High reduction of 4-nitrophenol using reduced graphene oxide/Ag synthesized with tyrosine

There is a demand for the development of environmental friendly methods for the synthesis of graphene composites. Reduced graphene oxide/silver (RGO/Ag) nanocomposites are very good catalysts. Here, we propose a simple, green method for the synthesis of RGO/Ag nanocomposite using the amino acid tyrosine as bioreductant and stabilizing agent. RGO/Ag nanocomposite was characterized by using various analytical techniques and studied for its catalytic degradation of 4-nitrophenol. Results of attenuated total reflectance Fourier transform infrared spectroscopy and Zeta potential at ?55 mV reveal the surface capping of tyrosine onto the reduced graphene oxide nanosheets. RGO/Ag nanocomposites show excellent catalytic reduction of 4-nitrophenol with NaBH₄, when compared to actual individual silver nanoparticles.     

石墨烯与抑癌基因p53 DNA片段相互作用的分子模拟与光谱学验证

石墨烯(graphene,G)及其衍生物由于具有独特的理化性质,被广泛应用于能源、生物医学等领域,但尚缺乏其对生物体和环境潜在危害的研究。采用分子动力学模拟并结合光谱学方法(紫外可见吸收光谱、紫外变温实验及荧光光谱),分析了石墨烯与抑癌基因p53启动子区DNA片段(p53-DNA)间的相互作用,并探讨了相关作用机制。石墨烯的部分芳香环与p53-DNA碱基的芳香环之间存在π-π堆积作用,两者可以通过嵌插作用进行结合,同时还通过沟槽作用进一步结合。光谱实验进一步证实,在石墨烯作用下,p53-DNA的熔点(Tm)值升高,EB-DNA体系发生静态荧光淬灭,说明石墨烯能与p53-DNA结合;同时,p53-DNA与石墨烯结合后在260 nm处的吸光度升高,说明石墨烯对p53-DNA的双螺旋结构具有一定的破坏作用。上述研究结果从分子水平上分析了石墨烯与p53-DNA间的相互作用机制,有助于进一步阐明石墨烯的毒性作用机理。     

石墨烯纳米材料对哺乳动物的毒性及其作用机制

石墨烯是一种新兴纳米材料,具有独特的电学和光学性质、超大的比表面积以及潜在的生物相容性,在材料和电子产业、能源、环境以及生物医学等领域得到广泛应用。与此同时,石墨烯的环境行为和生物毒性也随之引起日益广泛的关注。本文通过对石墨烯纳米材料的生物毒性、细胞毒性、毒性影响因素和毒性机制等相关研究进展进行总结。石墨烯纳米材料可通过气管滴注、吸入、静脉注射、腹腔注射以及口服等方式进入体内,通过机械屏障、血脑屏障和血液胎盘屏障等积累在肺、肝、脾等部位引起急性或者慢性损伤;目前有关石墨烯毒性机制的研究主要集中于线粒体损伤、DNA损伤、炎性反应、凋亡等终点及氧化应激参与的复杂信号通路,不同石墨烯纳米材料的浓度、尺寸、表面结构和官能团等对石墨烯的生物毒性影响不同。鉴于当前该领域研究的局限性,对石墨烯纳米材料生物毒性研究的发展方向进行了展望,进而为石墨烯材料的安全应用提供理论借鉴和实践参考。     

Unusual thermal properties of graphene origami crease:A molecular dynamics study

Graphene is a two-dimensional material that can be folded into diverse and yet interesting nanostructures like macro-scale paper origami. Folding of graphene not only makes different morphological configurations but also modifies their mechanical and thermal properties. Inspired by paper origami, herein we studied systemically the effects of creases, where sp2 to sp3 bond transformation occurs, on the thermal properties of graphene origami using molecular dynamics (MD) simulations. Our MD simulation results show that tensile strain reduces (not increases) the interfacial thermal resistance owing to the presence of the crease. This unusual phenomenon is explained by the micro-heat flux migration and stress distribution. Our findings on the graphene origami enable the design of the next-generation thermal management devices and flexible electronics with tuneable properties.     

