Salicylhydroxamic Acid Research Articles

Four Mixed 3d-4f 12-Metallacrown-4 Complexes: Syntheses, Structures and Magnetic Properties

The incorporation of LnIII ions into the 12-metallacrown-4 topology affords the formation of four mixed 3d-4f pentanuclear complexes of compositions [NH(C2H5)3]{[Ln(OAc)4] [12-MCMnIII(N)shi-4]}·xH2O (Ln = Sm (1), Gd (2), Tb (3), Dy (4); x = 0.5 for 1 and 3, x = 0.25 for 2, x = 0 for 4; H3shi = salicylhydroxamic acid). Compounds 1–4 were obtained from the reactions of H3shi with Mn(CH3COO)2·4H2O and Ln(NO3)3·6H2O, in the presence of N(C2H5)3. They all contain a crown-like [Mn4Ln(μ-NO)4]11+ core with four MnIII atoms being at the rim of the crown and an LnIII ion occupying the dome of the crown. The peripheral ligation about the core is provided by four η1:η1:µ acetate groups. The identity of the LnIII ions slightly affects the 12-metallacrown-4 frameworks, as demonstrated by the gradual decrease of the distances between the LnIII ions and the centres of the Mn4 planes (1.85 A for 1, 1.81 A for 2, 1.80 A for 3, and 1.77 A for 4). Variable-temperature dc magnetic susceptibility studies were carried out on polycrystalline samples of 1–4. Antiferromagnetic interactions are determined for complexes 1–4.

Synthesis of polymeric bismuth chlorido hydroxamato complexes; X-ray crystal structure and antibacterial activity of a novel Bi(III) salicylhydroxamato complex

Reaction of salicylhydroxamic acid (Sha) and 2-aminophenyl hydroxamic acid (2-NH2-pha) with BiCl3 affords the corresponding novel polymeric bismuth chlorido hydroxamato complexes; [BiCl2(μ-Sha-1H)]∞ and [BiCl3(2-NH3-Pha-1H)]∞ respectively. The X-ray crystal structure of the THF-solvated polymeric bismuth chlorido salicylhydroxamato complex, [BiCl2(μ-Sha-1H)(THF)]∞ was solved, confirming the polymeric structure of this class of compounds and the (O,μ-O′)-bidentate bridging coordination mode of the hydroxamato ligand. The antibacterial activity of the THF-free polymeric bismuth chlorido salicylhydroxamato complex, [BiCl2(μ-Sha-1H)]∞, was investigated against a broad panel of bacteria, further highlighting the antibacterial properties of Bi-based compounds against Gram-positive and Gram-negative pathogenic and environmental strains of bacteria.

Responses of photosystem II photochemistry and the alternative oxidase pathway to heat stress in grape leaves

To study the photochemical responses of photosystem II (PSII) and mitochondrial alternative oxidase (AOX) to heat stress in grapevine (Vitis vinifera L. cv. ‘Cabernet Sauvignon’), we exposed grape leaves to a range of temperatures (25, 30, 35, 40, and 42.5 °C) in the light (600 µmol m−2 s−1). At temperatures >35 °C, the rate of photosynthetic O2 evolution and the maximal photochemistry efficiency of PSII (Fv/Fm) decreased significantly. We observed that the relative variable fluorescence increased at the J step, and there was also an accumulation of H2O2. In addition, there was an increase in both the non-photochemical quenching (NPQ) and the capacity of the alternative oxidase pathway (AOX) at higher temperatures. When the leaves were treated with the AOX inhibitor salicylhydroxamic acid, a significant decrease in the PSII electron transport rate and NPQ and an increase in H2O2 content occurred. Our results suggest that high temperature limits electron transport beyond Q A − , resulting in a strong accumulation of H2O2 in grape leaves. Inhibition of the AOX pathway increases the formation and accumulation of H2O2 in grape leaves, and may thereby increase photoinhibition in leaves experiencing heat stress.

