Catching an Oxo Vanadate Porous Acetylacetonate Covalent Adaptive Catalytic Network that Renders Mustard-Gas Simulant Harmless.

In this work, we illustrated the design and development of a metal-coordinated porous organic polymer (POP) namely VO@TPA-POP via a post-synthetic metalation strategy to incorporate oxo-vanadium sites in a pristine polymer (TPA-POP) having acetylacetonate (acac) as anchoring moiety. The as-synthesized VO@TPA-POP exhibited highly robust and porous framework, which has been utilized for thioanisole (TA) oxidation to its corresponding sulfoxide. The catalyst demonstrated notable stability and recyclability by maintaining its catalytic activity over multiple reaction cycles without any significant loss in activity. The X-ray absorption spectroscopy (XAS) and density functional theory (DFT) analysis establish the existence of V(+4) oxidation state along with the VO(O)4 active sites into the porous network and the most energetically feasible mechanistic pathway involved in the TA oxidation, respectively, indicating the role of electron density associated with vanadium center during the catalytic transformation. Thus, this work aims at the demonstration of versatility and potential of VO@TPA-POP as a porous heterogeneous catalyst for the TA oxidation followed by decontamination of sulfur mustards (HD's) to their corresponding less toxic sulfoxides in a more efficient and greener way.

Hierarchical assembly of tryptophan zipper peptides into stress-relaxing bioactive hydrogels.

Soft materials in nature are formed through reversible supramolecular assembly of biological polymers into dynamic hierarchical networks. Rational design has led to self-assembling peptides with structural similarities to natural materials. However, recreating the dynamic functional properties inherent to natural systems remains challenging. Here we report the discovery of a short peptide based on the tryptophan zipper (trpzip) motif, that shows multiscale hierarchical ordering that leads to emergent dynamic properties. Trpzip hydrogels are antimicrobial and self-healing, with tunable viscoelasticity and unique yield-stress properties that allow immediate harvest of embedded cells through a flick of the wrist. This characteristic makes Trpzip hydrogels amenable to syringe extrusion, which we demonstrate with examples of cell delivery and bioprinting. Trpzip hydrogels display innate bioactivity, allowing propagation of human intestinal organoids with apical-basal polarization. Considering these extensive attributes, we anticipate the Trpzip motif will prove a versatile building block for supramolecular assembly of soft materials for biotechnology and medicine.

Identification of 1,3,4-oxadiazoles as tubulin-targeted anticancer agents: a combined field-based 3D-QSAR, pharmacophore model-based virtual screening, molecular docking, molecular dynamics simulation, and density functional theory calculation approach.

Cancer is one of the most prominent causes of death worldwide and tubulin is a crucial protein of cytoskeleton that maintains essential cellular functions including cell division as well as cell signalling, that makes an attractive drug target for cancer drug development. 1,3,4-oxadiazoles disrupt microtubule causing G2-M phase cell cycle arrest and provide anti-proliferative effect. In this study, field-based 3D-QSAR models were developed using 62 bioactive anti-tubulin 1,3,4-oxadiazoles. The best model characterized by PLS factor 7 was rigorously validated using various statistical parameters. Generated 3D-QSAR model having high degree of confidence showed favourable and unfavourable contours around 1,3,4-oxadiazole core that assisted in defining proper spatial positioning of desired functional groups for better bioactivity. A five featured pharmacophore model (AAHHR_1) was developed using same ligand library and validated through enrichment analysis (BEDROC160.9 value = 0.59, Average EF 1% = 27.05, and AUC = 0.74). Total 30,212 derivatives of 1,3,4-oxadiazole obtained from PubChem database was prefiltered through validated pharmacophore model and docked in XP mode on binding cavity of tubulin protein (PDB code: 1SA0) which led into the identification of 11 HITs having docking scores between -7.530 and -9.719 kcal/mol while the reference compound Colchicine exerted docking score of -7.046 kcal/mol. Following the analysis of MM-GBSA and ADME studies, HIT1 and HIT4 emerged as the two promising hits. To verify their thermodynamic stability at the target site, molecular dynamic simulations were carried out. Both HITs were further subjected to DFT analysis to determine their HOMO-LUMO energy gap for ensuring their biological feasibility. Finally, molecular docking based structural exploration for 1,3,4-oxadiazoles to set up a lead of Formula I for further advancements of tubulin polymerization inhibitors as anti-cancer agents.Communicated by Ramaswamy H. Sarma.

