Electrically induced cancellation and inversion of piezoelectricity in ferroelectric Hf0.5Zr0.5O2.

HfO2-based thin films hold huge promise for integrated devices as they show full compatibility with semiconductor technologies and robust ferroelectric properties at nanometer scale. While their polarization switching behavior has been widely investigated, their electromechanical response received much less attention so far. Here, we demonstrate that piezoelectricity in Hf0.5Zr0.5O2 ferroelectric capacitors is not an invariable property but, in fact, can be intrinsically changed by electrical field cycling. Hf0.5Zr0.5O2 capacitors subjected to ac cycling undergo a continuous transition from a positive effective piezoelectric coefficient d33 in the pristine state to a fully inverted negative d33 state, while, in parallel, the polarization monotonically increases. Not only can the sign of d33 be uniformly inverted in the whole capacitor volume, but also, with proper ac training, the net effective piezoresponse can be nullified while the polarization is kept fully switchable. Moreover, the local piezoresponse force microscopy signal also gradually goes through the zero value upon ac cycling. Density functional theory calculations suggest that the observed behavior is a result of a structural transformation from a weakly-developed polar orthorhombic phase towards a well-developed polar orthorhombic phase. The calculations also suggest the possible occurrence of a non-piezoelectric ferroelectric Hf0.5Zr0.5O2. Our experimental findings create an unprecedented potential for tuning the electromechanical functionality of ferroelectric HfO2-based devices.

Impact of phase lag on synchronization in frustrated Kuramoto model with higher-order interactions.

The study of first order transition (explosive synchronization) in an ensemble (network) of coupled oscillators has been the topic of paramount interest among the researchers for more than one decade. Several frameworks have been proposed to induce explosive synchronization in a network and it has been reported that phase frustration in a network usually suppresses first order transition in the presence of pairwise interactions among the oscillators. However, on the contrary, by considering networks of phase frustrated coupled oscillators in the presence of higher-order interactions (up to 2-simplexes) we show here, under certain conditions, phase frustration can promote explosive synchronization in a network. A low-dimensional model of the network in the thermodynamic limit is derived using the Ott-Antonsen ansatz to explain this surprising result. Analytical treatment of the low-dimensional model, including bifurcation analysis, explains the apparent counter intuitive result quite clearly.

Perfect synchronization in complex networks with higher-order interactions.

Achieving perfect synchronization in a complex network, specially in the presence of higher-order interactions (HOIs) at a targeted point in the parameter space, is an interesting, yet challenging task. Here we present a theoretical framework to achieve the same under the paradigm of the Sakaguchi-Kuramoto (SK) model. We analytically derive a frequency set to achieve perfect synchrony at some desired point in a complex network of SK oscillators with higher-order interactions. Considering the SK model with HOIs on top of the scale-free, random, and small world networks, we perform extensive numerical simulations to verify the proposed theory. Numerical simulations show that the analytically derived frequency set not only provides stable perfect synchronization in the network at a desired point but also proves to be very effective in achieving a high level of synchronization around it compared to the other choices of frequency sets. The stability and the robustness of the perfect synchronization state of the system are determined using the low-dimensional reduction of the network and by introducing a Gaussian noise around the derived frequency set, respectively.

Piezoelectricity in hafnia.

Because of its compatibility with semiconductor-based technologies, hafnia (HfO2) is today's most promising ferroelectric material for applications in electronics. Yet, knowledge on the ferroic and electromechanical response properties of this all-important compound is still lacking. Interestingly, HfO2 has recently been predicted to display a negative longitudinal piezoelectric effect, which sets it apart from classic ferroelectrics (e.g., perovskite oxides like PbTiO3) and is reminiscent of the behavior of some organic compounds. The present work corroborates this behavior, by first-principles calculations and an experimental investigation of HfO2 thin films using piezoresponse force microscopy. Further, the simulations show how the chemical coordination of the active oxygen atoms is responsible for the negative longitudinal piezoelectric effect. Building on these insights, it is predicted that, by controlling the environment of such active oxygens (e.g., by means of an epitaxial strain), it is possible to change the sign of the piezoelectric response of the material.