石墨烯纳米材料对哺乳动物的毒性及其作用机制

石墨烯是一种应用广泛的新兴非金属纳米材料，具有独特的电学机械性能、超大的比表面积以及潜在的生物相容性，在材料、电子、能源、光学以及生物医学等领域得到广泛应用。与此同时，石墨烯的环境行为和生物毒性也随之引起日益广泛的关注。本文通过对石墨烯纳米材料的动物毒性、细胞毒性、毒性影响因素和毒性机制等相关研究进展进行总结。石墨烯纳米材料可通过气管滴注、吸入、静脉注射、腹腔注射以及口服等方式进入体内，通过机械屏障、血脑屏障和血液胎盘屏障等积累在肺、肝、脾等部位引起急性或者慢性损伤；目前有关石墨烯毒性机制的研究主要集中于线粒体损伤、DNA损伤、炎性反应、凋亡等终点及氧化应激参与的复杂信号通路，不同石墨烯纳米材料的浓度、尺寸、表面结构和官能团等对石墨烯的生物毒性影响不同。鉴于当前该领域研究的局限性，对石墨烯纳米材料生物毒性研究的发展方向进行了展望，进而为石墨烯材料的安全应用提供理论借鉴和实践参考。     

Nanosensors and nanobiosensors in food and agriculture

The food and agriculture sector controls the economic growth of a developing country. The food industries have practices of growing crops, raising livestock and sea foods, food processing and packaging, regulating production and distribution with quality and safety. The process control and monitoring quality are crucial steps. Here we review nanosensors and nanobiosensors as alternative of classical quantification methods. Nanoscale dimensions of metal nanoparticles, metal nanoclusters, metal oxide nanoparticles, metal and carbon quantum dots, graphene, carbon nanotubes, and nanocomposites expand the sensitivity by signal amplification and integrate several novel transduction principles such as enhanced electrochemical, optical, Raman, enhanced catalytic activity, and superparamagnetic properties into the nanosensors. The electrochemical nanosensors, optical nanosensors, electronic nose and electronic tongue, nanobarcode technology, and wireless nanosensors have revolutionized the sensing in food and agriculture sectors with multiplex and real-time sensing capabilities. Despite previous success stories of the remunerative health sector, the approaches are transferred subsequently to food and agriculture sector; with potential application in detection of food contaminants such as preservatives, antibiotics, heavy metal ions, toxins, microbial load, and pathogens along with the rapid monitoring of temperature, traceability, humidity, gas, and aroma of the food stuff.     

Supported single-atom catalysts: synthesis,characterization, properties,and applications

In recent years, there has been a wide research in supported single-atom catalysts (SACs), which contain only isolated individual metal atoms dispersed on an appropriate support or coordinated with the surface atoms of the support. The SACs exhibit many fascinating characteristics including high activity, selectivity, and maximum atomic utilization. These characteristics arise from the low coordination status, quantum size effect, and the strong metal–support interaction, which have proved to be very powerful in many typical heterogeneous catalysis field including oxidation, hydrogenation, the water–gas shift reaction, methanol steam reforming, electrocatalysis, and photocatalysis. In this review, we summarized the recent progress in synthesis, characterizations, properties, and applications of SACs.     

Synthesis and potential applications of cyclodextrin-based metal–organic frameworks: a review

Metal–organic frameworks are porous polymeric materials formed by linking metal ions with organic bridging ligands. Metal–organic frameworks are used as sensors, catalysts for organic transformations, biomass conversion, photovoltaics, electrochemical applications, gas storage and separation, and photocatalysis. Nonetheless, many actual metal–organic frameworks present limitations such as toxicity of preparation reagents and components, which make frameworks unusable for food and pharmaceutical applications. Here, we review the structure, synthesis and properties of cyclodextrin-based metal–organic frameworks that could be used in bioapplications. Synthetic methods include vapor diffusion, microwave-assisted, hydro/solvothermal, and ultrasound techniques. The vapor diffusion method can produce cyclodextrin-based metal–organic framework crystals with particle sizes ranging from 200 nm to 400 μm. Applications comprise food packaging, drug delivery, sensors, adsorbents, gas separation, and membranes. Cyclodextrin-based metal–organic frameworks showed loading efficacy of the bioactive compounds ranging from 3.29 to 97.80%.

     

Cerium dioxide and composites for the removal of toxic metal ions

The presence of contaminants in potable water is a cause of worldwide concern. In particular, the presence of metals such as arsenic, lead, cadmium, mercury, chromium can affect human health. There is thus a need for advanced techniques of water decontamination. Adsorbents based on cerium dioxide (CeO₂), also named ‘ceria,’ have been used to remove contaminants such as arsenic, fluoride, lead and cadmium. Ceria and composites display high surface area, controlled porosity and morphology, and abundance of functional groups. They have already found usage in many applications including optical, semiconductor and catalysis. Exploiting their attractive features for water treatment would unravel their potential. We review the potential of ceria and its composites for the removal of toxic metal ions from aqueous medium. The article discusses toxic contaminants in water and their impact on human health; the synthesis and adsorptive behavior of ceria-based materials including the role of morphology and surface area on the adsorption capacity, best fit adsorption isotherms, kinetic models, possible mechanisms, regeneration of adsorbents; and future perspectives of using metal oxides such as ceria. The focus of the report is the generation of cost-effective oxides of rare-earth metal, cerium, in their standalone and composite forms for contaminant removal.     

Exigency for fusion of graphene and carbon nanotube with biomaterials

Biomaterial industry is a widely growing field that is closely related to advanced materials. With development in fabrication techniques new materials are being created by researchers daily. The currently used biomaterials for biomedical applications have some limitations. This review examines those limitations such as corrosion, short fatigue life, less wear resistance, and inadequate mechanical properties. These limitations may lead to adverse effects. To overcome these limitations carbon-based nanomaterials may be incorporated such that these biomaterials reach the level of ideal biomaterials. Upgrade of biomaterials with graphene and carbon nanotubes (CNTs) needs to be done only after checking the safety profile of these materials. Biocompatibility of functionalized graphene and CNT is found to be adequate for the use in many applications such as drug delivery, biosensing and imaging, cancer therapeutics, and tissue regeneration whereas pristine graphene and CNT may produce adverse effects. The potential of carbon-based nanomaterials and graphene (and its derivatives) in overcoming those limitations and enhancing biological activities of ongoing biomaterials by acting as composites and coating material is examined. In addition, nanomaterials employ new techniques in biomedical application such as cancer therapy for more efficient results.     

Effective and selective separation of perrhenate from acidic wastewater by super-stable,superhydrophobic, and recyclable biosorbent

• A ZnO-biochar hybrid composite was prepared by solvothermal-pyrolysis synthesis. • The superhydrophobic composite is suitable for selective recovery of Re(VII). • The adsorption mechanism is elucidated by experiments and material characterization. The recovery of scattered metal ions such as perrhenate (Re(VII)) from industrial effluents has enormous economic benefits and promotes resource reuse. Nanoscale-metal/biochar hybrid biosorbents are attractive for recovery but are limited by their insufficient stability and low selectivity in harsh environments. Herein, a superstable biochar-based biosorbent composed of ZnO nanoparticles with remarkable superhydrophobic features is fabricated, and its adsorption/desorption capabilities toward Re(VII) in strongly acidic aqueous solutions are investigated. The ZnO nanoparticle/biochar hybrid composite (ZBC) exhibits strong acid resistance and high chemical stability, which are attributable to strong C-O-Zn interactions between the biochar and ZnO nanoparticles. Due to the advantages of its hydrolytic stability, superhydrophobicity, and abundance of Zn-O sites, the ZBC proves suitable for the effective and selective separation of Re(VII) from single, binary and multiple ion systems (pH= 1), with a maximum sorption capacity of 29.41 mg/g. More importantly, this material also shows good recyclability and reusability, with high adsorption efficiency after six adsorption-desorption cycles. The findings in this work demonstrate that a metal/biochar hybrid composite is a promising sorbent for Re(VII) separation.     

The influence of physicochemical parameters on bioaccessibility-adjusted hazard quotients for copper,lead and zinc in different grain size fractions of urban street dusts and soils

