Postdengue Acute Disseminated Encephalomyelitis.

A 38-year-old gentleman, following an uncomplicated dengue fever 2 weeks back, developed acute onset bilateral lower limb weakness and numbness for 5 days, associated with bladder and bowel incontinence and a band-like sensation in T4 dermatome. On examination, he had paraparesis with normal cranial nerves except for left upper motor neuron-type 7th cranial nerve palsy and normal higher mental function. Magnetic resonance imaging (MRI) of the brain and spine detected multiple demyelinating lesions. A diagnosis of postdengue acute disseminated encephalomyelitis (ADEM) was made as part of postinfective inflammatory process after the fever had subsided. Cerebrospinal fluid study ruled out active infection. He was treated with intravenous steroids and is currently recovering. An interesting point in our case was that the patient had significant imaging findings in MRI of the brain with no symptoms or signs suggestive of intracranial involvement-ADEM without evidence of encephalitis.

Understanding the mechanism of the energy transfer process from non-plasmonic fluorescence bimetallic nanoparticles to plasmonic gold nanoparticles.

Understanding the fundamentals behind the photophysical response of a fluorescing species in the vicinity of plasmonic nanoparticles is of great interest due to the importance of this event in various applications. The present work has been carried out to throw light on how plasmonic nanoparticles electronically interact with non-plasmonic nanoparticles. Specifically, in this work, the excitation energy transfer (EET) from fluorescence bimetallic silver capped gold (F-AgAu) to gold nanoparticles (AuNPs) and how this process can be modulated by cetyltrimethylammonium bromide (CTAB) have been investigated at both ensemble average and single particle levels. Steady-state and time-resolved fluorescence studies have revealed that the fluorescence intensity and lifetime of F-AgAu in the presence of AuNPs are significantly quenched. Cyclic voltammetry (CV) and polarity-dependent studies have ruled out the possibility of an electron transfer mechanism. The increased non-radiative decay rate has substantiated that the photoluminescence quenching is due to excitation energy transfer from F-AgAu to AuNPs. Interestingly, investigations have revealed that the energy transfer efficiency is reduced from 87% to 28% in the presence of CTAB due to the formation of a CTAB bilayer over AuNPs. Analysis of the data by conventional EET, nano surface energy transfer (NSET), and stretched exponential models have firmly established that the EET process follows a 1/d4 distance dependence (NSET) rather than conventional 1/d6 distance dependence as predicted with the Förster resonance energy transfer model. Additionally, single particle level measurements through fluorescence lifetime imaging microscopy (FLIM) studies have clearly demonstrated that the surfactant (CTAB) can play an important role in controlling the EET process from non-plasmonic to plasmonic nanoparticles. The outcome of the present EET between two different classes of nanoparticles is expected to be useful in developing nanoscale systems for various optoelectronic applications.

Role of polymer template in crystal structure and photoactivity of Cu-TiO2 heterojunction nanostructures towards environmental remediation.

Exploring porous heterojunction nanomaterials as a photocatalyst for water depollution strategies towards environmental restoration is exceedingly difficult in the perspective of sustainable chemistry. Herein, we first report a porous Cu-TiO2 (TC40) heterojunction by using microphase separation of a novel penta-block copolymer (PLGA-PEO-PPO-PEO-PLGA) as a template through an evaporation induced self-assembly (EISA) method having nanorod-like particle shape. Furthermore, two types of photocatalyst were made with or without polymer template to clarify the function of that template precursor on the surface and morphology, as well as which variables are the most critical for a photocatalyst. TC40 heterojunction nanomaterial displayed higher BET surface area along with lower band gap value viz.2.98 eV compared to the other and these features make it a robust photocatalyst for wastewater treatment. In order to improve water quality, we have carried out experiments on the photodegradation of methyl orange (MO), highly toxic pollutants that cause health hazards and bioaccumulate in the environment. Our catalyst, TC40 exhibits the 100% photocatalytic efficiency towards MO dye degradation in 40 and 360 min at a rate constant of 0.104 ± 0.007 min-1 and 0.440 ± 0.03 h-1 under UV + Vis and visible light irradiation, respectively.