Wake-up Free Ferroelectric Rhombohedral Phase in Epitaxially Strained ZrO2 Thin Films.

Zirconia- and hafnia-based thin films have attracted tremendous attention in the past decade because of their unexpected ferroelectric behavior at the nanoscale, which enables the downscaling of ferroelectric devices. The present work reports an unprecedented ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown directly on (111)-Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal (111)-oriented ZrO2 films under epitaxial compressive strain exhibiting switchable ferroelectric polarization of about 20.2 µC/cm2 with a coercive field of 1.5 MV/cm. Moreover, the time-dependent polarization reversal characteristics of Nb:SrTiO3/ZrO2/Au film capacitors exhibit typical bell-shaped curve features associated with the ferroelectric domain reversal and agree well with the nucleation limited switching (NLS) model. The polarization-electric field hysteresis loops point to an activation field comparable to the coercive field. Interestingly, the studied films show ferroelectric behavior per se, without the need to apply the wake-up cycle found in the orthorhombic phase of ZrO2. Overall, the rhombohedral ferroelectric ZrO2 films present technological advantages over the previously studied zirconia- and hafnia-based thin films and may be attractive for nanoscale ferroelectric devices.

Profiles of Two Glycaemia Modifying Drugs on the Expression of Rat and Human Sulfotransferases.

AIMS: To study the effects of blood glucose regulating compounds on human and rat sulfotransferases (SULTs) expressions. BACKGROUND: Phase-II enzymes, sulfotransferases catalyze the sulfuryl-group-transfer to endogenous/exogenous compounds. The alteration of expressions of SULTs may have influence on the sulfation of its substrate and other biomolecules. OBJECTIVES: The influence of the altered biotransformation might alter different biochemical events, drug-drug interactions and bioaccumulation or excretion pattern of certain drug. METHODS: In this brief study, diabetes-inducing drug streptozotocin (STZ; 10 or 50 mg/kg to male Sprague Dawley rat for 2 weeks) or hyperglycemia controlling drug tolbutamide (TLB 0.1 or 10µM to human hepato-carcinoma cells, HepG2 for 10 days) was applied and the SULTs expressions were verified. Extensive protein-protein (STa, SULT2A1/DHEAST) interactions were studied by the STRING (Search-Tool-for-the-Retrieval-of-Interacting Genes/Proteins) Bioinformatics-software. RESULTS: Present result suggests that while STZ increased the STa (in rat) (dehydroepiandrosterone catalyzing SULT; DHEAST in human HepG2), tolbutamide decreased PPST (phenol catalyzing SULT) and DHEAST activity in human HepG2 cells. Moderate decreases of MPST (monoamine catalyzing SULT) and EST (estrogen catalyzing) activities are noticed in this case. STa/DHEAST was found to be highly interactive to SHBG/- sex-hormone-binding-globulin; PPARα/lipid-metabolism-regulator; FABP1/fatty-acid-binding-protein. CONCLUSION: Streptozotocin and tolbutamide, these two glycaemia-modifying drugs demonstrated regulation of rat and human SULTs activities. The reciprocal nature of these two drugs on SULTs expression may be associated with their contrasting abilities in influencing glucose-homeostasis. Possible association of certain SULT-isoform with hepatic fat-regulations may indicate an unfocused link between calorie-metabolism and the glycemic-state of an individual. Explorations of this work may uncover the role of sulfation metabolism of specific biomolecule on cellular glycemic regulation.

Oxidative Stress-induced Toxicity and DNA Stability in Some Agri-field Based Livestock/Insect by Widely used Pesticides.