Importance of the mitochondrial alternative oxidase (AOX) pathway in alleviating photoinhibition in cucumber leaves under chilling injury and subsequent recovery when leaves are subjected to high light intensity

ABSTRACTThe aim of this study was to assess the impact of the mitochondrial alternative oxidase (AOX) pathway on energy metabolism in chloroplast, and evaluate the importance of the AOX pathway in alleviating photoinhibition in cucumber (Cucumis sativus L.) leaves during chilling and the subsequent recovery period. Chilling (12°C) induced up-regultaion of the AOX pathway, which is important for chilled leaves to avoid overreduction of PSII and maintain photosynthetic electron transport. High light (200–300 µmol m−2 s−1) induced the decreases of maximal quantum yield of PSII photochemistry (Fv/Fm) and nonphotochemical quenching (NPQ), which was aggravated by 1 mM salicylhydroxamic acid (SHAM; AOX inhibitor), in cucumber leaves during chilling. However, Fv/Fm did not change and NPQ increased significantly in SHAM-treated leaves by chilling under low light. During recovery periods after chilling under low light, Fv/Fm, qP, ΦPSII, NPQ, and Fv’/Fm’ could return to normal degree in chilled leaves with or without SHAM. In contrast, high light induced more decrease of chlorophyll fluorescence parameters in chilled leaves during the recovery period, and SHAM treatment further aggravated the decrease. These results implied that up-regulation of AOX pathway in chilled leaves plays a critical role in protection against photoinhibition in leaves under excess light energy condition during chilling and the subsequent recovery period. However, thermal energy dissipation was more important to prevent photoinhibition in leaves exposed to chilling under low light.

The use of similarity analysis for evaluation of the chromatographic separation of salicylic acid and its selected derivatives studied by adsorption and partition thin-layer chromatography techniques

The aim of the work was the chromatographic separation of salicylic acid and their derivatives, i.e., acetylsalicylic acid, salicylanilide, salicylaldehyde, salicylamide, methyl salicylate, phenyl salicylate, 2,5-dihydroxybenzoic acid, salicylhydroxamic acid, 3,5-dinitrosalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, and 5-aminosalicylic acid by use of adsorption thin-layer chromatography (normal-phase thin-layer chromatography [NPTLC]) and partition thin-layer chromatography (reversed-phase thin-layer chromatography/high-performance thin-layer chromatography [RP-TLC/HPTLC]). Three qualitatively and quantitatively different mobile phases were used for the separation of salicylic acid and its derivatives. Cluster analysis (single linkage method, Euclidean distance) allowed the evaluation of the suitability of the chromatographic conditions used to separate the pairs of tested compounds. The cluster analysis data indicate that the composition of the mobile phase is fundamental in the process o...

A pivotal role of the jasmonic acid signal pathway in mediating radiation-induced bystander effects in Arabidopsis thaliana

Although radiation-induced bystander effects (RIBE) in Arabidopsis thaliana have been well demonstrated in vivo, little is known about their underlying mechanisms, particularly with regard to the participating signaling molecules and signaling pathways. In higher plants, jasmonic acid (JA) and its bioactive derivatives are well accepted as systemic signal transducers that are produced in response to various environmental stresses. It is therefore speculated that the JA signal pathway might play a potential role in mediating radiation-induced bystander signaling of root-to-shoot. In the present study, pretreatment of seedlings with Salicylhydroxamic acid, an inhibitor of lipoxigenase (LOX) in JA biosynthesis, significantly suppressed RIBE-mediated expression of the AtRAD54 gene. After root irradiation, the aerial parts of A. thaliana mutants deficient in JA biosynthesis (aos) and signaling cascades (jar1-1) showed suppressed induction of the AtRAD54 and AtRAD51 genes and TSI and 180-bp repeats, which have been extensively used as endpoints of bystander genetic and epigenetic effects in plants. These results suggest an involvement of the JA signal pathway in the RIBE of plants. Using the root micro-grafting technique, the JA signal pathway was shown to participate in both the generation of bystander signals in irradiated root cells and radiation responses in the bystander aerial parts of plants. The over-accumulation of endogenous JA in mutant fatty acid oxygenation up-regulated 2 (fou2), in which mutation of the Two Pore Channel 1 (TPC1) gene up-regulates expression of the LOX and allene oxide synthase (AOS) genes, inhibited RIBE-mediated expression of the AtRAD54 gene, but up-regulated expression of the AtKU70 and AtLIG4 genes in the non-homologous end joining (NHEJ) pathway. Considering that NHEJ is employed by plants with increased DNA damage, the switch from HR to NHEJ suggests that over-accumulation of endogenous JA might enhance the radiosensitivity of plants in terms of RIBE.