Realization of a Model-Free Pathway for Quantum Dot-Protein Interaction Beyond Classical Protein Corona or Protein Complex.

Although in recent times nanoparticles (NPs) are being used in various biological applications, their mechanism of binding interactions still remains hazy. Usually, the binding mechanism is perceived to be mediated through either the protein corona (PC) or protein complex (PCx). Herein, we report that the nanoparticle (NP)-protein interaction can also proceed via a different pathway without forming the commonly observed PC or PCx. In the present study, the NP-protein interaction between less-toxic zinc-silver-indium-sulfide (ZAIS) quantum dots (QDs) and bovine serum albumin (BSA) was investigated by employing spectroscopic and microscopic techniques. Although the analyses of data obtained from fluorescence and thermodynamic studies do indicate the binding between QDs and BSA, they do not provide clear experimental evidence in favor of PC or PCx. Quite interestingly, high-resolution transmission electron microscopy (HRTEM) studies have shown the formation of a new type of species where BSA protein molecules are adsorbed onto some portion of a QD surface rather than the entire surface. To the best of our knowledge, we believe that this is the first direct experimental evidence in favor of a model-free pathway for NP-protein interaction events. Thus, the outcome of the present study, through experimental evidence, clearly suggests that NP-protein interaction can proceed by following a pathway that is different from classical PC and PCx.

Probing the Interaction of Bovine Serum Albumin with Copper Nanoclusters: Realization of Binding Pathway Different from Protein Corona.

With an aim to understand the interaction mechanism of bovine serum albumin (BSA) with copper nanoclusters (CuNCs), three different types CuNCs having chemically different surface ligands, namely, tannic acid (TA), chitosan, and cysteine (Cys), have been fabricated, and investigations are carried out in the absence and presence of protein (BSA) at ensemble-averaged and single-molecule levels. The CuNCs, capped with different surface ligands, are consciously chosen so that the role of surface ligands in the overall protein-NCs interactions is clearly understood, but, more importantly, to find whether these CuNCs can interact with protein in a new pathway without forming the "protein corona", which otherwise has been observed in relatively larger nanoparticles when they are exposed to biological fluids. Analysis of the data obtained from fluorescence, ζ-potential, and ITC measurements has clearly indicated that the BSA protein in the presence of CuNCs does not attain the binding stoichiometry (BSA/CuNCs > 1) that is required for the formation of "protein corona". This conclusion is further substantiated by the outcome of the fluorescence correlation spectroscopy (FCS) study. Further analysis of data and thermodynamic calculations have revealed that the surface ligands of the CuNCs play an important role in the protein-NCs binding events, and they can alter the mode and thermodynamics of the process. Specifically, the data have demonstrated that the binding of BSA with TA-CuNCs and Chitosan-CuNCs follows two types of binding modes; however, the same with Cys-CuNCs goes through only one type of binding mode. Circular dichroism (CD) measurements have indicated that the basic structure of BSA remains almost unaltered in the presence of CuNCs. The outcome of the present study is expected to encourage and enable better application of NCs in biological applications.

Intraluminal Thrombi in the Cervico-Cephalic Arteries.