Hydrogels with intrinsic antibacterial activity prepared from naphthyl anthranilamide (NaA) capped peptide mimics.

In this study, we prepared antibacterial hydrogels through the self-assembly of naphthyl anthranilamide (NaA) capped amino acid based cationic peptide mimics. These ultra-short cationic peptide mimics were rationally designed with NaA as a capping group, L-phenylalanine, a short aliphatic linker, and a cationic group. The synthesized peptide mimics efficiently formed hydrogels with minimum gel concentrations between 0.1 and 0.3%w/v. The resulting hydrogels exhibited desirable viscoelastic properties which can be tuned by varying the cationic group, electronegative substituent, or counter anion. Importantly, nanofibers from the NaA-capped cationic hydrogels were found to be the source of hydrogels' potent bacteriacidal actvity against both Gram-positive and Gram-negative bacteria while remaining non-cytotoxic. These intrinsically antibacterial hydrogels are ideal candidates for further development in applications where bacterial contamination is problematic.

Piezo-responsive bismuth ferrite nanoparticle-mediated catalytic degradation of rhodamine B and pathogenic E. coli in aqueous medium and its extraction using external magnetic stimulation after successful treatment.

This work reports a solvothermal synthesis of ferromagnetic bismuth ferrite (BFO) nanoparticle and its piezo activity in the domain of catalytic degradation of carcinogenic and genotoxic rhodamine B (RhB) dye and pathogenic Escherichia coli bacteria as well. After synthesis and characterization, the structural and morphological features of the catalyst were further investigated using density functional theory (DFT), which enabled us to estimate the polarizability and many other important electrical properties of the synthesized material. The DFT study reveals remarkably high polarizability and dipole moment, which were utilized to validate the generation of piezo response by the synthesized material. Interestingly, we found enhanced piezo catalytic degradation efficiency (η ∼ 99%) along with a high rate constant (k ∼ 2.259 × 10-2 min-1), indicating a fast and efficient degradation process. In the case of pathogenic bacteria E. coli, the degradation efficacy was found to be ∼94%. Moreover, the extraction of this catalyst is quite simple. Due to its high remanent magnetization (retentivity ∼0.08 emu g-1), the catalyst can be extracted from the treated water sample by using external magnetic stimulation, making it a potential candidate for sustainable wastewater treatment.

Assembly of surface-independent polyphenol/liquid gallium composite nanocoatings.

The development of functional nanocoatings using natural compounds is a hallmark of sustainable strategies in the field of green synthesis. Herein, we report a surface-independent nanocoating strategy using natural polyphenols and gallium-based room temperature liquid metal nanoparticles. The nanocoating matrix is composed of tannic acid, crosslinked with group (IV) transition metal ions. Liquid gallium nanoparticles are incorporated into the coatings as a gallium ion releasing depot. The coating deposition is rapid and can be applied to a range of substrates including glass, plastics, paper, and metal surfaces, owing to the versatile adhesive nature of the catechol/gallol functional groups of tannic acid. The coating thickness can be controlled from 100 to 700 nm and the content of liquid gallium nanoparticles can be modulated. This enables the tunable release behaviour of gallium ions into the surrounding from the composite coatings. The coatings are highly biocompatible and display antioxidant and antibacterial properties that can be useful for diverse applications.

Advanced descriptors for long-range noncovalent interactions between SARS-CoV-2 spikes and polymer surfaces.

