Antimicrobial activity of metal based nanoparticles against microbes associated with diseases in aquaculture

The emergence of diseases and mortalities in aquaculture and development of antibiotics resistance in aquatic microbes, has renewed a great interest towards alternative methods of prevention and control of diseases. Nanoparticles have enormous potential in controlling human and animal pathogens and have scope of application in aquaculture. The present investigation was carried out to find out suitable nanoparticles having antimicrobial effect against aquatic microbes. Different commercial as well as laboratory synthesized metal and metal oxide nanoparticles were screened for their antimicrobial activities against a wide range of bacterial and fungal agents including certain freshwater cyanobacteria. Among different nanoparticles, synthesized copper oxide (CuO), zinc oxide (ZnO), silver (Ag) and silver doped titanium dioxide (Ag–TiO₂) showed broad spectrum antibacterial activity. On the contrary, nanoparticles like Zn and ZnO showed antifungal activity against fungi like Penicillium and Mucor species. Since CuO, ZnO and Ag nanoparticles showed higher antimicrobial activity, they may be explored for aquaculture use.     

Root development and heavy metal phytoextraction efficiency: comparison of different plant species in the field

Heavy metal phytoextraction is a soil remediation technique which implies the optimal use of plants to remove contamination from soil. Plants must thus be tolerant to heavy metals, adapted to soil and climate characteristics and able to take up large amounts of heavy metals. Their roots must also fit the spatial distribution of pollution. Their different root systems allow plants to adapt to their environment and be more or less efficient in element uptake. To assess the impact of the root system on phytoextraction efficiency in the field, we have studied the uptake and root systems (root length and root size) of various high biomass plants (Brassica juncea, Nicotiana tabacum, Zea mays and Salix viminalis) and one hyperaccumulator (Thlaspi caerulescens) grown in a Zn, Cu and Cd contaminated soil and compared them with total heavy metal distribution in the soil. Changes from year to year have been studied for an annual (Zea mays) and a perennial plant (Salix viminalis) to assess the impact of the climate on root systems and the evolution of efficiency with time and growth. In spite of a small biomass, T. caerulescens was the most efficient plant for Cd and Zn removal because of very high concentrations in the shoots. The second most efficient were plants combining high metal concentrations and high biomass (willows for Cd and Zn and tobacco for Cu and Cd). A large cumulative root density/aboveground biomass ratio (L_A/B), together with a relative larger proportion of fine roots compared to other plants seemed to be additional favourable characteristics for increased heavy metal uptake by T. caerulescens. In general, for all plants correlations were found between L _A/B and heavy metal concentrations in shoots (r=0.758^***, r=0.594^***, r=0.798^*** (P<0.001) for Cd, Cu and Zn concentrations resp.). Differences between years were significant because of variations in climatic conditions for annual plants or because of growth for perennial plants. The plants exhibited also different root distributions along the soil profile: T. caerulescens had a shallow root system and was thus best suited for shallow contamination (0.2 m) whereas maize and willows were the most efficient in colonising the soil at depth and thus more applicable for deep contamination (0.7 m). In the field situation, no plant was able to fit the contamination properly due to heterogeneity in soil contamination. This points out to the importance and the difficulty of choosing plant species according to depth and heterogeneity of localisation of the pollution.     

Yield of submerged paddy and uptake of Zn,P and N as affected by liming and Zn fertilizers