Background and Purpose- Intraluminal thrombus (ILT) is an uncommon finding among patients with ischemic stroke. We report clinical-imaging manifestations, treatment offered, and outcome among patients with ischemic stroke/transient ischemic attack and ILT in their cervico-cephalic arteries. Methods- Sixty-one of 3750 consecutive patients with acute ischemic stroke/transient ischemic attack (within 24 hours of onset) and ILT on initial arch-to-vertex computed tomography angiography from April 2015 through September 2017 constituted the prospective study cohort. Functional outcome was assessed using the modified Rankin Scale score with functional independence at discharge defined as modified Rankin Scale score ≤2. Results- Prevalence of ILT on computed tomography angiography was 1.6% (95% CI, 1.2%-2.1%). Median age was 67 years (interquartile range, 56-73), and 40 subjects (65%) were male. The initial clinical presentation included transient ischemic attack in 12 (20%) and stroke in 49 patients (80%); most strokes (76%) were mild (National Institutes of Health Stroke Scale ≤5). The most common ILT location was cervical carotid or vertebral artery (n=48 [79%]) followed by intracranial (n=11 [18%]) and tandem lesions (n=2 [3%]). The most common initial treatment strategy was combination antithrombotics (heparin with single antiplatelet agent) among 57 patients (93%). Follow-up computed tomography angiography (n=59), after a median 6 days (interquartile range 4-10 days), revealed thrombus resolution in 44 patients (75% [completely in 27%]). Twenty four of 30 patients (80%) with >50% residual carotid stenosis underwent carotid revascularization (endarterectomy in 15 and stenting in 9 patients) without peri-procedural complications a median of 9 days after symptom onset. In-hospital stroke recurrence occurred in 4 patients (6.6%). Functional independence was achieved in 46 patients (75%) at discharge. Conclusions- Patients presenting with acute stroke/transient ischemic attack with ILT on baseline imaging have a favorable clinical course in hospital with low stroke recurrence, high rate of thrombus resolution, and good functional outcome when treated with combination antithrombotic therapy.

Computational assessment of growth of connective tissues around textured hip stem subjected to daily activities after THA.

Longer-term stability of uncemented femoral stem depends on ossification at bone-implant interface. Although attempts have been made to assess the amount of bone growth using finite element (FE) analysis in combination with a mechanoregulatory algorithm, there has been little research on tissue differentiation patterns on hip stems with proximal macro-textures. The primary goal of this investigation is to qualitatively compare the formation of connective tissues around a femoral implant with/without macro-textures on its proximal surfaces. This study also predicts formation of different tissue phenotypes and their spatio-temporal distribution around a macro-textured femoral stem under routine activities. Results from the study show that non-textured implants (80 to 94%) encourage fibroplasia compared to that in textured implants (71 to 85.38%) under similar routine activity, which might trigger aseptic loosening of implant. Formation of bone was more on medio-lateral sides and towards proximal regions of Gruen zones 2 and 6, which was found to be in line with clinical observations. Fibroplasia was higher under stair climbing (85 to 91%) compared to that under normal walking (71 to 85.38%). This study suggests that stair climbing, although falls under recommended activity, might be detrimental to patient compared to normal walking in the initial rehabilitation period.

When Task is Huge but Time is Short! An Interesting Case of Stroke Thrombolysis.

A 64-year-old gentleman, diabetic, and smoker attended the emergency room (ER) with acute stroke. He had expressive aphasia with right upper limb weakness. His blood pressure was extremely high, and he presented in the final half an hour of the permissible window period for thrombolysis. Bringing down his blood pressure to make him eligible for the procedure within the available time was a real challenge for us. Fortunately, we succeeded in our attempt and he gradually improved. Truly, the maximum blood pressure allowable in his case to make him still eligible for thrombolysis was not clear to us. He had an explainable intracranial arterial stenosis and was probably auto-regulating during his acute presentation. Hence, we could have been more lenient in bringing down his blood pressure and thrombolyzed him earlier. A modified guideline will help us to handle these special situations more confidently and allow more patients to get the benefit of thrombolysis.

Recent Developments on the Catalytic and Biosensing Applications of Porous Nanomaterials.

Nanoscopic materials have demonstrated a versatile role in almost every emerging field of research. Nanomaterials have come to be one of the most important fields of advanced research today due to its controllable particle size in the nanoscale range, capacity to adopt diverse forms and morphologies, high surface area, and involvement of transition and non-transition metals. With the introduction of porosity, nanomaterials have become a more promising candidate than their bulk counterparts in catalysis, biomedicine, drug delivery, and other areas. This review intends to compile a self-contained set of papers related to new synthesis methods and versatile applications of porous nanomaterials that can give a realistic picture of current state-of-the-art research, especially for catalysis and sensor area. Especially, we cover various surface functionalization strategies by improving accessibility and mass transfer limitation of catalytic applications for wide variety of materials, including organic and inorganic materials (metals/metal oxides) with covalent porous organic (COFs) and inorganic (silica/carbon) frameworks, constituting solid backgrounds on porous materials.

