entropies, pertaining to the transfer of L-tryptophanfrom water to binary solvent blends of acetonitrile and water. Mathematical expressions are utilized to determine the transfer Gibbs free energies for chemical interactions, and the consequent entropies are clarified within the framework of solvent-solvent interactions. To expound upon the stability of L-tryptophan within the water-acetonitrile mixed system, we investigate the energetic aspects related to the transfer of chemicals Gibbs free energies. Additionally, standard temperature (298.15 K) is employed to calculate various related physicochemical parameters of solute/solvent.

Solvent-Free Synthesis of S,N-Doped Carbon Dots for Extended Visible-Light-Induced Oxidase-Mimicking Activities and Antimicrobial Applications.

Photo-oxidase nanozymes are emerging enzyme-mimicking materials that produce reactive oxygen species (ROS) upon light illumination and subsequently catalyze the oxidation of the substrate. Carbon dots are promising photo-oxidase nanozymes due to their biocompatibility and straightforward synthesis. Carbon dot-based photo-oxidase nanozymes become active for ROS generation under UV or blue light illumination. In this work, sulfur and nitrogen doped carbon dots (S,N-CDs) were synthesized by solvent-free, microwave assisted technique. We demonstrated that sulfur, nitrogen doping of carbon dots (band gap of 2.11 eV) has enabled photo-oxidation of 3,3,5,5'-tetramethylbenzidine (TMB) with extended visible light (up to 525 nm) excitation at pH 4. The photo-oxidase activities by S,N-CDs produce Michaelis-Menten constant (Km ) of 1.18 mM and the maximum initial velocity (Vmax ) as 4.66×10-8  Ms-1 , under 525 nm illumination. Furthermore, visible light illumination can also induce bactericidal activities with growth inhibition of Escherichia coli (E. coli). These results demonstrate that S,N-CDs can increase intracellular ROS in the presence of LED light illumination.

NIR-Driven Photocatalytic Hydrogen Production by Silane- and Tertiary Amine-Bound Plasmonic Gold Nanoprisms.

Near-infrared (NIR) photon-driven H2 production from water is regarded as one of the best routes for establishing a sustainable hydrogen-based energy economy. Here, we have developed a gold nanoprism-based photocatalytic assembly, rationally capped with an amine and a silane ligand pair, which exhibited an excellent H2 production rate (146 µL mg-1 h-1) in neutral water while achieving an absolute incident photon-to-hydrogen conversion efficiency of 0.53%. An array of spectroscopic and microscopic experiments unravel that the amine ligand scavenges the hot hole while the silane aids the H2 production via hydrolysis during the photocatalysis on the plasmon surface. This photocatalytic H2 production reactivity can be retained for multiple cycles following the replenishment of amine and silane. Hence, this photocatalytic assembly can set up the template for a large-scale NIR-driven H2 production unit.

Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects.

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7, 5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions, additional gate-dependent emission lines appear, which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6, 5) nanotubes. We also compare functionalized (7, 5) electroluminescence data with photoluminescence of pristine and functionalized (7, 5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.

Positive Antinuclear Antibody (ANA)-Negative Systemic Lupus Erythematosus (SLE) Presenting With Acute Pancreatitis.

Systemic lupus erythematosus (SLE) is an autoimmune disease with multisystem involvement and most commonly affects women of childbearing age. Most of the patients, if not all, have positive antinuclear antibody (ANA) in their serum. ANA-negative SLE is extremely rare. Here, we present a case of a 15-year-old girl presenting with pancreatitis due to ANA-negative SLE.

Perspectives About Modulating Host Immune System in Targeting SARS-CoV-2 in India.

Severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2), the causative agent of coronavirus induced disease-2019 (COVID-19), is a type of common cold virus responsible for a global pandemic which requires immediate measures for its containment. India has the world's largest population aged between 10 and 40 years. At the same time, India has a large number of individuals with diabetes, hypertension and kidney diseases, who are at a high risk of developing COVID-19. A vaccine against the SARS-CoV-2, may offer immediate protection from the causative agent of COVID-19, however, the protective memory may be short-lived. Even if vaccination is broadly successful in the world, India has a large and diverse population with over one-third being below the poverty line. Therefore, the success of a vaccine, even when one becomes available, is uncertain, making it necessary to focus on alternate approaches of tackling the disease. In this review, we discuss the differences in COVID-19 death/infection ratio between urban and rural India; and the probable role of the immune system, co-morbidities and associated nutritional status in dictating the death rate of COVID-19 patients in rural and urban India. Also, we focus on strategies for developing masks, vaccines, diagnostics and the role of drugs targeting host-virus protein-protein interactions in enhancing host immunity. We also discuss India's strengths including the resources of medicinal plants, good food habits and the role of information technology in combating COVID-19. We focus on the Government of India's measures and strategies for creating awareness in the containment of COVID-19 infection across the country.

Rare case of autoimmune hypothyroidism presenting with pancytopenia.

Hypothyroidism can involve any organ system in the body with the involvement of haematopoietic system seen in about 30% of the cases. Anaemia is the most common haematological involvement with the affection of other cell lines being exceedingly rare and limited to occasional case reports. Here we present a case of a 14-year-old boy who presented with fever and pancytopenia and was later diagnosed to be a case of autoimmune hypothyroidism.

A novel zinc sulfide impregnated carbon composite derived from zeolitic imidazolate framework-8 for sodium-ion hybrid solid-state flexible capacitors.

The pyrolysis of metal-organic frameworks (MOFs) is an easy approach to prepare metal oxides as well as nanoporous carbon with high specific surface area. In the present work, for the first time, ZIF-8 (zeolitic imidazolate framework-8) has been pyrolyzed under different conditions to derive two products, i.e., highly porous carbon (C) and zinc sulfide (ZnS) infused carbon (ZnS@C). These two materials, i.e., nanoporous C and ZnS@C, have been investigated as a negative and a positive electrode, respectively, for potential application in a hybrid asymmetrical solid-state supercapacitor device (HASD). The controlled pyrolysis approach for the preparation of ZnS@C has yielded uniformly distributed ZnS nanoparticles inside the carbon structure. A 1.8 V HASD has been assembled, which delivered an excellent energy density of 38.3 W h kg-1 (power density of 0.92 kW kg-1) along with the greatly desirable feature of cycling stability. The proposed selection of materials as electrodes is promising to develop futuristic hybrid capacitors.

MBA: Mini-Batch AUC Optimization.

Area under the receiver operating characteristics curve (AUC) is an important metric for a wide range of machine-learning problems, and scalable methods for optimizing AUC have recently been proposed. However, handling very large data sets remains an open challenge for this problem. This article proposes a novel approach to AUC maximization based on sampling mini-batches of positive/negative instance pairs and computing U-statistics to approximate a global risk minimization problem. The resulting algorithm is simple, fast, and learning-rate free. We show that the number of samples required for good performance is independent of the number of pairs available, which is a quadratic function of the positive and negative instances. Extensive experiments show the practical utility of the proposed method.

Hidden Fine Structure of Quantum Defects Revealed by Single Carbon Nanotube Magneto-Photoluminescence.

Organic color-center quantum defects in semiconducting carbon nanotube hosts are rapidly emerging as promising candidates for solid-state quantum information technologies. However, it is unclear whether these defect color-centers could support the spin or pseudospin-dependent excitonic fine structure required for spin manipulation and readout. Here we conducted magneto-photoluminescence spectroscopy on individual organic color-centers and observed the emergence of fine structure states under an 8.5 T magnetic field applied parallel to the nanotube axis. One to five fine structure states emerge depending on the chirality of the nanotube host, nature of chemical functional group, and chemical binding configuration, presenting an exciting opportunity toward developing chemical control of magnetic brightening. We attribute these hidden excitonic fine structure states to field-induced mixing of singlet excitons trapped at sp3 defects and delocalized band-edge triplet excitons. These findings provide opportunities for using organic color-centers for spintronics, spin-based quantum computing, and quantum sensing.

Mod(n-m,3) Dependence of Defect-State Emission Bands in Aryl-Functionalized Carbon Nanotubes.