AIM AND OBJECTIVE: Humans continuously use pesticides in the field to control the pest population and weeds for considerable agricultural productivity. Side-by species like grazinganimals, insects and other species are adversely affected by or become resistant to pesticides. Insects, birds and cattle are highly abundant dwellers of the agriculture-field and represent three distinct phyla having versatile physiological features. Besides higher agricultural-productivity, protection to several species will maintain ecological/environmental balance. Studies on the effect of widely used pesticides on their DNA-stability and important enzymatic-activities are insufficient. MATERIALS AND METHODS: Antioxidant-activity (Superoxide-dismutase; SOD/Catalase- by gelzymogram- assay) and DNA-stability (fragmentation-assay) in hepatic/gut tissues were studied after in vitro exposure of Chlorpyrifos, Fenvalerate, Nimbecidine or Azadirachtin to goat/cow/poultry-hen/insect. RESULTS: In general, all pesticides were found to impair enzymatic-activities. However, lower organisms were affected more than higher vertebrates by azadirachtin-treatment. DNA fragmentation was found more in insects/poultry-birds than that of the cattle in hepatic/gut tissues. Inversely, toxicity/antioxidant marker-enzymes were more responsive in insect gut-tissues. However, mitochondrialtoxicity revealed variable effects on different species. It has been noticed that chlorpyrifos is the most toxic pesticide, followed by Fenvalerate/Nimbecidine (Azadirachtin, AZT). Nevertheless, AZT revealed its higher DNA-destabilizing effects on the field-insects as compared to the other animals. CONCLUSION: Field-insects are highly integrated into the ecosystem and the local bio-geo-chemical cycle, which may be impaired. Pesticides may have toxic effects on higher vertebrates and may sustain in the soil after being metabolized into their different derivatives. Some of the sensitive biochemical parameters of this organism may be used as a biomarker for pesticide toxicity.

Protection against Mitochondrial Oxidative-Stress by Flesh-Extract of Edible Freshwater Snail Bellamya bengalensis Prevents Arsenic Induced DNA and Tissue Damage.

AIMS: Arsenic has carcinogenic properties because of the formation of Reactive Oxygen Species (ROS). ROS damages different macromolecules, tissues and organs, and severely exhausts cellular antioxidants. BACKGROUND: Cytosolic and mitochondrial contribution of ROS production by arsenic are not well reported. In regard to the issues of therapy against arsenic or any other toxicity, natural product has gained its popularity due to its less side-effects and non-invasive nature. OBJECTIVES: Here, as an ethnomedicine, the flesh-extract (BBE; 100mg/100g bw) of Bellamya bengalensis (an aquatic mollusk) was applied in arsenic intoxicated (0.6 ppm/100g bw/for 28 days alone or in combination with BBE) experimental rats. Our objective was to study the anti-oxidative and anti-apoptotic role of BBE in hepato-gastrointestinal tissue damage by arsenic. METHODS: DNA fragmentation assay, catalase activity (gel-zymogram assay) suggests that BBE has a strong protective role against arsenic toxicity, which is decisively demonstrated in hepatic histoarchitecture study by HE (hematoxylin and eosin) staining and by intestinal PAS (Periodic Acid Schiff) staining. RESULTS: Measurement of mitochondrial-membrane-potential by fluorescent microcopy clearly demonstrated less membrane damage and lower release of the redox-active inner-membrane product (cytochrome-C, ubiquinone, etc.) in BBE supplemented group compared to that of the only arsenic fed group. The present study clearly suggests that mitochondrial disintegrity is one of the major causes of ROS mediated tissue damage by arsenic. CONCLUSION: This study also offers an option for prevention/treatment against arsenic toxicity and its carcinogenicity by widely available low-cost, non-invasive Bellamya extract by protecting cytoskeleton, DNA and mitochondria in the cell.

Biomonitoring role of some cellular markers during heat stress-induced changes in highly representative fresh water mollusc, Bellamya bengalensis: Implication in climate change and biological adaptation.