The effects of CaCO₃, Zn sources and levels on the yield of submerged paddy and uptake of Zn, P and N to paddy were studied in green-house at Haryana Agricultural University, Hissar. Powdered CaCO₃ was mixed at 0,4 and 8 per cent and Zn was added at 0,5 and 10 ppm through ZnSO₄.7H₂O, ZnO and Zn EDTA separately. Dry weight at tillering and heading and grain and straw at maturity decreased significantly with 4 and 8 per cent CaCO₃ in comparison to the control. Increasing Zn application increased the dry weight and grain yield. Zn EDTA gave highest yield of paddy followed by ZnSO₄.7H₂O and ZnO.Increasing the application of CaCO₃ from 0–8 per cent decreased the concentration and uptake of Zn and increasing Zn application from 0–10 ppm increased concentration and uptake of Zn in paddy at tillering, heading and maturity. Zn EDTA gave the highest concentration and uptake of Zn followed by ZnSO₄.7H₂O and ZnO. There was interaction between Zn sources and CaCO₃.The concentration and uptake of N and P in paddy dry matter at tillering and heading and straw and grain at maturity decreased as compared to control with increasing CaCO₃ addition. The concentration and uptake of N increased and that of P decreased in paddy dry matter straw and grain with increasing Zn application. The highest concentration of N was observed with ZnO, followed by ZnSO₄.7H₂O and Zn EDTA. But highest uptake of N was observed with Zn EDTA followed by ZnSO₄.7H₂O and ZnO. As regards concentration and uptake of P, it was highest with ZnO followed by ZnSO₄.7H₂O and Zn EDTA.     

Selective hydrogenolysis of raw glycerol to 1,2-propanediol over Cu–ZnO catalysts in fixed-bed reactor

The catalytic properties of Cu–ZnO catalysts for glycerol hydrogenolysis to 1,2-propanediol (1,2-PDO) were tested in a fixed-bed reactor at 250 °C and 2.0 MPa H₂. The relation between composition, surface properties, and catalytic performance of glycerol hydrogenation of Cu–ZnO catalysts was studied using nitrogen adsorption (BET methods), XRD, H₂ temperature-programmed reduction, and N₂O chemisorptions. It was found that there was a close link between the surface CuO amount of Cu–ZnO catalyst and the reactivity for glycerol hydrogenation. The Cu–ZnO catalyst (Cu/Zn = 1.86) which had the highest surface Cu amount showed the best catalytic activity for glycerol hydrogenolysis. Furthermore, Cu–ZnO catalyst presented good stability and remarkable catalytic activity for glycerol hydrogenolysis to 1,2-PDO using raw glycerol derived from the fat saponification as feedstock.     

Association of the physical and chemical properties and the cytotoxicity of metal oxide nanoparticles: metal ion release, adsorption ability and specific surface area

Association of cellular influences and physical and chemical properties were examined for 24 kinds of industrial metal oxide nanoparticles: ZnO, CuO, NiO, Sb(2)O(3), CoO, MoO(3), Y(2)O(3), MgO, Gd(2)O(3), SnO(2), WO(3), ZrO(2), Fe(2)O(3), TiO(2), CeO(2), Al(2)O(3), Bi(2)O(3), La(2)O(3), ITO, and cobalt blue pigments. We prepared a stable medium dispersion for each nanoparticle and examined the influence on cell viability and oxidative stress together with physical and chemical characterizations. ZnO, CuO, NiO, MgO, and WO(3) showed a large amount of metal ion release in the culture medium. The cellular influences of these soluble nanoparticles were larger than insoluble nanoparticles. TiO(2), SnO(2), and CeO(2) nanoparticles showed strong protein adsorption ability; however, cellular influences of these nanoparticles were small. The primary particle size and the specific surface area seemed unrelated to cellular influences. Cellular influences of metal oxide nanoparticles depended on the kind and concentrations of released metals in the solution. For insoluble nanoparticles, the adsorption property was involved in cellular influences. The primary particle size and specific surface area of metal oxide nanoparticles did not affect directly cellular influences. In conclusion the most important cytotoxic factor of metal oxide nanoparticles was metal ion release.     

Fungicidal synergistic effect of biogenically synthesized zinc oxide and copper oxide nanoparticles against Alternaria citri causing citrus black rot disease

Citrus black rot disease being caused by Alternaria citri is a major disease of citrus plants with 30–35% economic loss annually. Fungicides had not been effective in the control of this disease during last few decades. In the present study, antifungal role of green synthesized zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs) were studied against Alternaria citri. Alternaria citri was isolated from disease fruits samples and was identified by staining with lacto phenol cotton blue. Furthermore, CuO and ZnO NPs were synthesized by utilizing the lemon peels extract as the reducing and capping agent. Nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. From the XRD data, the calculated size of CuO NPs was to be 18 nm and ZnO NPs was16.8 nm using Scherrer equation. The SEM analyses revealed the surface morphology of all the metal oxide NPs synthesized were rounded, elongated and or spherical in the shape. The zone of inhibition was observed to be 50 ± 0.5 mm by CuO NPs, followed by 51.5 ± 0.5 mm by ZnO NPs and maximum zone of antifungal inhibition was observed to be 53 ± 0.6 mm by mix metal oxide NPs. The results of minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) of the synthesized nanoparticles showed that at the certain concentrations (80 mg ml^?1), these NPs were capable of inhibiting the fungal growth, whereas above that specified concentrations (100 mg ml^?1), NPs completely inhibited the fungal growth. Based on these findings, the green synthesized NPs can be used as alternative to fungicide in order to control the citrus black rot disease.     

Effects of liming on the extractability of Fe,Mn, Zn and Cu from a peat medium and the growth and micronutrient uptake of highbush blueberry plants

Summary Levels of extractable micronutrients in a peat and the growth and nutrient uptake of young highbush blueberry plants (Vaccinium corymbosum L cv. Blueray) were studied in a greenhouse experiment in response to liming and two rates of addition of Fe, Mn, Zn and Cu.Levels of extractable micronutrients showed different trends with liming depending upon the extractant used and the element being considered. Levels of 0.05M CaCl₂-extractable Fe, Mn and Zn decreased as the pH was raised whilst those of Cu first decreased and then increased again. There was a general decline in 0.1M HCl-extractable Fe, Mn and Cu with increasing pH but levels of Zn were not greatly affected. Levels of 0.005M DTPA extractable Fe, Mn Zn and Cu generally declined but those extractable with 0.04M EDTA were either unaffected or increased as the pH was raised. Levels of CaCl₂-extractable Mn and Zn were the same order of magnitude as those extractable with HCl, DTPA and EDTA. In contrast, the latter reagents extracted considerably more Fe and Cu than did CaCl₂.Dry matter yields of plants were increased as the pH was raised from 3.9 to 4.3 but then decreased markedly as the pH was raised further to 6.7. With increasing pH, concentrations of plant Fe generally increased those of Mn were decreased and those of Zn and Cu were not greatly affected except for a marked decline in plant Cu at pH 6.7.     

Green synthesis and characterization of zinc oxide nanoparticles using Cayratia pedata leaf extract

The synthesis of Zinc oxide nanoparticles using a plant-mediated approach is presented in this paper. The nanoparticles were successfully synthesized using the Nitrate derivative of Zinc and plant extract of the indigenous medicinal plant Cayratia pedata. 0.1 mM of Zn (NO₃)₂.6H₂O was made to react with the plant extract at different concentrations, and the reaction temperature was maintained at 55 °C, 65 °C, and 75 °C. The yellow coloured paste obtained was wholly dried, collected, and packed for further analysis. In the UV visible spectrometer (UV–Vis) absorption peak was observed at 320 nm, which is specific for Zinc oxide nanoparticles. The characterization carried out using Field Emission Scanning Electron Microscope (FESEM) reveals the presence of Zinc oxide nanoparticles in its agglomerated form. From the X-ray diffraction (XRD) pattern, the average size of the nanoparticles was estimated to be 52.24 nm. Energy Dispersive Spectrum (EDX) results show the composition of Zinc and Oxygen, giving strong energy signals of 78.32% and 12.78% for Zinc and Oxygen, respectively. Fourier Transform - Infra-Red (FT-IR) spectroscopic analysis shows absorption peak of Zn–O bonding between 400 and 600 cm^?1. The various characterization methods carried out confirm the formation of nano Zinc oxide. The synthesized nanoparticles were used in the immobilization of the enzyme Glucose oxidase. Relative activity of 60% was obtained when Glucose oxidase was immobilized with the green synthesized ZnO nanoparticles. A comparative study of the green synthesized with native ZnO was also carried out. This green method of synthesis was found to be cost-effective and eco-friendly.     

The role of heavy-metal ATPases,HMAs, in zinc and cadmium transport in rice

The P_1B-type heavy metal ATPases (HMAs) are diverse in terms of tissue distribution, subcellular localization, and metal specificity. Functional studies of HMAs have shown that these transporters can be divided into two subgroups based on their metal-substrate specificity: a copper (Cu)/silver (Ag) group and a zinc (Zn)/cobalt (Co)/cadmium (Cd)/lead (Pb) group. Studies on Arabidopsis thaliana and metal hyperaccumulator plants indicate that HMAs play an important role in the translocation or detoxification of Zn and Cd in plants. Rice possesses nine HMA genes, of which OsHMA1–OsHMA3 belong to the Zn/Co/Cd/Pb subgroup. OsHMA2 plays an important role in root-to-shoot translocation of Zn and Cd, and participates in Zn and Cd transport to developing seeds in rice. OsHMA3 transports Cd and plays a role in the sequestration of Cd into vacuoles in root cells. Modification of the expression of these genes might be an effective approach for reducing the Cd concentration in rice grains.     

Comparative Study of Antibiofilm Activity of Copper Oxide and Iron Oxide Nanoparticles Against Multidrug Resistant Biofilm Forming Uropathogens

The effectiveness of the metal oxide nanoparticles viz. CuO and Fe₂O₃ as antibacterial agents against multidrug resistant biofilm forming bacteria was evaluated. CuO nanoparticles were also experimented for antibiofilm and time kill assay. The CuO displayed maximum antibacterial activity with zone of inhibition of (22 ± 1) mm against methicillin resistant Staphylococcus aureus (MRSA) followed by Escherichia coli (18 ± 1) mm. The Fe₂O₃ showed the zone of inhibition against MRSA of (14 ± 1) mm followed by E. coli (12 ± 1) mm. CuO proved to be more toxic than Fe₂O₃ nanoparticles showing significantly high antibacterial activity and found to possess dose dependent antibiofilm properties.     

Rapid,controllable, one‐pot and room‐temperature aqueous synthesis of ZnO:Cu nanoparticles by pulsed UV laser and its application for photocatalytic degradation of methyl orange

Zinc oxide (ZnO) and ZnO:Cu nanoparticles (NPs) were synthesized using a rapid, controllable, one‐pot and room‐temperature pulsed UV‐laser assisted method. UV‐laser irradiation was used as an effective energy source in order to gain better control over the NPs size and morphology in aqueous media. Parameters effective in laser assisted synthesis of NPs such as irradiation time and laser shot repetition rate were optimized. Photoluminescence (PL) spectra of ZnO NPs showed a broad emission with two trap state peaks located at 442 and 485 nm related to electronic transition from zinc interstitial level (I_Zn) to zinc vacancy level (V_Zn) and electronic transition from conduction band to the oxygen vacancy level (V_O), respectively. For ZnO:Cu NPs, trap state emissions disappeared completely and a copper (Cu)‐related emission appeared. PL intensity of Cu‐related emission increased with the increase in concentration of Cu²⁺, so that for molar ratio of Cu:Zn 2%, optimal value of PL intensity was obtained. The photocatalytic activity of Cu‐doped ZnO revealed 50 and 100% increasement than that of undoped NPs under UV and visible irradiation, respectively. The enhanced photocatalytic activity could be attributed to smaller crystal size, as well as creation of impurity acceptor levels (T₂) inside the ZnO energy band gap.     

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn_1-xMg_xO thin films onto p-type thermally oxidized Cu₂O substrates outside vacuum at low temperature. The performance of photovoltaic devices featuring atmospherically fabricated ZnO/Cu₂O heterojunction was dependent on the conditions of AP-SALD film deposition, namely, the substrate temperature and deposition time, as well as on the Cu₂O substrate exposure to oxidizing agents prior to and during the ZnO deposition. Superficial Cu₂O to CuO oxidation was identified as a limiting factor to heterojunction quality due to recombination at the ZnO/Cu₂O interface. Optimization of AP-SALD conditions as well as keeping Cu₂O away from air and moisture in order to minimize Cu₂O surface oxidation led to improved device performance. A three-fold increase in the open-circuit voltage (up to 0.65 V) and a two-fold increase in the short-circuit current density produced solar cells with a record 2.2% power conversion efficiency (PCE). This PCE is the highest reported for a Zn_1-xMg_xO/Cu₂O heterojunction formed outside vacuum, which highlights atmospheric pressure spatial ALD as a promising technique for inexpensive and scalable fabrication of Cu₂O-based photovoltaics.     

Tailoring size and structural distortion of Fe3O4 nanoparticles for the purification of contaminated water

Fe₃O₄ magnetic nanoparticles with different particle sizes were synthesized using two methods, i.e., a co-precipitation process and a polyol process, respectively. The atomic pair distribution analyses from the high-energy X-ray scattering data and TEM observations show that the two kinds of nanoparticles have different sizes and structural distortions. An average particle size of 6–8 nm with a narrow size distribution was observed for the nanoparticles prepared with the co-precipitation method. Magnetic measurements show that those particles are in ferromagnetic state with a saturation magnetization of 74.3 emu g⁻¹. For the particles synthesized with the polyol process, a mean diameter of 18–35 nm was observed with a saturation magnetization of 78.2 emu g⁻¹. Although both kinds of nanoparticles are well crystallized, an obviously higher structural distortion is evidenced for the co-precipitation processed nanoparticles. The synthesized Fe₃O₄ particles with different mean particle size were used for treating the wastewater contaminated with the metal ions, such as Ni(II), Cu(II), Cd(II) and Cr(VI). It is found that the adsorption capacity of Fe₃O₄ particles increased with decreasing the particle size or increasing the surface area. While the particle size was decreased to 8 nm, the Fe₃O₄ particles can absorb almost all of the above-mentioned metal ions in the contaminated water with the adsorption capacity of 34.93 mg/g, which is ∼7 times higher than that using the coarse particles. We attribute the extremely high adsorption capacity to the highly-distorted surface.     

Characterization of metal tolerance and accumulation in Grevillea exul var exul

Grevillea exul var exul (Proteaceae), a tree species native to serpentine soils in New Caledonia, is a reported manganese accumulator. Since the metal tolerance of this species remains unknown, its growth and metal accumulation were studied for seven heavy metals under controlled conditions. Brassica juncea, a popular species for metal phytoremediation, was used as a reference. G. exul seedlings were more tolerant to Cr, Zn, Ni, and Cu than B. juncea. There were no differences in Hg, and Cd tolerance between both species. B. juncea seedlings concentrated more Cd, Hg, and Cr in their shoot than G. exul seedlings, while Ni, Zn, and Mn levels were similar for both species. Comparison then focused on tolerance at toxic doses of Ni and Mn using older individuals of both species. No growth inhibition for G. exul plants was observed, whereas the growth of B. juncea was significantly inhibited at the higher metal concentrations. Shoot Mn and Ni concentrations were again lower in G. exul plants as compared to B. juncea, suggesting a mechanism of partial Ni and Mn exclusion in G. exul. In a subsequent study, 1-year-old G. exul plants favored Ni accumulation in roots while Mn accumulated preferentially in shoots.     

Effects of soil acidification on the chemical extractability of Fe,Mn, Zn and Cu and the growth and micronutrient uptake of highbush blueberry plants

Summary The effects of soil acidification and micronutrient addition on levels of extractable Fe, Mn, Zn and Cu in a soil, and on the growth and micronutrient uptake of young highbush blueberry plants (Vaccinium corymbosum L. cv. Blueray) was investigated in a greenhouse study.Levels of 0.05M CaCl₂-extractable Fe, Mn, Zn and Cu increased as the pH was lowered from 7.0 to 3.8. However, the solubility (CaCl₂-extractability) of Fe and Cu was considerably less pH-dependent than that of Mn and Zn. With the exception of HCl-and DTPA-extractable Mn, micronutrients extractable with 0.1M HCl, 0.005M DTPA and 0.04M EDTA were unaffected or raised only slightly as the pH was lowered from 6.0 to 3.8. Quantities of Mn and Zn extractable with CaCl₂ were similar in magnitude to those extractable with HCl, DTPA and EDTA whilst, in contrast, the latter reagents extracted considerably more Cu and Fe than did CaCl₂. A fractionation of soil Zn and Cu revealed that soil acidification resulted in an increase in the CaCl₂- and pyrophosphate-extractable fractions and a smaller decrease in the oxalate-extractable fraction.Plant dry matter production increased consistently when the soil pH was lowered from 7.0 to 4.6 but there was a slight decline in dry matter as the pH was lowered to 3.8. Micronutrient additions had no influence on plant biomass although plant uptake was increased. As the pH was lowered, concentrations of plant Fe first decreased and then increased whilst those of Mn, and to a lesser extent Zn and Cu, increased markedly.     

Availability of cadmium and zinc accumulated in the leaves of Thlaspi caerulescens incorporated into soil

When grown on contaminated soil, hyperaccumulator plants contain high concentrations of metals which may return to the soil after senescence. This work was undertaken to assess the availability of Cd and Zn associated to the leaves of the hyperaccumulator Thlaspi caerulescens after incorporation into an uncontaminated soil. A Zn- and Cd- accumulator population of T. caerulescens was grown on a Cd- and Zn- contaminated soil previously labelled with ¹⁰⁹Cd. Leaves (TCL) were harvested, dried, ground and incorporated into the soil at a rate of 2.07 mg Cd kg⁻¹ and 51.9 mg Zn kg⁻¹. Then a pot experiment was conducted for 3 months with rye grass (Lolium perenne) and T. caerulescens. Rye grass was harvested monthly and T. caerulescens at the end of the experiment. Plant biomass was measured, along with the concentration of Cd, Zn and ¹⁰⁹Cd. Results showed that water-extractable metals in TCL were 69% for Zn and 33% for Cd. Addition of TCL to soil, depleted growth of rye grass, and improved that of T. caerulescens. At harvest, concentrations of both metals were increased in plants by TCL. Concentrations of Cd in rye grass increased with the cut number, while that of Zn decreased slightly. Rye grass extracted 1.6% of the total Cd and 0.9% of the total Zn, and T. caerulescens extracted up to 22.4% of the Cd and 7% of the Zn. About 94% of the Cd in rye grass and 86% in T. caerulescens was derived from TCL. In conclusion, metals associated with leaves of the hyperaccumulator T. caerulescens were very mobile after incorporation into the soil. This revised version was published online in June 2006 with corrections to the Cover Date.     

Phytoextraction of zinc, copper, nickel and lead from a contaminated soil by different species of Brassica

In a pot culture experiment, five different species of Brassica (Brassica juncea, Brassica campestris, Brassica carinata, Brassica napus, and Brassica nigra) were grown for screening possible accumulators of heavy metals, viz. Zn, Cu, Ni, and Pb. The plants were grown to maturity in a soil irrigated with sewage effluents for more than two decades in West Delhi, India. The soil analysis showed enhanced accumulation of Zn, Cu, Ni, and Pb in this sewage-irrigated soil. Among all species, B. carinata showed the highest concentration (mg kg(-1)) as well as uptake (microg pot(-1)) of Ni and Pb at maturity. Although B. campestris showed a higher concentration of Zn in its shoots (stem plus leaf), B. carinata extracted the largest amount of this metal due to greater biomass production. However, B. juncea phytoextracted the largest amount of Cu from the soil. In general, the highest concentration and uptake of metal was observed in shoots compared to roots or seeds of the different species. Among the Brassica spp., B. carinata cv. DLSC1 emerged as the most promising, showing greater uptake of Zn, Ni, and Pb, while B. juncea cv. Pusa Bold showed the highest uptake of Cu. The B. napus also showed promise, as it ranked second with respect to total uptake of Pb, Zn, and Ni, and third for Cu. Total uptake of metals by Brassica spp. correlated negatively with available as well as the total soil metal concentrations. Among the root parameters, root length emerged as the powerful parameter to dictate the uptake of metals by Brassica spp. Probably for the first time, B. carinata was reported as a promising phytoextractor for Zn, Ni, and Pb, which performed better than B. juncea.