Molecularly functionalized single-walled carbon nanotubes (SWCNTs) are potentially useful for fiber optical applications due to their room temperature single-photon emission capacity at telecommunication wavelengths. Several distinct defect geometries are generated upon covalent functionalization. While it has been shown that the defect geometry controls electron localization around the defect site, thereby changing the electronic structure and generating new optically bright red-shifted emission bands, the reasons for such localization remain unexplained. Our joint experimental and computational studies of functionalized SWCNTs with various chiralities show that the value of mod(n-m,3) in an (n,m) chiral nanotube plays a key role in the relative ordering of defect-dependent emission energies. This dependence is linked to the complex nodal characteristics of electronic wave function extending along specific bonds in the tube, which justifies the defect-geometry dependent exciton localization. This insight helps to uncover the essential structural motifs allowing tuning the redshifts of emission energies in functionalized SWCNTs.

Tuning electron transfer in supramolecular nano-architectures made of fullerenes and porphyrins.

The current work focuses on self-assembled nano-architectures in which metal-ligand coordination between a zinc tetraphenyl-porphyrin (ZnP) and a zinc tetrakis(4-((1,3-dithiol-2-ylidene)methyl)phenyl)-porphyrin (ZnP-TDP), as electron donors, and functionalized fullerenes (C60) featuring different conjugated pyridine substituents as electron acceptors have been designed and investigated. Stoichiometric ratios and binding constants were derived from absorption and fluorescence measurements. Important insight into the free-energy change of charge separation and recombination was obtained from differential pulse voltammetry studies. Compelling evidence for energy transfer, charge separation and recombination was obtained from femtosecond and nanosecond transient-absorption measurements in a wide temperature range. Intramolecular energy transfer is found to take place from TDP to ZnP followed by intramolecular charge transfer from ZnP to C60. Semiempirical and density-functional theory calculations were used to help understand the excited-state deactivation mechanisms.

Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes.

The introduction of sp3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show here that such selectivity can be obtained through aryl functionalization of so-called 'zigzag' nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. We show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

Understanding Charge-Transfer Characteristics in Crystalline Nanosheets of Fullerene/(Metallo)porphyrin Cocrystals.

Cocrystals in the form of crystalline nanosheets comprised of C70 and (metallo)porphyrins were prepared by using the liquid-liquid interfacial precipitation (LLIP) method where full control over the morphologies in the C70/(metallo)porphyrins nanosheets has been accomplished by changing the solvent and the relative molar ratio of fullerene to (metallo)porphyrin. Importantly, the synergy of integrating C70 and (metallo)porphyrins as electron acceptors and donors, respectively, into nanosheets is substantiated in the form of a near-infrared charge-transfer absorption. The presence of the latter, as reflection of ground-state electron donor-acceptor interactions in the nanosheets, in which a sizable redistribution of charge density from the electron-donating (metallo)porphyrins to the electron-accepting C70 occurs, leads to a quantitative quenching of the localized (metallo)porphyrin fluorescence. Going beyond the ground-state characterization, excited-state electron donor-acceptor interactions are the preclusion to a full charge transfer featuring formation of a radical ion pair state, that is, the one-electron reduced fullerene and the one-electron oxidized (metallo)porphyrin.

Interfacial charge transfer in functionalized multi-walled carbon nanotube@TiO2 nanofibres.

A new insight into photoinduced charge transfer processes across carbon nanotube@TiO2 interfaces has been gained based on experimental details from transient absorption spectroscopy. We show that photoinduced, interfacial hole transfer to carboxylic acid-functionalized multiwalled carbon nanotubes (oxMWCNTs) from TiO2 results in hole-doped oxMWCNTs and reduced TiO2. The latter is inferred from femto- and nanosecond transient absorption spectroscopy performed with oxMWCNT@TiO2 dispersions and complemented with investigations using methyl viologen and N,N,N',N'-tetramethyl-p-phenylenediamine as an electron scavenger and a hole scavenger, respectively. The results of ultraviolet photoemission spectroscopy (UPS) of the compounds corroborate the findings, highlighting the strong coupling between oxMWCNTs and TiO2 in these hybrids.

Sulfur rich electron donors - formation of singlet versus triplet radical ion pair states featuring different lifetimes in the same conjugate.