The recent pandemic triggered numerous societal efforts aimed to control and limit the spread of SARS-CoV-2. One of these aspects is related on how the virion interacts with inanimate surfaces, which might be the source of secondary infection. Although recent works address the adsorption of the spike protein on surfaces, there is no information concerning the long-range interactions between spike and surfaces, experimented by the virion when is dispersed in the droplet before its possible adsorption. Some descriptors, namely the interaction potentials per single protein and global potentials, were calculated in this work. These descriptors, evaluated for the closed and open states of the spike protein, are correlated to the long-range noncovalent interactions between the SARS-CoV-2 spikes and polymeric surfaces. They are associated with the surface's affinity towards SARS-CoV-2 dispersed in respiratory droplets or water solutions. Molecular-Dynamics simulations were performed to model the surface of three synthetic polymeric materials: Polypropylene (PP), Polyethylene Terephthalate (PET), and Polylactic Acid (PLA), used in Molecular Mechanics simulations to define the above potentials. The descriptors show a similar trend for the three surfaces, highlighting a greater affinity towards the spikes of PP and PLA over PET. For closed and open structures, the long-range interactions with the surfaces decreased in the following order PP âˆ¼ PLA > PET and PLA > PP > PET, respectively. Thus, PLA and PP interact with the virion quite distant from these surfaces to a greater extent concerning the PET surface, however, the differences among the considered surfaces were small. The global potentials show that the long-range interactions are weak compared to classic binding energy of covalent or ionic bonds. The proposed descriptors are useful most of all for a comparative study aimed at quickly preliminary screening of polymeric surfaces. The obtained results should be validated by more accurate method which will be subject of a subsequent work.

Recent Advances in Cardiac Tissue Engineering for the Management of Myocardium Infarction.

Myocardium Infarction (MI) is one of the foremost cardiovascular diseases (CVDs) causing death worldwide, and its case numbers are expected to continuously increase in the coming years. Pharmacological interventions have not been at the forefront in ameliorating MI-related morbidity and mortality. Stem cell-based tissue engineering approaches have been extensively explored for their regenerative potential in the infarcted myocardium. Recent studies on microfluidic devices employing stem cells under laboratory set-up have revealed meticulous events pertaining to the pathophysiology of MI occurring at the infarcted site. This discovery also underpins the appropriate conditions in the niche for differentiating stem cells into mature cardiomyocyte-like cells and leads to engineering of the scaffold via mimicking of native cardiac physiological conditions. However, the mode of stem cell-loaded engineered scaffolds delivered to the site of infarction is still a challenging mission, and yet to be translated to the clinical setting. In this review, we have elucidated the various strategies developed using a hydrogel-based system both as encapsulated stem cells and as biocompatible patches loaded with cells and applied at the site of infarction.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Tweaking Nickel with Minimal Silver in a Heterogeneous Alloy of Decahedral Geometry to Deliver Platinum-like Hydrogen Evolution Activity.

Five-fold intertwined Agx Ni1-x (x=0.01-0.25) heterogeneous alloy nanocrystal (NC) catalysts, prepared through unique reagent combinations, are presented. With only ca. 5 at % Ag (AgNi-5), Pt-like activity has been achieved at pH 14. To reach a current density of 10 mA cm-2 the extremely stable AgNi-5 requires an overpotential of 24.0±1.2 mV as compared to 20.1±0.8 mV for 20 % Pt/C, both with equal catalyst loading of 1.32 mg cm-2 . The turnover frequency (TOF) is as high as 2.1 H2  s-1 at 50 mV (vs. RHE). Site-specific elemental analyses show the Ag:Ni compositional variation, where the apex and edges of the decahedra are Ag-rich, thereby exposing Ni onto the faces to achieve maximum charge transport for an exceptional pH universal HER activity. DFT calculations elucidate the relative H-atom adsorption capability of the Ni centers as a function of their proximity to Ag atom.

Design and evaluation of Konjac glucomannan-based bioactive interpenetrating network (IPN) scaffolds for engineering vascularized bone tissues.

Synthetic bone grafts are being developed to overcome the limitations of conventional treatments for bone defects. In this study, we have fabricated bioactive binary and novel ternary interpenetrating polymer network (IPN) scaffolds using a combination of natural and synthetic polymers. The binary IPN scaffolds were prepared using Konjac glucomannan (KGM) and polyvinyl alcohol (PVA). In the novel ternary IPN scaffolds, polycaprolactone (PCL) was added to PVA and KGM. SEM images showed that these scaffolds were microporous with good interconnectivity. Compression testing confirmed that both the scaffolds are mechanically strong, with the ternary scaffolds having moduli comparable to the natural bone. In vitro cytocompatibility studies performed with NIH/3T3 fibroblasts cells and MG-63 osteosarcoma cells demonstrated the non-toxic and osseointegrating nature of the scaffolds. Confocal images confirmed that the cells migrated into the interconnected pores of the scaffolds. RT-PCR analysis showed that both binary and ternary scaffolds enhanced the expression of the major bone marker genes, viz., ALP, BMP-2, COLLAGEN-1, and OSTEOCALCIN. However, the expression of these osteogenic markers was significantly enhanced in the ternary scaffolds compared to the binary scaffolds. In vivo chick chorioallantoic membrane (CAM) assay shows that these scaffolds possess excellent pro-angiogenic properties. Hence, these desirable biological properties, coupled with the suitable physicochemical properties, make these IPN scaffolds ideal for treating bone defects.

Defected and Functionalized Germanene-based Nanosensors under Sulfur Comprising Gas Exposure.

Efficient sensing of sulfur containing toxic gases like H2S and SO2 is of the utmost importance due to the adverse effects of these noxious gases. Absence of an efficient 2D-based nanosensor capable of anchoring H2S and SO2 with feasible binding and an apparent variation in electronic properties upon the exposure of gas molecules has motivated us to explore the promise of a germanene nanosheet (Ge-NS) for this purpose. In the present study, we have performed a comprehensive computational investigation by means of DFT-based first-principles calculations to envisage the structural, electronic, and gas sensing properties of pristine, defected, and metal substituted Ge-NSs. Our initial screening has revealed that although interaction of SO2 with pristine Ge-NSs is within the desirable range, H2S binding however falls below the required values to guarantee an effective sensing. To improve the binding characteristics, we have considered the interactions between H2S and SO2 with defected and metal substituted Ge-NS. The systematic removals of Ge atoms from a reasonably large super cell lead to monovacancy, divacancies, and trivacancies in Ge-NS. Similarly, different transition metals like As, Co, Cu, Fe, Ga, Ge, Ni, and Zn have been substituted into the monolayer to realize substituted Ge-NS. Our van der Waals corrected DFT calculations have concluded that the vacancy and substitution defects not only improve the binding characteristics but also enhance the sensing propensity of both H2S and SO2. The total and projected density of states show significant variations in electronic properties of pristine and defected Ge-NSs before and after the exposure to the gases, which are essential in constituting a signal to be detected by the external circuit of the sensor. We strongly believe that our present work would not only advance the knowledge towards the application of Ge-NS-based sensing but also provide motivation for the synthesis of such efficient nanosensor for H2S and SO2 based on Ge monolayer.

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices.

Electrochemical energy production and storage at large scale and low cost, is a critical bottleneck in renewable energy systems. Oxides and lithium transition metal phosphates have been researched for over two decades and many technologies based on them exist. Much less work has been done investigating the use of sodium phosphates for energy storage. In this work, the synthesis of sodium nickel phosphate at different temperatures is performed and its performance evaluated for supercapacitor applications. The electronic properties of polycrystalline NaNiPO4 polymorphs, triphylite and maricite, t- and m-NaNiPO4 are calculated by means of first-principle calculations based on spin-polarized Density Functional Theory (DFT). The structure and morphology of the polymorphs were characterized and validated experimentally and it is shown that the sodium nickel phosphate (NaNiPO4) exists in two different forms (triphylite and maricite), depending on the synthetic temperature (300-550 °C). The as-prepared and triphylite forms of NaNiPO4vs. activated carbon in 2 M NaOH exhibit the maximum specific capacitance of 125 F g(-1) and 85 F g(-1) respectively, at 1 A g(-1); both having excellent cycling stability with retention of 99% capacity up to 2000 cycles. The maricite form showed 70 F g(-1) with a significant drop in capacity after just 50 cycles. These results reveal that the synthesized triphylite showed a high performance energy density of 44 Wh kg(-1) which is attributed to the hierarchical structure of the porous NaNiPO4 nanosheets. At a higher temperature (>400 °C) the maricite form of NaNiPO4 possesses a nanoplate-like (coarse and blocky) structure with a large skewing at the intermediate frequency that is not tolerant of cycling. Computed results for the sodium nickel phosphate polymorphs and the electrochemical experimental results are in good agreement.

Revealing an unusual transparent phase of superhard iron tetraboride under high pressure.

First principles-based electronic structure calculations of superhard iron tetraboride (FeB4) under high pressure have been undertaken in this study. Starting with a "conventional" superconducting phase of this material under high pressure leads to an unexpected phase transition toward a semiconducting one. This transition occurred at 53.7 GPa, and this pressure acts as a demarcation between two distinct crystal symmetries, metallic orthorhombic and semiconducting tetragonal phases, with Pnnm and I41/acd space groups, respectively. In this work, the electron-phonon coupling-derived superconducting T(c) has been determined up to 60 GPa and along with optical band gap variation with increasing pressure up to 300 GPa. The dynamic stability has been confirmed by phonon dispersion calculations throughout this study.

Pediatric priapism: a rare first manifestation of leukemia.

Priapism is a rare disease. It is an emergency condition with a poor prognosis, and the risk of impotence is 50% despite appropriate management. Though about 20% cases of all priapism are related to hematological disorders, the incidence of priapism in adult leukemic patients is only about 1-5 percent. The incidence in pediatric leukemia patient is even rarer. Here we present a case of priapism in a 14-year-old apparently healthy boy who found to have chronic myeloid leukemia on subsequent investigations.

Seven-year retrospective clinical study evaluating efficacy of stainless steel mesh in mandibular fractures.

PURPOSE: The use of titanium mesh in communited mandibular fractures has been substantially documented. However, the use of stainless steel mesh for routine fixation in mandibular fractures has not been widely reported. The aim of the present study was to evaluate the efficacy of stainless steel mesh for routine osteosynthesis of mandibular fractures. MATERIALS AND METHODS: A total of 252 patients who had been diagnosed with 287 single or multiple mandibular fractures at Guru Nanak Institute of Dental Science and Research from 2002 to 2009 were selected for the present study. Those with condylar fractures and other maxillofacial injuries were excluded from the study. The patients were evaluated preoperatively, intraoperatively, and postoperatively at 1 day, 6 weeks, and 3 and 6 months. The local complications, occlusion (for static function), and chewing (for dynamic function) were evaluated postoperatively. RESULTS: The intraoperative time taken for implant fixation (from site exposure to fixation of the last screw) was 32 minutes. Of the 252 patients, 40 (15.8%) had local complications and 24 patients required implant removal. Of the 252 patients, 82% had bilaterally satisfactory occlusion according to the surgeon at 6 months postoperatively. Discomfort in chewing unilaterally or bilaterally was reported by 17% of the patients. CONCLUSION: The results of our study have shown that stainless steel mesh has acceptable complication rates and the ability to maintain occlusion and chewing postoperatively compared with the present standards of care of mandibular fractures using miniplates. The lower cost and versatile placement of screws were the principal advantages. However, placement near the mental foramen with an extraoral approach for certain sites is the primary disadvantage.

Laparoscopic versus open pyeloplasty: comparison of two surgical approaches- a single centre experience of three years.

UPJO causes hydronephrosis and progressive renal impairment may ensue if left uncorrected. Open pyeloplasty remains the standard against which new technique must be compared. We analyzed the comparison of Laparoscopic and open pyeloplasty in a randomized prospective trial. A prospective randomized study was done from January 2004 to January 2007 in which a total of 28 Laparoscopic and 34 open pyeloplasty were done. All laparoscopic pyeloplasties were performed transperitoneally. Standard open Anderson Hynes pyeloplasty, spiral flap or VY plasty was done depending on anatomic consideration. Patients were followed with DTPA scan at 3 months and IVP at 6 months. Perioperative parameters including operative time, analgesic use, hospital stay, and complication and success rates were compared. Mean total operative time with stent placement in LP group was 244.2 min (188-300 min) compared to 122 min (100-140 min) in open group. Compared to open pyeloplasty the post operative diclofenac requirement was significantly less in LP group (mean107.14 mg) and open group required mean of (682.35 mg) The duration of analgesic requirement was also significantly less in LP group. The post operative hospital stay in LP was mean 8.29 days (7-11) and was significantly less than open group (mean 3.14 Days (2-7 days). Open pyeloplasty has been the gold standard for UPJO repair and achieves success rates exceeding 90%. Laparoscopic pyeloplasty provides a minimally invasive alternative to repair UPJO and has developed world wide as the first minimally option to match success rate of open pyeloplasty. Its potential advantages including less post op pain, shorter hospital stay an improved cosmesis has been proved in some comparative series. The only disadvantage seems to be longer operative time. LP has a minimal level of morbidity and short hospital stay compared to open approach Although Laparoscopic pyeloplasty has the disadvantages of longer operative time and requires significant skill of intracorporeal knotting but it is here to stay and represents an emerging standard of care.

Healing of cervical necrotizing fasciitis using amniotic membrane as a dressing material.

AIMS AND OBJECTIVES: Early recognition, aggressive surgical debridement, removal of cause, appropriate antibiotic therapy, improvement of immunocompromised state and dressing of the wound is the treatment of necrotizing cervical fasciitis. There are so many reported cases of burn and some reported cases of necrotizing fasciitis where amniotic membrane has been used as a dressing material, and that encouraged us to use it as a dressing material in our cases. MATERIALS AND METHODS: Six cases of necrotizing cervical fasciitis reported to our department in a span of five years (2005 to 2010). Amniotic membrane taken from placenta of suitable donors had been used as a dressing material in these cases. Data collection included age, sex, medical history of the patients, size of the wound, pain felt by the patient, time taken for granulation tissue formation, total healing time, size of the scar and need for future reconstruction. RESULTS: The sample consisted of six patients with a mean age of 45 years. Four of them were male. Etiology was always odontogenic. Five patients were immunocompromised. Three patients were chronic alcoholic. Average size of the wound was 42 square centimeter. Mean time taken for formation of granulation tissue was 22 days; mean total healing time was 36 days. In every case patient reported with pain, which gradually diminished after first application of amniotic membrane. In three cases, pain on fourth day after first application of amniotic membrane was nil (VAS scale). In rest three cases, pain on sixth day after first application of amniotic membrane was nil (VAS scale). Average size of the scar was 9 cm(2). Secondary scar revision was required in all six cases. CONCLUSION: Our study concludes that amniotic membrane can be used effectively as a dressing material in necrotizing cervical fasciitis.

Xanthogranulomatous pyelonephritis in a horse-shoe kidney.

Xanthogranulomatous pyelonephritis (XGPN) represents an unusual suppurative granulomatous reaction to chronic infection, often in the presence of chronic obstruction from a calculus. We present a case of XGPN in a horse shoe kidney in an adult. Hemi-nephrectomy of the involved side was followed by clinical improvement. The case highlights the importance of early hemi-nephrectomy in XPGN with horse shoe kidney.