Owing to increasing concern of global climate-change, temperature rise is of great interest which can be primarily evaluated from the seasonal variations in some organisms. Aquatic environment can be extremely stressful to its inhabitants because most of them are poikilothermous. In the present study, attempt was made to evaluate the biological effects of oxidative-stress and adaptive/antioxidant capacities during temperature variations (36-40 °C for 24hrs to 72hrs) in Bellamya bengalensis both in environmental and laboratory conditions by testing some biomarkers like HSP70, catalase (CAT), superoxide dismutase (SOD), reduced glutathione (GSH) and glutathione reductase (GR). The biomarker potency of the molecules and the anti-oxidative metabolic-network was postulated and extrapolated to find its resemblance to the climate-change associated organismal variations. In a natural and eco-restored environment in the Eastern part of India, 10-20 fold increases in CAT, SOD and HSP70 protein expressions (Western blot results) were noticed in Bellamya paralleling to their increased enzymatic activities (gel zymogram studies) due to the seasonal (summer versus winter) temperature variation. It is evident from the consecutive three years' study that this variation resulted in the unfavorable physico-chemical changes of water quality parameters like dissolved oxygen, biochemical oxygen demand, alkalinity and consequently decreased the animal density in summer. And that was revived due to their higher reproduction-rate in post rainy/winter season when temperature normalizes resulting in a restoration of favorable environment. In laboratory condition, the reduced GR and increased GPx indicated the oxidative damage as evident by higher tissue MDA level following to higher mortality. Changes in SOD and CAT activities suggest activation of physiological mechanism to scavenge the ROS produced during heat stress. However, when mortality increased at different time points (36 °C - 72 h and 38 °C - 72 h), these enzyme activities also decreased as they failed to save the tissues from ROS. The results suggest that temperature variation does alter the active oxygen metabolism by modulating antioxidant enzyme activities, which can be used as biomarker to detect sub-lethal effects of climate change-associated pollution. The parity in environmental and laboratory experimental results may justify this laboratory experiment as model heat-stress experiment and indicate temperature as a universal stressor which alone or in combination with other water parameters initiates a consistent adapting behavior. The Bellamya bengalensis being the highest faunal representative in its habitat may serve as a good bioindicator species.

Impact of bi-axial strain on the structural, electronic and optical properties of photo-catalytic bulk bismuth oxyhalides.

The structural, electronic and optical properties of bulk bismuth oxyhalides, BiOX (X = F, Cl, Br, and I), were studied using state-of-the-art density functional theory (DFT)-based calculations. The effects of compressive and tensile strains on the in-plane lattice parameters were analyzed to better understand their good performance in photo-catalytic applications. Our present first-principles calculations show that at least 4% in-plane bi-axial compressive strain over the experimental lattice parameters of BiOF is needed for phonon stability of this material, whereas other BiOX systems can accept up to 2% in-plane bi-axial compressive strain and retain their dynamical stability. On the other hand, 2% in-plane tensile strain breaks the structural stability of all bulk BiOX structures. Tuning the electronic band structures with such external compressive strain indeed helps to enhance the separation of charge carriers due to larger electron-hole effective mass differences in the BiOBr and BiOI structures. The optical properties are discussed from their calculated absorption spectra and optical conductivity within independent particle approximations. The average values of the calculated optical band gaps are in the range of 3.8-3.9 eV, 3.3-3.4 eV, 2.7-2.8 eV and 1.7-1.8 eV for the unstrained and compressive strained structures, respectively, of the BiOF, BiOCl, BiOBr and BiOI materials, which are reasonably good compared to their known experimental ultra-violet visible spectroscopy measured data.

Theoretical Formalism To Estimate the Positron Scattering Cross Section.

A theoretical formalism is introduced in this article to calculate the total cross sections for positron scattering. This method incorporates positron-target interaction in the spherical complex optical potential formalism. The study of positron collision has been quite subtle until now. However, recently, it has emerged as an interesting area due to its role in atomic and molecular structure physics, astrophysics, and medicine. With the present method, the total cross sections for simple atoms C, N, and O and their diatomic molecules C2, N2, and O2 are obtained and compared with existing data. The total cross section obtained in the present work gives a more consistent shape and magnitude than existing theories. The characteristic dip below 10 eV is identified due to the positronium formation. The deviation of the present cross section with measurements at energies below 10 eV is attributed to the neglect of forward angle-discrimination effects in experiments, the inefficiency of additivity rule for molecules, empirical treatment of positronium formation, and the neglect of annihilation reactions. In spite of these deficiencies, the present results show consistent behavior and reasonable agreement with previous data, wherever available. Besides, this is the first computational model to report positron scattering cross sections over the energy range from 1 to 5000 eV.

Assessment of thermal stress adaptation by monitoring Hsp70 and MnSOD in the freshwater gastropod, Bellamya bengalensis (Lamark 1882).

Expression of the stress biomarkers 70-kDa heat shock proteins (Hsp70) and manganese superoxide dismutase (MnSOD) was measured as the molecular basis of adaptive response against increased experimental temperatures (32-40 °C for a span of 24-72 h) on the fresh water molluscan species, Bellamya bengalensis (Lamark 1882). The experimental snail specimens were collected during summer and winter seasons from two contrasting wetlands: an ecorestored (free from human interference) site (SI) and other experiencing anthropogenic stresses (SII). The mortality rate of the B. bengalensis and the immunoblotting of MnSOD and Hsp70 of their digestive glands were performed at regular intervals during the period of heat stress. The SI provided a lower stress environment based on physicochemical parameters such as pH, dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen demand (COD), and alkalinity for the survival of test species, although both sites experienced mortality due to thermal stresses. The parity in protein expressions displayed a uniform mode of adaptive impact to temperature elevations in both field and laboratory exposure. The Hsp70 expression was minimal at lower thermal stress, but increased with a rise in temperature. It is very likely that higher Hsp70 levels are not directly related to survival or adaptation. In contrast, MnSOD levels appeared to be an indicator of adaptive responses vis-a-vis survival of the animals. So, the expression levels of a universal free radical scavenger like MnSOD are recognized as a potential biomarker in a bioindicator species like Bellamya.

Enzymatic, antimicrobial and toxicity studies of the aqueous extract of Ananas comosus (pineapple) crown leaf.

ETHNOPHARMACOLOGICAL RELEVANCE: Various parts of the plant pineapple (Ananas comosus) are used in traditional medicine worldwide for treatment of a number of diseases and disorders. In folk medicine, pineapple leaf extract was used as an antimicrobial, vermicide, purgative, emmenagoogue, abortifacient, anti-oedema and anti-inflammatory agent. Compared to the fruit and stem extracts of pineapple, information about its leaf extract is limited. The potential of pineapple crown leaf extract as an ethno-medicine has been evaluated in terms of its enzymatic activities related to wound healing, antimicrobial property and toxicity. MATERIALS AND METHODS: Major protein components of the extract were revealed by 2-D gel electrophoresis followed by MS/MS analysis. Zymography, DQ-gelatin assay were performed to demonstrate proteolytic, fibrinolytic, gelatinase and collagenase activities. DNase and RNase activities were revealed from agarose gel electrophoresis. Antimicrobial activity was evaluated spectrophotometrically from growth inhibition. Sprague-Dawley rat model was used to measure acute and sub-acute toxicity of the extract by analyzing blood markers. RESULT: The extract contains several proteins that were clustered under native condition. Proteomic studies indicated presence of fruit bromelain as major protein constituent of the extract. It showed nonspecific protease activity, gelatinolytic, collagenase, fibrinolytic, acid and alkaline phosphatase, peroxidase, DNase and RNase activities along with considerable anti-microbial property. The leaf extract did not induce any toxicity in rats after oral administration of acute and sub-acute doses. CONCLUSION: Pineapple leaf extract is nontoxic, contains enzymes related to damage tissue repairing, wound healing and possibly prevents secondary infections from microbial organisms.

Reverse zymography alone does not confirm presence of a protease inhibitor.

Reverse zymography is applied for identification and semi-quantification of protease inhibitors that are of protein in nature. However, a protein that shows band in reverse zymography against a protease used for digestion of the gel need not be an inhibitor; it might be resistant to degradation by the protease. We demonstrate that in reverse zymography, avidin, streptavidin and the leaf extract of Catharanthus roseus behave like inhibitors of proteases like papain, ficin, bromelain extracts from pineapple leaf, stem and fruit and trypsin. Still, they do not act as inhibitors of those proteases when enzyme assays were done in solution. In reverse zymography, the extract of pineapple crown leaf shows two major inhibitor bands against its own proteases. Identification of these proteins from sequences derived from MALDI TOF MS analysis indicated that they are fruit and stem bromelains. Avidin, streptavidin and bromelains are 'kinetically stable proteins' that are usually resistant to proteolysis. Thus, it is recommended that identification of an inhibitor of a protease by reverse zymography should be supported by independent assay methods for confirmation.

Induction of Cr(VI) reduction activity in an Anoxybacillus strain under heat stress: a biochemical and proteomic study.

A bacterial strain, designated as TSB-6, was isolated from the sediments of a Tantloi (India) hot spring at 65 °C. The strain showed 98% 16S rRNA gene sequence similarity with Anoxybacillus kualawohkensis strain KW12 and was found to grow optimally at 37 °C. However, growing cells, cell suspensions, and cell-free extracts from 65 °C cultures showed higher Cr(VI) reduction activities when assayed at either 37 or 65 °C than those obtained from 37 °C cultures. On fractionation of extracts from cells grown at 65 °C, the chromate reductase activity assayed at 65 °C was found mostly in the soluble fraction. When log-phase cells growing at 37 °C were shifted to 65 °C, the stressed cells produced larger quantities of reactive oxygen species. Consequently, growth of the cells was retarded, but specific Cr(VI) reduction activity increased. 2D gel electrophoresis followed by MALDI-TOF MS/MS identified the proteins whose expression level changed as a result of heat stress. The upregulated set included proteins involved in cellular metabolism of sugar, nucleotide, amino acids, lipids and vitamins, oxidoreductase activity, and protein folding. The downregulated proteins are also involved in cellular metabolism, DNA binding, and environmental signal processing.

Effect of folic acid on methotrexate induction of sulfotransferases in rats.

Our earlier investigation showed that MTX is an inducer of rat and human sulfotransferases. Here we report that folic acid treatment inhibited MTX induction of aryl sulfotransferase (AST-IV) in female rat liver and hydroxysteroid sulfotransferase (STa) in male rat liver. This is important for understanding the clinical mechanisms of MTX.

In vivo and in vitro oxidative regulation of rat aryl sulfotransferase IV (AST IV).

Sulfotransferase catalyzed sulfation is important in the regulation of different hormones and the metabolism of hydroxyl containing xenobiotics. In the present investigation, we examined the effects of hyperoxia on aryl sulfotransferase IV in rat lungs in vivo. The enzyme activity of aryl sulfotransferase IV increased 3- to 8-fold in >95% O2 treated rat lungs. However, hyperoxic exposure did not change the mRNA and protein levels of aryl sulfotransferase IV in lungs as revealed by Western blot and RT-PCR. This suggests that oxidative regulation occurs at the level of protein modification. The increase of nonprotein soluble thiol and reduced glutathione (GSH)/oxidized glutathione (GSSG) ratios in treated lung cytosols correlated well with the aryl sulfotransferase IV activity increase. In vitro, rat liver cytosol 2-naphthol sulfation activity was activated by GSH and inactivated by GSSG. Our results suggest that Cys residue chemical modification is responsible for the in vivo and in vitro oxidative regulation. The molecular modeling structure of aryl sulfotransferase IV supports this conclusion. Our gel filtration chromatography results demonstrated that neither GSH nor GSSG treatment changed the existing aryl sulfotransferase IV dimer status in cytosol, suggesting that oxidative regulation of aryl sulfotransferase IV is not caused by dimer-monomer status change.