Construction of N-Rich Aminal-Linked Porous Organic Polymers for Outstanding Precombustion CO2 Capture and H2 Purification: A Combined Experimental and Theoretical Study.

A large number of scientific investigations are needed for developing a sustainable solid sorbent material for precombustion CO2 capture in the integrated gasification combined cycle (IGCC) that is accountable for the industrial coproduction of hydrogen and electricity. Keeping in mind the industrially relevant conditions (high pressure, high temperature, and humidity) as well as good CO2/H2 selectivity, we explored a series of sorbent materials. An all-rounder player in this game is the porous organic polymers (POPs) that are thermally and chemically stable, easily scalable, and precisely tunable. In the present investigation, we successfully synthesized two nitrogen-rich POPs by extended Schiff-base condensation reactions. Among these two porous polymers, TBAL-POP-2 exhibits high CO2 uptake capacity at 30 bar pressure (57.2, 18.7, and 15.9 mmol g-1 at 273, 298, and 313 K temperatures, respectively). CO2/H2 selectivities of TBAL-POP-1 and 2 at 25 °C are 434.35 and 477.93, respectively. On the other hand, at 313 K the CO2/H2 selectivities of TBAL-POP-1 and 2 are 296.92 and 421.58, respectively. Another important feature to win the race in the search of good sorbents is CO2 capture capacity at room temperature, which is very high for TBAL-POP-2 (15.61 mmol g-1 at 298 K for 30 to 1 bar pressure swing). High BET surface area and good mesopore volume along with a large nitrogen content in the framework make TBAL-POP-2 an excellent sorbent material for precombustion CO2 capture and H2 purification.

Influence of sequential opening/closing of interface gaps and texture density on bone growth over macro-textured implant surfaces using FE based mechanoregulatory algorithm.

Intramedullary implant fixation is achieved through a press-fit between the implant and the host bone. A stronger press-fit between the bone and the prosthesis often introduces damage to the bone canal creating micro-gaps. The aim of the present investigation is to study the influences of simultaneous opening/closing of gaps on bone growth over macro-textured implant surfaces. Models based on textures available on CORAIL and SP-CL hip stems have been considered and 3D finite element (FE) analysis has been carried out in conjunction with mechanoregulation based tissue differentiation algorithm. Additionally, using a full-factorial approach, different combinations (between 5 µm to 15 µm) of sliding and gap distances at the bone-implant interface were considered to understand their combined influences on bone growth. All designs show an elevated fibrous tissue formation (10.96% at 5 µm to 29.38% at 40 µm for CORAIL based textured model; 11.45% at 5 µm to 32.25% at 40 µm for SP-CL based textured model) and inhibition of soft cartilaginous tissue (75.64% at 5 µm to 53.94% at 40 µm for CORAIL based model; 76.02% at 5 µm to 53.60% at 40 µm SP-CL based model) at progressively higher levels of normal micromotion, leading to a fragile bone-implant interface. These results highlight the importance of minimizing both sliding and gap distances simultaneously to enhance bone growth and implant stability. Further, results from the studies with differential texture density over CORAIL based implant reveal a non-linear complex relationship between tissue growth and texture density which might be investigated in a machine learning framework.

Application of finite element analysis to tissue differentiation and bone remodelling approaches and their use in design optimization of orthopaedic implants: A review.