An unprecedented family of novel electron-donor acceptor conjugates based on fullerenes as electron acceptors, on one hand, and triphenyl amines as electron donors, on the other hand, have been synthesized and characterized in a variety of solvents using steady state absorption/emission as well as transient absorption spectroscopy. These are unprecedented in terms of their outcome of radical ion pair formation, that is, the singlet versus triplet excited state. This was corroborated by femto/nanosecond pump probe experiments and by molecular orbital calculations. Not only has the donor strength of the triphenylamines been systematically altered by appending one or two sulfur rich dithiafulvenes, but the presence of the latter changed the nature of the radical ion pair state. Importantly, depending on the excitation wavelength, that is, either where the fullerenes or where the triphenylamines absorb, short-lived or long-lived radical ion pair states, respectively, are formed. The short-lived component with a lifetime as short as 6 ps has singlet character and stems from a fullerene singlet excited state precursor. In contrast, the long-lived component has a lifetime of up to 130 ns in THF, has triplet character, and evolves from a triplet excited state precursor. Key in forming more than three orders of magnitude longer lived radical ion pair states is the presence of sulfur atoms, which enhance spin-orbit coupling and, in turn, intersystem crossing. Independent confirmation for the singlet versus triplet character came from temperature dependent measurements with a focus on the radical ion pair state lifetimes. Here, activation barriers of 2.4 and 10.0 kJ mol-1 for the singlet and triplet radical ion pair state, respectively, were established.

Bulbous gold-carbon nanodot hybrid nanoclusters for cancer therapy.

Assemblies of inorganic nanoparticles and carbon nanodots have emerged as promising candidates for hybrid materials in biomedical applications. In this work, the formation and properties of gold nanoparticles synthesized with the aid of carbon nanodots (CND) as reducing/stabilizing agents was investigated. Through careful modification of the reaction conditions, such as precursor concentrations and temperature, the size and shape of the particles can be controlled. In general, CNDs provide reductive sites at which gold seeds can be formed. As the gold nanoparticles grow, the CNDs form a polar solubilizing shell in the polar aqueous environment, yielding bulbous Au@pCND nanoclusters. In fact, charge-transfer interactions between the pCND shell and the Au core are implicit, as confirmed by steady state and time resolved absorption and fluorescence spectroscopies. Finally, this work demonstrated via in cell internalization tests that the size and the shape of the Au@pCND nanoclusters play a crucial role for the cancer cell toxicity. Also the Au@pCND prove to be good candidates as sensitizers in cancer radio-therapy.

Modeling 4D Pathological Changes by Leveraging Normative Models.

With the increasing use of efficient multimodal 3D imaging, clinicians are able to access longitudinal imaging to stage pathological diseases, to monitor the efficacy of therapeutic interventions, or to assess and quantify rehabilitation efforts. Analysis of such four-dimensional (4D) image data presenting pathologies, including disappearing and newly appearing lesions, represents a significant challenge due to the presence of complex spatio-temporal changes. Image analysis methods for such 4D image data have to include not only a concept for joint segmentation of 3D datasets to account for inherent correlations of subject-specific repeated scans but also a mechanism to account for large deformations and the destruction and formation of lesions (e.g., edema, bleeding) due to underlying physiological processes associated with damage, intervention, and recovery. In this paper, we propose a novel framework that provides a joint segmentation-registration framework to tackle the inherent problem of image registration in the presence of objects not present in all images of the time series. Our methodology models 4D changes in pathological anatomy across time and and also provides an explicit mapping of a healthy normative template to a subject's image data with pathologies. Since atlas-moderated segmentation methods cannot explain appearance and locality pathological structures that are not represented in the template atlas, the new framework provides different options for initialization via a supervised learning approach, iterative semisupervised active learning, and also transfer learning, which results in a fully automatic 4D segmentation method. We demonstrate the effectiveness of our novel approach with synthetic experiments and a 4D multimodal MRI dataset of severe traumatic brain injury (TBI), including validation via comparison to expert segmentations. However, the proposed methodology is generic in regard to different clinical applications requiring quantitative analysis of 4D imaging representing spatio-temporal changes of pathologies.

Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes.

Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs.