Three in One: Superoleophilic, Chemically and Mechanically Resistant ZIF-7 and ZIF-11 Percolation Networks for Selective Permeation of Oils and Chlorinated Solvents.

Imbuing superwetting functions to organic-inorganic hybrid networks displaying chemical resistance, self-cleaning ability, and selective permeation of liquids has received increasing attention in recent years. Here we report superhydrophobic ZIF-7 and ZIF-11 on multilayer fluorinated graphene (FG) nanosheets with long-lasting water-repellent features. By exploring the solution processing of these chemically resistant dispersions, superoleophilic FG-ZIF-7 stainless steel mesh (FG-ZIF-7-SSM) and FG-ZIF-11 over cotton cloth (FG-ZIF-11-CC) possessing superior adhesion were fabricated. These permselective oil-liking prototypes were explored toward mesitylene and crude oil pickup from chemically harsh marine conditions such as seawater, acidic water, and alkaline water, with a separation efficiency of 96-94% up to 10 cycles. Furthermore, using an FG-ZIF-11-CC-wrapped glass pipet, upward diffusion of chloroform from sea, acidic, and alkaline water in 45 s was demonstrated with a separation efficacy of 94% up to 20 cycles. In addition to the chemical resistance and reusability, the mechanical stability of FG-ZIF-7-SSM and FG-ZIF-11-CC was investigated through folding, tape peeling, and dragging through sandpaper up to 250 cycles, showing no signs of changes in the hydrophobic responses. This research sheds light on the application of physiochemically resistant percolation coatings based on fluorinated graphene multilayers supporting ZIF-7 and ZIF-11 toward oil/water separation.

Stochastic Polarization Instability in PbTiO_{3}.

Although discussions of structural phase transitions in prototypical ferroelectric systems with the perovskite structure, such as BaTiO_{3} and PbTiO_{3}, started almost seventy years ago, an atomic-level description of the polar characteristics as a function of temperature, pressure, and composition remains topical. Here we provide a novel quantitative description of the temperature-driven local structural correlations in PbTiO_{3} via the development of characteristic relative cationic shifts. The results give new insights into the phase transition beyond those reliant on the long-range order. The ferroelectric-to-paraelectric transition of PbTiO_{3} is realized by the extent of a stochastic polarization instability driven by a progressive misalignment instead of a complete disappearance of the local dipoles, which further suggests that such polarization instability is chemically induced at the morphotropic phase boundary of PbTiO_{3}-based solid solutions with giant piezoelectric effect. As such, our results not only identify the evolving atomistic disorder in a perovskite-based ferroelectric system, but also suggest that polarization instability can serve as a generic fingerprint for phase transitions as well as for better understanding structure-property relationships in PbTiO_{3}-based ferroelectric solid solutions.

A comparison of 24 chemicals in the six-well bacterial reverse mutation assay to the standard 100-mm Petri plate bacterial reverse mutation assay in two laboratories.

The bacterial reverse mutation assay (Ames) is a fundamental genetic toxicology test, and efforts to miniaturize the regulatory GLP version are essential in assessing genotoxic liabilities earlier in the drug development pipeline. Two versions of the Ames were compared: the six-well (miniaturized) plate and the standard 100-mm plate test at two different laboratories. Of twenty-four chemicals tested, a subset of six chemicals was tested in the six-well test only and the remaining eighteen were evaluated in both versions of the test. The plate incorporation procedure was used with one Escherichia coli and four different Salmonella strains. The six-well test uses the same plating procedure and evaluation methods as the standard Ames assay in 100-mm plates, but the smaller format requires 20% of the test chemical. Additionally, the six-well test uses a limit concentration of 1000 µg/well versus the standard Petri plate test limit concentration of 5000 µg/plate. Testing across the two formats resulted in 100% concordance in overall mutagenicity judgement and 94% concordance across all tester strains and conditions. Known mutagenic positive control chemicals were correctly detected as positive in both formats. The overall conclusion is that the six-well assay results are concordant with the standard assay format in this evaluation and could be a reliable alternative.

Favorable Concurrence of Static and Dynamic Phenomena at the Morphotropic Phase Boundary of xBiNi_{0.5}Zr_{0.5}O_{3}-(1-x)PbTiO_{3}.

We reveal that concurrent events of inherent entropy boosting and increased synchronization between A- and B-site cation vibrations of an ABO_{3}-type perovskite structure give rise to a larger piezoelectric response in a ferroelectric system at its morphotropic phase boundary (MPB). It is further evident that the superior piezoelectric properties of xBiNi_{0.5}Zr_{0.5}O_{3}-(1-x)PbTiO_{3} in comparison to xBiNi_{0.5}Ti_{0.5}O_{3}-(1-x)PbTiO_{3} are due to the absolute flattening of the local potentials for all ferroelectrically active cations with a higher spontaneous polarization at the MPB. These distinctive features are discovered from the analyses of neutron pair distribution functions and Raman scattering data at ambient conditions, which are particularly sensitive to mesoscopic-scale structural correlations. Altogether this uncovers more fundamental structure-property connections for ferroelectric systems exhibiting a MPB, and thereby has a critical impact in contriving efficient novel materials.

Neuropilin-2 and its ligand VEGF-C predict treatment response after transurethral resection and radiochemotherapy in bladder cancer patients.

The standard treatment for invasive bladder cancer is radical cystectomy. In selected patients, bladder-sparing therapy can be performed by transurethral resection (TURBT) and radio-chemotherapy (RCT) or radiotherapy (RT). Our published in vitro data suggest that the Neuropilin-2 (NRP2)/VEGF-C axis plays a role in therapy resistance. Therefore, we studied the prognostic impact of NRP2 and VEGF-C in 247 bladder cancer patients (cN0M0) treated with TURBT and RCT (n = 198) or RT (n = 49) and a follow-up time up to 15 years. A tissue microarray was analyzed by immunohistochemistry. NRP2 expression emerged as a prognostic factor in overall survival (OS; HR: 3.42; 95% CI: 1.48 - 7.86; p = 0.004) and was associated with a 3.85-fold increased risk of an early cancer specific death (95% CI: 0.91 - 16.24; p = 0.066) in multivariate analyses. Cancer specific survival (CSS) dropped from 166 months to 85 months when NRP2 was highly expressed (p = 0.037). Patients with high VEGF-C expression have a 2.29-fold increased risk of shorter CSS (95% CI: 1.03-5.35; p = 0.043) in univariate analysis. CSS dropped from 170 months to 88 months in the case of high VEGF-C expression (p = 0.041). Additionally, NRP2 and VEGF-C coexpression is a prognostic marker for OS in multivariate models (HR: 7.54; 95% CI: 1.57-36.23; p = 0.012). Stratification for muscle invasiveness (T1 vs. T2-T4) confirmed the prognostic role of NRP2 and NRP2/VEGF-C co-expression in patients with T2-T4 but also with high risk T1 disease. In conclusion, immunohistochemistry for NRP2 and VEGF-C has been determined to predict therapy outcome in bladder cancer patients prior to TURBT and RCT.

Impaired expression of protein phosphatase 2A subunits enhances metastatic potential of human prostate cancer cells through activation of AKT pathway.

BACKGROUND: Protein phosphatase 2A (PP2A) is a dephosphorylating enzyme, loss of which can contribute to prostate cancer (PCa) pathogenesis. The aim of this study was to analyse the transcriptional and translational expression patterns of individual subunits of the PP2A holoenzyme during PCa progression. METHODS: Immunohistochemistry (IHC), western blot, and real-time PCR was performed on androgen-dependent (AD) and androgen-independent (AI) PCa cells, and benign and malignant prostate tissues for all the three PP2A (scaffold, regulatory, and catalytic) subunits. Mechanistic and functional studies were performed using various biochemical and cellular techniques. RESULTS: Through immunohistochemical analysis we observed significantly reduced levels of PP2A-A and -B'γ subunits (P<0.001 and P=0.0002) in PCa specimens compared with benign prostate. Contemporarily, there was no significant difference in PP2A-C subunit expression between benign and malignant tissues. Similar to the expression pattern observed in tissues, the endogenous levels of PP2A-A and B'γ subunits were abrogated from the low metastatic to high metastatic and AD to AI cell line models, without any change in the catalytic subunit expression. Furthermore, using in vitro studies we demonstrated that PP2A-Aα scaffold subunit has a role in dampening AKT, ß-catenin, and FAK (focal adhesion kinase) signalling. CONCLUSION: We conclude that loss of expression of scaffold and regulatory subunits of PP2A is responsible for its altered function during PCa pathogenesis.

Isavuconazole activity against Aspergillus lentulus, Neosartorya udagawae, and Cryptococcus gattii, emerging fungal pathogens with reduced azole susceptibility.

Isavuconazole is an extended-spectrum triazole with in vitro activity against a wide variety of fungal pathogens. Clinical isolates of molds Aspergillus lentulus and Neosartorya udagawae and yeast Cryptococcus gattii VGII (implicated in the outbreak in the Pacific Northwest, North America) exhibit reduced susceptibilities to several azoles but higher susceptibilities to isavuconazole.

Carbon spheres assisted synthesis of porous oxides with foam-like architecture.

Herein, we report a facile route for the synthesis of foam-like porous oxides using carbon spheres and polyvinylpyrrolidone (PVP) as sacrificial templates. The as-prepared porous structures were characterized by XRD, FESEM, TEM and BET methods. These foam-like macroporous oxides are formed through the fusion of oxide nanoparticles around the gas bubbles liberated during the combustion of composites and show good BET surface areas.

Aminoclay-supported copper nanoparticles for 1,3-dipolar cycloaddition of azides with alkynes via click chemistry.

Aminoclay supported copper nanoparticles are effective in promoting [3+2] cycloaddition of azides with terminal alkynes to produce the corresponding 1,2,3-triazoles in excellent yields. The copper nanoparticles are highly reactive in water and can be recycled for four cycles with consistent activity.

Application of lamellar nickel hydroxide membrane as a tunable platform for ionic thermoelectric studies.

The recent trend in thermoelectric literature suggests that ionic thermoelectric (i-TE) materials are ideal for directly converting low-grade waste heat into electricity. Here, we developed a unique platform for i-TE studies by stacking two-dimensional sheets of ß-Ni(OH)2 prepared by a bottom-up method. The lamellar membrane of ß-Ni(OH)2 (Ni-M) itself does not display significant thermovoltages, but when doped with mobile anion-generating species (like aminopropyl functionalized magnesium phyllosilicate or organic halide salts), it exhibits significant negative Seebeck coefficient (up to -13.7 ± 0.2 mV K-1). Similarly, upon doping with cation-generating species like poly(4-styrene sulfonic acid) (PSS), it displays positive Seebeck coefficient values (up to +12 ± 1.9 mV K-1). The positive and negative i-TE materials prepared by doping Ni-M are assembled into ionic thermopiles capable of generating thermovoltages up to 1 V, at ΔT = 12 K. The Ni-M-based nanofluidic systems demonstrated an additional path of electricity harvesting by connecting colder zones of the positive and negative i-TE materials with other ion conducting membranes. In contrast to organic polymer-based i-TE systems, the Ni-M based system exhibited consistent performance despite being exposed to high temperatures (∼200 °C, 5 minutes).

Light-harvesting hybrid assemblies.

Light-harvesting hybrids have gained much importance as they are considered as potential mimics for photosynthetic systems. In this Concept article we introduce the design concepts involved in the building up of light-harvesting hybrids; these resemble the well-studied organic-based assemblies for energy transfer. We have structured this article into three parts based on the strategies adopted in the synthesis of hybrid assemblies, as covalent, semicovalent, and noncovalent procedures. Furthermore, the properties and structural features of the hybrids and analogous organic assemblies are compared. We also emphasize the challenges involved in the processability of these hybrid materials for device applications and present our views and results to address this issue through the design of soft-hybrids by a solution-state, noncovalent, self-assembly process.

Pd-aminoclay nanocomposite as an efficient recyclable catalyst for hydrogenation and Suzuki cross coupling reactions.

A highly water dispersible Pd-aminoclay nanocomposite is found to be effective catalytic system for the hydrogenation of alpha,beta-unsaturated carbonyl compounds and Suzuki coupling reactions in aqueous media. The catalytic hydrogenation of alpha,beta-unsaturated carbonyl compounds proceeds at room temperature to afford the corresponding products in excellent yields with high chemoselectivity. The cross coupling of aryl bromides and iodides with aryl boronic acids proceeds efficiently under aqueous conditions at 90 degrees C to afford the corresponding biaryls in excellent yields with high selectivity. The Suzuki reaction proceeds smoothly even in the absence of external base due to the basic nature of the catalyst support. The catalyst could be easily recovered and recycled three times without a significant loss of activity in hydrogenation and Suzuki cross coupling reactions.

Honey derivatized Au and Ag nanoparticles and evaluation of its antimicrobial activity.

Biomolecules hosting the synthesis of nanoparticles has achieved considerable attention in recent decades due to their abundant availability, excellent biocompatibility and low toxicity. The present study demonstrates a rapid, cost-effective and eco-friendly fabrication of gold and silver nanoparticles at room temperature using natural honey as a source of stabilizing and reducing agent. The nanoparticles obtained were unambiguously characterized by using various characterization techniques such as transmission electron microscopy (TEM), UV-Visible absorption spectroscopy, X-ray diffraction and energy dispersive (EDX) X-ray analysis. The average size of Au and Ag nanoparticles are 10 and 12 nm respectively. Ag nanoparticles capped by honey exhibited superior antimicrobial activity while Au nanoparticles revealed passable activity against pathogenic bacteria and Candida albicans, including multi-resistant strains for the first time.

Carbon nanocage: super-adsorber of intercalators for DNA protection.

In this research, we report the binding behaviors of two kinds of intercalators, methyl violet and 3,6-diaminoacridine hydrochloride, to various mesoporous materials, carbon nanocage, mesoporous carbon CMK-3, activated carbon, and mesoporous silica SBA-15. Due to its unique cage type structure, carbon nanocage shows greater adsorption capacity than the other adsorbents. In addition, competitive adsorption of methyl violet between DNA and mesoporous materials confirmed that carbon nanocage can very efficiently inhibit intercalation of methyl violet by DNA. Carbon nanocage might then be useful for entrapment of harmful aromatic molecules.

Base-selective adsorption of nucleosides to pore-engineered nanocarbon, carbon nanocage.

Selective molecular recognition is an important subject in supramolecular science as well as in practical applications such as sensing, drug delivery, and biomedical processes. In this research we have investigated adsorption behavior of nucleosides (adenosine, guanosine, and thymidine) onto various porous supports. When compared with mesoporous silica, porous carbons exhibit superior adsorptive performance. We serendipitously observed a pronounced selectivity between purine-base and pyrimidine-base nucleosides by carbon naonocage. These findings are useful for design of materials for applications in adsorption-based separations and as column stationary phases for separation of costly and important biomolecules.

Open-mouthed metallic microcapsules: exploring performance improvements at agglomeration-free interiors.

Although artificial capsule structures have been thoroughly investigated, functionality at the surfaces of their interiors has been surprisingly overlooked. In order to exploit this aspect of capsular structure, we here report the breakthrough fabrication of metallic (platinum) microcapsules with sufficient accessibility and electroactivity at both interior and exterior surfaces (open-mouthed platinum microcapsules), and also we demonstrate improvements in electrochemical and catalytic functions to emphasize the practical importance of our concept. The open-mouthed platinum microcapsules were prepared by template synthesis using polystyrene spheres, where surface-fused crystalline nanoparticles formed a capsule shell. Subsequent removal of the polystyrene spheres induced formation of mouth-like openings. The open-mouthed platinum microcapsules exhibit a substantial increase of their electrode capability for methanol oxidation and catalytic activities for carbon monoxide (CO) oxidation. Notably, activity loss during CO oxidation due to undesirable particle agglomeration can be drastically suppressed using the open-mouthed microcapsules.

Serious neutropenia following etanercept administration in a 62 years female patient of rheumatoid arthritis.

Tumor necrosis factor (TNF) plays an important role in the inflammatory process of RA and the resulting joint pathology. Etanercept is a member of anti TNF family which is indicated in patients with moderate to severe active rheumatoid arthritis either alone or in combination with MTX. Very few cases of neutropenia with etanercept treatment have been reported worldwide so far. The mechanism of etanercept induced neutropenia is not yet established. We report a case of 62 year female patient, developing etanercept induced neutropenia after 1 month of starting treatment. The absolute neutrophil count (ANC) came down to 150/microl on the 6th day of diagnosis. Bone marrow examination revealed a maturation arrest of granulocytic cells. Other marrow components were normal. Causality assessment of adverse drug reactions was done as per Naranjo's Algorithm. It was a probable ADR. We propose the possible mechanism of neutropenia is bone marrow toxicity. This is contrary to a previous case report which suggested peripheral consumption of neutrophil as a cause of neutropenia. Recently, there are some reports of leukemia and other hematological malignancies associated with the use of etanercept and in those conditions neutropenia could be the first manifestation. Neither product label of the drug nor US FDA warns for periodic blood investigation during etanercept therapy. There is a definite need for total and differential count estimation at the beginning and regular interval during etanercept treatment to rule out possibilities of neutropenia.

Economic analysis of risk of gastrointestinal parasitic infection in cattle in North Eastern States of India.

Gastrointestinal parasitic infection is highly prevalent in the North Eastern States (NEH) of India and accounted for significant economic losses across various livestock species. Productivity of cattle in terms of milk yield was estimated to be considerably higher (3,715, 3,590, and 3,154 L) due to strategic anthelmintic treatment as compare to control group (2,928 L). Based on the probability of occurrence of parasitic infection as well as increase in value of milk production, the possible economic gain at state level has been estimated to be Rs. 46 million, Rs. 35 million, and Rs. 14 million, depending upon the different strategic treatment. The government may take up the program to educate the cattle farmers on strategic management against parasitic infection and simultaneously making available various anthelmintic medicines. This public responsibility of the government to minimize the risk and economic loss due to gastrointestinal parasite infection may reduce the private cost and thereby would increase the social benefits in North Eastern states of India.

Acclimatory response to hydrogen peroxide and glutathione under salt-boron stress through their impact on mineral nutrition and antioxidant defense system in pigeonpea (Cajanus cajan L.).

Investigations were carried out on a salt tolerant (Manak, H77-216) and a comparatively salt sensitive (ICPL 88039) genotypes of pigeonpea (Cajanus cajan L. Millsp.) under NaCl, B and NaCl + B stress to examine the acclimatory response to H2O2, glutathione and H2O2 + glutathione through their effect on mineral nutrition, morpho-physiological parameters and antioxidant defense system. Both B and NaCl alone and their combinations had deleterious effect on dry biomass of plumule, enhanced relative stress injury (RSI), lipid peroxidation with concomitant increase in Na, Cl and B contents. However it did not bear any correlation with osmotic potential of plumule and K contents. Antioxidative enzymes like superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), peroxidase (POX) and glutathione reductase (GR) also decreased with salt, B and salt + B treatments. However contents of H2O2 enhanced and that of ascorbate declined under aforementioned treatments. These injurious effects are partially alleviated by exogenous application of H2O2; glutathione (GSH) and H2O2 + GSH treatments. The role of H2O2 and GSH in the present study is suggestive of triggering multifunctional signal transduction in plant defense mechanisms to prevent cellular oxidation, membrane injury, lipid peroxidation and protein enzyme inactivation.

Laryngopharyngeal Reflux : Larynx on Fire.

Laryngopharyngeal Reflux (LPR) is a commonly occurring and recently described clinical entity due to the retrograde flow of gastric contents into the pharynx. It accounts for many symptoms of upper airway including hoarseness, chronic throat irritation and globus sensation. The sensitive laryngeal mucosa is prone to damage by the combination of acid and pepsin. The inflammatory changes that follow are presumed to cause the symptoms and predispose the individual to laryngeal disorders. Diagnosis can usually be made clinically based on symptoms and laryngeal signs but a 24 hour pH metry is essential to establish diagnosis. Treatment centres on lifestyle modifications, vocal hygiene measures and long term use of proton pump inhibitors. Recent research in this field may lead to a better understanding of the pathophysiology of the disease and change the way LPR is managed.