Post-operative bone growth and long-term bone adaptation around the orthopaedic implants are simulated using the mechanoregulation based tissue-differentiation and adaptive bone remodelling algorithms, respectively. The primary objective of these algorithms was to assess biomechanical feasibility and reliability of orthopaedic implants. This article aims to offer a comprehensive review of the developments in mathematical models of tissue-differentiation and bone adaptation and their applications in studies involving design optimization of orthopaedic implants over three decades. Despite the different mechanoregulatory models developed, existing literature confirm that none of the models can be highly regarded or completely disregarded over each other. Not much development in mathematical formulations has been observed from the current state of knowledge due to the lack of in vivo studies involving clinically relevant animal models, which further retarded the development of such models to use in translational research at a fast pace. Future investigations involving artificial intelligence (AI), soft-computing techniques and combined tissue-differentiation and bone-adaptation studies involving animal subjects for model verification are needed to formulate more sophisticated mathematical models to enhance the accuracy of pre-clinical testing of orthopaedic implants.

When time is short, and we are late!: A story of chronic meningitis.

We often face situations when the exact etiological diagnosis of meningitis is difficult. The reason behind this is that many pathogens have similar clinical, radiological, and laboratory pictures. The low yield of the pathogen in cerebrospinal fluid (CSF), non-availability of detail tests in all corners of the world, delay in availability of reliable results (like cultures), and difficulty in performing confirmatory tests like brain biopsy (in inconclusive cases) make the job of a clinician challenging. We report here a case where a late diagnosis of a disease owing to inconclusive results leads to dissemination. The complications following the introduction of the treatment based on presumption lead to further difficulty. We remained inclined to our diagnosis based on clinical judgement, acknowledged and managed the inflammatory changes secondary to the infection, and finally won the long battle. So, sometimes we need to make decisions based on clinical grounds. We need to depend on the fact that uncommon presentations of common diseases are commoner than a common presentation of uncommon diseases.

Vessel wall calcification and vascular event: Are we concerned enough?

A 49-year-old lady, hypertensive with dyslipidaemia, had thalamic bleed with intracranial multiple micro-haemorrhages. An extensive search was done and vasculitis was ruled out in the patient. Henceforth, she remained strict with medications and maintained blood pressure and lipids under control. After a lucid interval of 3 years, she attended emergency with complex partial seizure. We detected extensive microbleeds (significant increment) in magnetic resonance imaging of the brain and periventricular ischemic changes. A cerebrospinal fluid study and digital subtraction angiography of the brain were consistent with primary central nervous system (CNS) vasculitis (small vessel). She improved and currently is well on follow-up with immunosuppressive therapy. Interesting learning part in our case was late presentation of the patient with primary CNS vasculitis after a latency. It implies requirement of strong suspicion and stringent follow-up in these types of patients.

Strategic optimization of phase-selective thermochemically amended terra-firma originating from excavation-squander for geogenic fluoride adsorption: a combined experimental and in silico approach.

An inimitable adsorbent "FI-TM-BWCC," emanated from meta-phase-selective thermochemical modulation of excavation-squander (mine waste)-derived terra-firma (blackish white china clay, i.e., BWCC), is explored in the present work for fluoride (F-) adsorption purpose. FI-TM-BWCC portrayed an excellent adsorption efficiency (95% removal capacity and Qe: 99 mg/g, at initial adsorbate dose: 10 mg/L, pH: 7±0.5, adsorbent dosage: ~600 mg, exposure time: 60 min). At identical experimental conditions, the F- scavenging phenomenon was superior than two analogous adsorbents: (i) biopolymer chitosan and glutaraldehyde cross-linked BWCC (CG@BWCC, wherein F- removal efficiency: 74%) and (ii) meta-phase-selective thermally moduled BWCC (TM-BWCC, removal efficiency: 75%). BWCC predominantly comprises kaolinite and a trace amount of anatase along with prime elemental compositions: 41.71% Al2O3, 49.80 % SiO2, 4.25% Fe2O3, and 3.93% TiO2, as revealed by PXRD and XRF analyses. The thermochemical modulation pathway significantly escalated the BET surface area of BWCC (~11.92 m2/g, avg. pore radius: 23.64 Å, i.e., mesoporous in nature) to FI-TM-BWCC (216.95 m2/g, avg. pore radius: 31.41 Å). The fluoride-adsorbed F-•••FI-TM-BWCC species revealed a reduced surface area of 21.5 m2/g, which was explained in the light of ion exchange pathway on FI-TM-BWCC's non-uniform surface (surface roughness/SA of 1597 nm, reduced to 1179 nm after F- uptake). The spontaneous F-•••FI-TM-BWCC interaction (ΔG0 = -6.25 kJ) occurred following chemisorption-controlled ion exchange (CCIE) pathway as appearance of a F1s band at 685.5 eV was rationalized for Si-F bond formation; corroborating pseudo second-order (PSO) kinetics and resembling Freundlich isotherm. The usefulness of FI-TM-BWCC was diversified through field validation with natural groundwater specimens and proposition of a gravity-fed defluoridation unit. The flow rate was documented to be ~11 liters per hour (LPH) by implementing viscous turbulence fluent model. The experimental findings certainly followed the premise conventions of sustainability metrics upholding socio-economic equipoise.