Rutile flotation with Pb2+ ions as activator: Adsorption of Pb2+ at rutile/water interface

The adsorption of Pb2+ at the rutile/water interface has been studied for the activation of rutile flotation with salicyl hydroxamic acid (SHA) as a collector in this work. This study was performed through measurement of the zeta potential, adsorption capacity, calorimetry and X-ray photoelectron spectroscopy. The experimental results showed that the adsorption of SHA on rutile and the flotability of rutile were significantly improved by the addition of Pb2+. This improvement was attributed to the specific adsorption of Pb2+ in the form of PbOH+, which interacted with the Ti-OH at the rutile surface and formed a surface Ti-O-Pb+ complex. This adsorption followed the Langmuir model. It reversed the zeta potential sign of rutile at pH 5.5⿿6.8 and had a heat of adsorption of ⿿46.71kJ/mol, suggesting the occurrence of a chemiosorptive process.

Metabolic activity in dormant conidia of Aspergillus niger and developmental changes during conidial outgrowth

The early stages of development of Aspergillus niger conidia during outgrowth were explored by combining genome-wide gene expression analysis (RNAseq), proteomics, Warburg manometry and uptake studies. Resting conidia suspended in water were demonstrated for the first time to be metabolically active as low levels of oxygen uptake and the generation of carbon dioxide were detected, suggesting that low-level respiratory metabolism occurs in conidia for maintenance. Upon triggering of spore germination, generation of CO2 increased dramatically. For a short period, which coincided with mobilisation of the intracellular polyol, trehalose, there was no increase in uptake of O2 indicating that trehalose was metabolised by fermentation. Data from genome-wide mRNA profiling showed the presence of transcripts associated with fermentative and respiratory metabolism in resting conidia. Following triggering of conidial outgrowth, there was a clear switch to respiration after 25min, confirmed by cyanide inhibition. No effect of SHAM, salicylhydroxamic acid, on respiration suggests electron flow via cytochrome c oxidase. Glucose entry into spores was not detectable before 1h after triggering germination. The impact of sorbic acid on germination was examined and we showed that it inhibits glucose uptake. O2 uptake was also inhibited, delaying the onset of respiration and extending the period of fermentation. In conclusion, we show that conidia suspended in water are not completely dormant and that conidial outgrowth involves fermentative metabolism that precedes respiration.

Management of benzimidazole fungicide resistance in eggplant brown rot (Phomopsis vexans) with pyraclostrobin

Brown rot (Phomopsis vexans) is a destructive disease of eggplant, which mainly causes fruit rot. It is currently managed through extensive foliar applications of fungicides, such as benzimidazole chemicals. In this research study, a total of 513 single-conidial isolates of P. vexans were collected between 2010 and 2013 for the purpose of characterizing their resistance to benzimidazole fungicides and diethofencarb. Two types of benzimidazole-resistant (Ben R) isolates, Ben R1 (benzimidazole-resistant and diethofencarb-sensitive), and Ben R2 (benzimidazole-resistant and diethofencarb-resistant), were detected. Ben R1 was associated with a point mutation from the GAG to GTG at codon 198 in the β-tubulin gene of the Ben S isolates, and was predicted to cause changes from glutamic acid to valine. Ben R2 was associated with a point mutation from the TTC to TAC at codon 200 in the β-tubulin gene of the Ben S isolates. It was determined that, whether the isolates of the P. vexans were sensitive or resistant to the benzimidazole fungicides, pyraclostrobin (a QoI fungicide) showed strong bioactivity against their mycelial growth, spore germination, and disease lesion development. Also, experiments in 2014 and 2015 at three testing sites showed that pyraclostrobin provided excellent control against brown rot disease in the eggplant fields, and significantly increased the yields of the eggplant fruits. Meanwhile, the applications of benzimidazole fungicides (carbendazim alone or mixed with diethofencarb) were found to aggravate the occurrences of the brown rot, and the eggplant yields were observed to decrease. The baseline sensitivity of the P. vexans to pyraclostrobin was further determined for these 513 isolates. In regard to inhibiting the mycelial growth, the mean EC50 values of the tested isolates were determined to be 3.19 ± 0.43 and 1.28 ± 0.14 mg l−1, respectively, in the absence and presence of the alternative oxidase specific inhibitor salicylhydroxamic acid (SHAM), and the range-of-variation factors were 49.6 and 35.1. For inhibiting spore germination, the mean EC50 values were 0.61 ± 0.12 and 0.39 ± 0.11 mg l−1, with the range-of-variation factors of 32.1 and 17.9, respectively. This study confirmed a serious resistance emergency to benzimidazole fungicides in the P. vexans populations, and indicated that pyraclostrobin may be a good alternative fungicide to control eggplant brown rot.