A Ni(II) Metal-Organic Framework with Mixed Carboxylate and Bipyridine Ligands for Ultrafast and Selective Sensing of Explosives and Photoelectrochemical Hydrogen Evolution.

We report a Ni-MOF (nickel metal-organic framework), Ni-SIP-BPY, synthesized by using two linkers 5-sulfoisophthalic acid (SIP) and 4,4'-bipyridine (BPY) simultaneously. It displays an orthorhombic crystal system with the Ama2 space group: a = 31.425 Å, b = 19.524 Å, c = 11.2074 Å, α = 90°, ß = 90°, γ = 90°, and two different types of nickel(II) centers. Interestingly, Ni-SIP-BPY exhibits excellent sensitivity (limit of detection, 87 ppb) and selectivity toward the 2,4,6-trinitrophenol (TNP)-like mutagenic environmental toxin in the pool of its other congeners via "turn-off" fluorescence response by the synergism of resonance energy transfer, photoinduced electron transfer, intermolecular charge transfer, π-π interactions, and competitive absorption processes. Experimental studies along with corroborated theoretical experimentation, vide density functional theory studies, shed light on determining the plausible mechanistic pathway in selective TNP detection, which is highly beneficial in the context of homeland security perspective. Along with the sensing of nitroaromatic explosives, the moderately low band gap and the p-type semiconducting behavior of Ni-SIP-BPY make it suitable as a photoanode material for visible-light-driven water splitting. Highly active surface functionalities and sufficient conduction band minima effectively reduce the water and result in a seven times higher photocurrent density under visible-light illumination.

Visible Light-Driven Metal-Organic Framework-Mediated Activation and Utilization of CO2 for the Thiocarboxylation of Olefins.

Visible light-mediated photoredox catalysis has emerged to be a fascinating approach for the activation of CO2 and its subsequent fixation into valuable chemicals utilizing renewable and inexhaustible solar energy. Although great progress has been made in CO2 photoreduction, visible light-assisted organic synthesis using CO2 as a reactive substrate is rarely explored. Herein, we report an efficient, facile, and economically viable photoredox-mediated approach for the synthesis of important ß-thioacids via carboxylation of olefins with CO2 and thiols over a porous functionalized metal-organic framework (MOF), Fe-MIL-101-NH2, as a photocatalyst under ambient conditions. This multicomponent reaction offers wide substrate scope, mild reaction conditions, easy work-up, cost-effective and reusable photocatalysts, and higher product selectivity. Computational studies suggested that CO2 interacts with the thiophenol-styrene adduct to facilitate the synthesis of ß-thioacids in almost quantitative yields.

Qualitative predictions of bone growth over optimally designed macro-textured implant surfaces obtained using NN-GA based machine learning framework.

The surface features on implant surface can improve biologic fixation of the implant with the host bone leading to improved secondary (biological) implant stability. Application of finite element (FE) based mechanoregulatory schemes to estimate the amount of bone growth for a wide range of implant surface features is either manually intensive or computationally expensive. This study adopts an integrated approach combining FE, back-propagation neural network (BPNN) and genetic algorithm (GA) based search to evaluate optimum surface macro-textures from three representative implant models so as to enhance bone growth. Initial surface textures chosen for the implant models were based on an earlier investigation. Based on FE predicted dataset, a BPNN was formulated for faster prediction of bone growth. Using the BPNN predicted output, a GA-based search was carried out to maximize bone growth subject to clinically admissible micromotion at the bone-implant interface. The results from FE analysis and bone growth predictions from the BPNN were found to have strong correlation. The optimal osseointegration-maximized-textures (OMTs) obtained were found to offer enhanced biological fixation, as compared to that offered by the textures in the initial models. Results from the present study reveal that certain reduction in the dimension of ribs/grooves promotes bone growth. However, periodic patterns of ribs with higher and lower rib dimensions provide uniform stress environment at the interface thus promoting osseointegration.

A Tetradentate Phosphonate Ligand-based Ni-MOF as a Support for Designing High-performance Proton-conducting Materials.

Developing a robust metal-organic framework (MOF) which facilitates proton hopping along the pore channels is very demanding in the context of fabricating an efficient proton-conducting membrane for fuel cells. Herein, we report the synthesis of a novel tetradentate aromatic phosphonate ligand H8 L (L=tetraphenylethylene tetraphosphonic acid) based Ni-MOF, whose crystal structure has been solved from single-crystal X-ray diffraction. Ni-MOF [Ni2 (H4 L)(H2 O)9 (C2 H7 SO)(C2 H7 NCO)] displays a monoclinic crystal structure with a space group of P 21 /c, a=11.887 Å, b=34.148 Å, c=11.131 Å, α=γ=90°, ß=103.374°, where a nickel-hexahydrate moiety located inside the void space of the framework through several H-bonding interactions. Upon treatment of the Ni-MOF in different pH media as well as solvents, the framework remained unaltered, suggesting the presence of strong H-bonding interactions in the framework. High framework stability of Ni-MOF bearing H-bonding interactions motivated us to explore this metal-organic framework material as proton-conducting medium after external proton doping. Due to the presence of a large number of H-bonding interactions and the presence of water molecules in the framework we have carried out the doping of organic p-toluenesulfonic acid (PTSA) and inorganic sulphuric acid (SA) in this Ni-MOF and observed high proton conductivity of 5.28×10-2  S cm-1 at 90 °C and 98% relative humidity for the SA-doped material. Enhancement of proton conductivity by proton doping under humid conditions suggested a very promising feature of this Ni-MOF.

Metal-Free Pyrene-Based Conjugated Microporous Polymer Catalyst Bearing N- and S-Sites for Photoelectrochemical Oxygen Evolution Reaction.

The development of an efficient, sustainable, and inexpensive metal-free catalyst for oxygen evolution reaction (OER) via photoelectrochemical water splitting is very demanding for energy conversion processes such as green fuel generators, fuel cells, and metal-air batteries. Herein, we have developed a metal-free pyrene-based nitrogen and sulfur containing conjugated microporous polymer having a high Brunauer-Emmett-Teller surface area (761 m2 g-1) and a low bandgap of 2.09 eV for oxygen evolution reaction (OER) in alkaline solution. The π-conjugated as-synthesized porous organic material (PBTDZ) has been characterized by Fourier transform infrared spectroscopy (FT-IR), solid-state 13C (cross-polarization magic angle spinning-nuclear magnetic resonance) CP-MAS NMR, N2 adsorption/desorption analysis, field-emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) experiments. The material acts as an efficient catalyst for photoelectrochemical OER with a current density of 80 mA/cm2 at 0.8 V vs. Ag/AgCl and delivered 104 µmol of oxygen in a 2 h run. The presence of low bandgap energy, π-conjugated conducting polymeric skeleton bearing donor heteroatoms (N and S), and higher specific surface area associated with inherent microporosity are responsible for this admirable photoelectrocatalytic activity of PBTDZ catalyst.