Electrochemical oxidation of salicylhydroxamic acid on Pt electrode

Abstract The electrochemical oxidation behavior of salicylhydroxamic acid (SHAM) on a Pt electrode was investigated in aqueous solution of different pHs, containing 10 mM of SHAM, at 25°C, by cyclic voltammetry technique. The results indicate that the SHAM was oxidized more easily in alkaline medium than acidic and neutral mediums, and the oxidation peaks of SHAM shifted toward lower potential values by increasing pH values. The SHAM electrooxidation involves an irreversible transfer of one or two electron, depending on the pH of solution. If solution pH is lower than 3 and higher than 7, the two electron transfer is involved in the electrooxidation. While, from pH=3 to pH=7, the SHAM electrooxidation involves an irreversible transfer of one electron and two protons in the first step, in agreement with the one step one-electron mechanism. The effect of SHAM concentration on the electrode reaction was investigated in artificial saliva solution. SHAM gives a single irreversible oxidation wave over the wide concentration range studied. Possible mechanism of SHAM electrooxidation was proposed.

Ferromagnetic Polarization: The Quantum Picture of Switching On/Off Single-Molecule Magnetism.

The mixed 3d-4f pentanuclear complex (Bu4N)[Mn(III)4Y(III)(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d-4f-5d hexanuclear complex (Et4N)5[Mn(III)4Y(III)(shi)4(OAc)4W(V)(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d-4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn-N-O]4 connection captures one Y(III) ion with four bridging acetate anions, completing the eight-coordinated environment around Y(III) ion, while four methanol molecules each coordinate to the Mn(III) ions on the other side of the Y(III) ion. After octacyanotungstate is introduced, the [W(V)(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between Mn(III) ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between Mn(III) ions and the W(V) ion. Complex 1 [Mn(III)4Y(III)] retains an S = 0 ground state, and complex 2 [Mn(III)4Y(III)W(V)] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four Mn(III) ions and one W(V) ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.

Baseline sensitivity and efficacy of trifloxystrobin against Sclerotinia sclerotiorum

The ascomycete fungus Sclerotinia sclerotiorum is a devastating plant pathogen notorious for its extremely broad host range. Trifloxystrobin has not been registered for control of S. sclerotiorum in China. In this study, baseline sensitivity of trifloxystrobin was established based on frequency distribution of 166 isolates' EC50 values and efficacy of trifloxystrobin was determined on potted oilseed rape plants. Trifloxystrobin EC50 values of the 166 isolates ranged from 0.01 to 0.80 μg/mL, with a mean value of 0.06 μg/mL. The frequency distribution of trifloxystrobin EC50 values was unimodal in shape, but with a long right-hand tail. After logarithmic transformation, the frequency distribution fitted closer to a normal distribution than did the original EC50 values. The preventive efficacies of trifloxystrobin at 5, 15, and 45 μg/mL were 71.4%, 96.5%, and 100.0%, respectively, while the curative efficacies were 40.6%, 48.7%, and 73.4%, respectively. Both preventive and curative efficacies of trifloxystrobin at 45 μg/mL were significantly higher (P ≤ 0.046) than those of the reference fungicide carbendazim. Assays with six arbitrarily selected isolates demonstrated that salicylhydroxamic acid (SHAM) at 20 μg/mL reduced trifloxystrobin EC50 values by 84.0% on average and greatly potentiated efficacy of trifloxystrobin. The average co-toxicity factor of SHAM and trifloxystrobin for preventive efficacy was 64.3, indicating considerable synergisms in planta. Hence, SHAM should not be included in in vitro assay of S. sclerotiorum sensitivity to trifloxystrobin.

Nitrogen deprivation induces cross-tolerance of Poa annua callus to salt stress

Alternative respiration pathway (AP) is an important pathway which can be induced by environment stresses in plants. In the present study, we show a new mechanism involving the AP in nitrogen deprivation-induced tolerance of Poa annua callus to salt stress. The AP capacity markedly increased under a 600 mM NaCl treatment or nitrogen deprivation pretreatment and reached a maximum under the nitrogen deprivation pretreatment combined with the NaCl treatment (–N+NaCl). Malondialdehyde (MDA) and H2O2 content and Na+/K+ ratio significantly increased under the 600 mM NaCl treatment but less under the–N+NaCl treatment. Moreover, both the nitrogen deprivation and the NaCl stress stimulated the plasma membrane (PM) H+-ATPase activity and increased pyruvate content. The maximal stimulating effect was found under the–N+NaCl treatment. When the AP capacity was reduced by salicylhydroxamic acid (SHAM, an inhibitor of AP), content of MDA and H2O2 and Na+/K+ ratio dramatically increased, whereas PM H+-ATPase activity decreased. Moreover, exogenous application of pyruvate produced a similar effect as the nitrogen deprivation pretreatment. The effects of SHAM on the Poa annua callus were counteracted by catalase (a H2O2 scavenger) and diphenylene iodonium (a plasma membrane NADPH oxidase inhibitor). Taken together, our results suggest that the nitrogen deprivation enhanced the capacity of AP by increasing pyruvate content, which in turn prevented the Poa annua callus from salt-induced oxidative damages and Na+ over-uptake.

Ga(3+)/Ln(3+) Metallacrowns: A Promising Family of Highly Luminescent Lanthanide Complexes That Covers Visible and Near-Infrared Domains.

Luminescent lanthanide(III)-based molecular scaffolds hold great promises for materials science and for biological applications. Their fascinating photophysical properties enable spectral discrimination of emission bands that range from the visible to the near-infrared (NIR) regions. In addition, their strong resistance to photobleaching makes them suitable for long duration or repeated biological experiments using a broad range of sources of excitation including intense and focalized systems such as lasers (e.g., confocal microscopy). A main challenge in the creation of luminescent lanthanide(III) complexes lies in the design of a ligand framework that combines two main features: (i) it must include a chromophoric moiety that possesses a large molar absorptivity and is able to sensitize several different lanthanide(III) ions emitting in the visible and/or in the near-infrared, and (ii) it must protect the Ln(3+) cation by minimizing nonradiative deactivation pathways due to the presence of -OH, -NH and -CH vibrations. Herein, a new family of luminescent Ga(3+)/Ln(3+) metallacrown (MC) complexes is reported. The MCs with the general composition [LnGa4(shi)4(C6H5CO2)4(C5H5N) (CH3OH)] (Ln-1, Ln = Sm(3+)-Yb(3+)) were synthesized in a one pot reaction using salicylhydroxamic acid (H3shi) with Ga(3+) and Ln(3+) nitrates as reagents. The molecular structure of [DyGa4(shi)4(C6H5CO2)4(C5H5N) (CH3OH)] was obtained by X-ray analysis of single crystals and shows that the complex is formed as a [12-MCGa(III)shi-4] core with four benzoate molecules bridging the central Dy(3+) ion to the Ga(3+) ring metals. The powder X-ray diffraction analysis demonstrates that all other isolated complexes are isostructural. The extended analysis of the luminescence properties of these complexes, excited by the electronic states of the chromophoric ligands, showed the presence of characteristic, sharp f-f transitions that can be generated not only in the NIR (Sm, Dy, Ho, Er, Yb) but also in the visible (Sm, Eu, Tb, Dy, Tm). All Ln-1 complexes possess very high quantum yield values with respect to other literature compounds, indicating a good sensitization efficiency of the [12-MCGa(III)shi-4] scaffold. Especially, as of today, the Yb-1 complex exhibits the highest NIR quantum yield reported for a lanthanide(III) complex containing C-H bonds with a value of 5.88(2)% in the solid state. This work is a significant step forward toward versatile, easily prepared luminescent lanthanide(III) complexes suitable for a variety of applications including highly in demand biological imaging, especially in the NIR domain.

Tracking biochemical changes during adventitious root formation in olive (Olea europaea L.)

The activity of oxidative enzymes and the levels of free auxins were determined during adventitious root formation in olive explants. Rooting trials were performed both with in vitro-cultured microshoots of the cultivar ‘Galega Vulgar’, treated with indole-3-butyric acid (IBA) and with salicylhydroxamic acid (SHAM)+IBA, as well as with semi-hardwood cuttings of the cultivars ‘Galega Vulgar’ (difficult-to-root) and ‘Cobrançosa’ (easy-to-root), treated with IBA. The auxin (IBA) was used in all experiments as a rooting promoter, while SHAM was used in micropropagation trials as rooting inhibitor, providing a negative control. Free indole-3-acetic acid (IAA) and IBA concentrations were determined in microshoots, as well as in semi-hardwood cuttings, throughout the rooting period at pre-established time-points. At the same time-points, the enzymatic activity of polyphenol oxidases (PPO), peroxidases (POX), and IAA oxidase (IAAox) was evaluated in the microshoots. Microshoots treated with SHAM+IBA revealed higher POX and IAAox activity, as well as lower PPO activity, than those treated only with IBA. IAA levels were higher in IBA-treated microshoots during induction phase, but lower during early initiation phase. In contrast, free IBA levels were higher in microshoots treated with SHAM+IBA during induction, but lower during initiation. A similar pattern of free auxin levels was observed in semi-hardwood cuttings of the two contrasting cultivars under evaluation. The similarities found on the auxin patterns of microshoots treated with SHAM and those of semi-hardwood cuttings of the difficult-to-root olive cultivar allow considering SHAM a reliable control for when simulation of a difficult-to-root behavior is necessary. The inhibitory effect of SHAM in root formation could be related with 1) the inhibition of alternative oxidase (AOX), leading to a downregulation of phenylpropanoid biosynthetic pathways, which would decrease the concentration of phenolic substrates for PPO; 2) an increase in IAAox activity resulting in lower free IAA levels or; 3) a defective conversion of IBA into IAA.

Enhanced fatty acid accumulation in Isochrysis galbana by inhibition of the mitochondrial alternative oxidase pathway under nitrogen deprivation

The purpose of this study was to clarify the interrelation between the mitochondrial alternative oxidase (AOX) pathway and fatty acid accumulation in marine microalga Isochrysis galbana. Under normal conditions, the activity of the AOX pathway was maintained at a low level in I. galbana. Compared with the normal condition, nitrogen deprivation significantly increased the AOX pathway activity and fatty acid accumulation. Under nitrogen deprivation, the inhibition of the AOX pathway by salicylhydroxamic acid caused the accumulation of reducing equivalents and the over-reduction of chloroplasts in I. galbana cells, leading to a decrease in the photosynthetic O2 evolution rate. The over-production of reducing equivalents due to the inhibition of the AOX pathway under nitrogen deprivation further enhanced the accumulation of fatty acids in I. galbana cells.

Probing the Role of Organic Additives on the Film Formation Mechanism Relevant to Metal CMP

With the increasing demand of high performance technology, the necessity to improve the mechanics of electronic devices is becoming of great importance. This requires atomic level planarization to avoid defects on the surface of integrated circuits (IC) and hard disk drive (HDD) media through CMP by removing the metal complex film formed. Traditional CMP systems incorporate a synergistic interaction between slurry chemistry and various mechanical parameters to achieve high surface quality while ensuring surface planarity. In order to understand this relationship, it is necessary to probe the film forming capabilities of oxidizers, complexing agents, and corrosion inhibitors on the substrate surface. The changes and dissolution of the film formed on the surface will be analyzed through the comparison of activation energy and Open Circuit Potential (OCP). More specifically, the separate molecular interaction of Benzotriazole (BTA) and Salicylhydroxamic Acid (SHA), and the substrate will be studied through the quantization of activation energy. The difference in the surface quality of the substrate, dependent on the film formation mechanism, will be understood through Atomic Force Microscopy (AFM). This work aims to show how the use of electrochemical techniques and surface spectroscopy can be useful in understanding the underlying mechanism of film formation on Cu and NiP substrates. Previous studies have shown promise that the use of various additives plays an intricate role on the films formed, relying heavily on the metal substrate used.

Root growth restraint can be an acclimatory response to low pH and is associated with reduced cell mortality: a possible role of class III peroxidases and NADPH oxidases.

Low pH (<5.0) can significantly decrease root growth but whether this is a direct effect of H(+) or an active plant response is examined here. Tomato (Solanum lycopersicum cv Micro-Tom) roots were exposed directly or gradually to low pH through step-wise changes in pH over periods ranging from 4 to 24h. Roots exposed gradually to pH 4.5 grew even less than those exposed directly, indicating a plant-coordinated response. Direct exposure to pH 4.0 suppressed root growth and caused high cell mortality, in contrast to roots exposed gradually, in which growth remained inhibited but cell viability was maintained. Total class III peroxidase activity increased significantly in all low pH treatments, but was not correlated with the observed differential responses. Use of the enzyme inhibitors salicylhydroxamic acid (SHAM) or diphenyleneiodonium chloride (DPI) suggest that peroxidase and, to a lesser extent, NADPH oxidase were required to prevent or reduce injury in all low pH treatments. However, a role for other enzymes, such as the alternative oxidase is also possible. The results with SHAM, but not DPI, were confirmed in tobacco BY-2 cells. Our results indicate that root growth inhibition from low pH can be part of an active plant response, and suggest that peroxidases may have a critical early role in reducing loss of cell viability and in the observed root growth constraint.

Alternative Oxidase Pathway Optimizes Photosynthesis During Osmotic and Temperature Stress by Regulating Cellular ROS, Malate Valve and Antioxidative Systems.

The present study reveals the importance of alternative oxidase (AOX) pathway in optimizing photosynthesis under osmotic and temperature stress conditions in the mesophyll protoplasts of Pisum sativum. The responses of photosynthesis and respiration were monitored at saturating light intensity of 1000 μmoles m–2 s–1 at 25°C under a range of sorbitol concentrations from 0.4 to 1.0 M to induce hyper-osmotic stress and by varying the temperature of the thermo-jacketed pre-incubation chamber from 25 to 10°C to impose sub-optimal temperature stress. Compared to controls (0.4 M sorbitol and 25°C), the mesophyll protoplasts showed remarkable decrease in NaHCO3-dependent O2 evolution (indicator of photosynthetic carbon assimilation), under both hyper-osmotic (1.0 M sorbitol) and sub-optimal temperature stress conditions (10°C), while the decrease in rates of respiratory O2 uptake were marginal. The capacity of AOX pathway increased significantly in parallel to increase in intracellular pyruvate and reactive oxygen species (ROS) levels under both hyper-osmotic stress and sub-optimal temperature stress under the background of saturating light. The ratio of redox couple (Malate/OAA) related to malate valve increased in contrast to the ratio of redox couple (GSH/GSSG) related to antioxidative system during hyper-osmotic stress. Further, the ratio of GSH/GSSG decreased in the presence of sub-optimal temperature, while the ratio of Malate/OAA showed no visible changes. Also, the redox ratios of pyridine nucleotides increased under hyper-osmotic (NADH/NAD) and sub-optimal temperature (NADPH/NADP) stresses, respectively. However, upon restriction of AOX pathway by using salicylhydroxamic acid (SHAM), the observed changes in NaHCO3-dependent O2 evolution, cellular ROS, redox ratios of Malate/OAA, NAD(P)H/NAD(P) and GSH/GSSG were further aggravated under stress conditions with concomitant modulations in NADP-MDH and antioxidant enzymes. Taken together, the results indicated the importance of AOX pathway in optimizing photosynthesis under both hyper-osmotic stress and sub-optimal temperatures. Regulation of ROS through redox couples related to malate valve and antioxidant system by AOX pathway to optimize photosynthesis under these stresses are discussed.

Genetic engineering of AtAOX1a in Saccharomyces cerevisiae prevents oxidative damage and maintains redox homeostasis.

This study aimed to validate the physiological importance of Arabidopsis thaliana alternative oxidase 1a (AtAOX1a) in alleviating oxidative stress using Saccharomyces cerevisiae as a model organism. The AOX1a transformant (pYES2AtAOX1a) showed cyanide resistant and salicylhydroxamic acid (SHAM)‐sensitive respiration, indicating functional expression of AtAOX1a in S. cerevisiae. After exposure to oxidative stress, pYES2AtAOX1a showed better survival and a decrease in reactive oxygen species (ROS) when compared to S. cerevisiae with empty vector (pYES2). Furthermore, pYES2AtAOX1a sustained growth by regulating GPX2 and/or TSA2, and cellular NAD +/NADH ratio. Thus, the expression of AtAOX1a in S. cerevisiae enhances its respiratory tolerance which, in turn, maintains cellular redox homeostasis and protects from oxidative damage.