When the hazard quotient for ingestion (HQI) of a trace element in soil and dust particles is adjusted for the element’s bioaccessibility, the HQI is typically reduced as compared to its calculation using pseudo-total element concentration. However, those studies have mostly used bulk particles (<2 mm or <250 µm), and the reduction in HQI when expressed as bioaccessible metal may not be similar among particle size fractions, the possibility probed by the present study of street dusts and soils collected in Tehran. The highest Cu, Pb and Zn near-total concentrations occurred in the finest particles of dusts and soils. Bioaccessible concentrations of Cu, Pb and Zn in the particles (mg kg^?1) were obtained using simple bioaccessibility extraction test (SBET). The bioaccessibility (%) did not vary much among near-total concentrations. In the bulk (<250 µm) sample, the bioaccessible concentration of Cu and Pb increased as the pH of sample increased, while Zn bioaccessibility (%) in the bulk particles was influenced by organic matter and cation exchange capacity. X-ray diffraction identified sulfide and sulfate minerals in all of the size-fractionated particles, which are insoluble to slightly soluble in acidic conditions and included most of the Cu and Pb in the samples. The only Zn-bearing mineral identified was hemimorphite, which would be highly soluble in the SBET conditions. The calculated HQI suggested potential non-carcinogenic health risk to children and adults from ingestions of soils and dusts regardless of particle size consideration, in the order of Zn > Pb ≥ Cu. The HQI calculated from near-total metal was not much different for particle size classes relative to bulk particles; however, the bioaccessibility percent-adjusted HQI for Pb was higher for the smaller particles than the bulk. This work is novel in its approach to compare HQI for a bulk sample of particles with its composite particle size fractions.     

Chelator-induced bioextraction of heavy metals from artificially contaminated soil by mushroom (Coprinus comatus)

This study investigated the potential use of chelator-induced bioextraction of heavy metals from soil by Coprinus comatus in a pot experiment. Two production waves of the mushroom were obtained to determine biomass and metal concentration. The application of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetate (NTA) slightly inhibited the growth of C. comatus, but significantly enhanced the accumulation of heavy metals in fruiting bodies compared with the control. The highest concentrations of Pb, Cu and Cd reached 900.60, 783.61 and 23.64 mg·kg^?1 in a single pot, respectively. However, application of citric acid (CA) had no effect on metal uptake. Moreover, chelators applied to soil after fructification increased the dry biomass and metal concentration in fruiting bodies compared with those applied before sowing mycelia. EDTA was more efficient for inducing metal uptake by C. comatus than NTA or CA, and split applications of EDTA after fructification resulted in the highest total metal uptake by mushroom, i.e. 19.08±2.84, 17.57±0.69 and 0.55±0.06 mg for Pb, Cu and Cd, respectively, which were 130, 12 and 5 times values obtained with the control. Interestingly, many mushrooms turned blue after soil had been treated with chelator, indicating that these mushrooms are rich in Cu.     

Evidence for microfloral succession on allochthonous plant litter in Apalachicola Bay,Florida, USA

Changes in hydrolytic, respiratory,catabolic and lipid biosynthetic activities depend at least in part on successional changes in the microfloral populations of allochthonous plant litter incubated in a semi-tropical estuary. Initial colonization is by populations which have a high content of muramic acid relative to the adenosine triphosphate (ATP) and which are progressively displaced by a microflora with a lower ratio of muramic acid to ATP. Scanning electron micrography of the plant-litter microflora shows a succession of forms, with an initial bacterial colonization and its progressive displacement by more complex forms. Estimates of the microbial mass and the rates of phospholipid synthesis suggest that the detrital microflora has a relatively slow growth rate compared to its growth potential.     

A low-maintenance,primary cell culture model for the assessment of carbon nanotube toxicity

Carbon nanotubes (CNTs) have gained substantial interest as a material for biomedical devices with reliable properties suitable for electrically conducting biomedical devices. While CNTs combine ideal properties for a number of tissue-interfacing applications, their biocompatibility and safety have been the source of considerable conjecture. This study outlines a method for evaluating biocompatibility, using a low-cost, short-term assessment model of CNT with primary cells, which are more representative of an in vivo situation than cell lines. It was demonstrated that carboxylate-modified, multi-walled CNTs exhibit cytotoxic behavior in as little as 6 hr of exposure to primary fibroblasts. The resultant cell death was concentration dependent, demonstrating the efficacy of acute assessment of cytocompatibility. Although cell viability remained relatively high (being above 85% for all CNT concentrations up to 500 μg/ml), these results reflect similar relationships found for longer term exposures. This method has reliable potential for high-throughput assessment and quality control of CNTs in biomedical applications using a primary cell model.     

Molecular dynamics of stability and structures in phytochelatin complexes with Zn,Cu, Fe,Mg, and Ca: Implications for metal detoxification

Phytochelatins, or (γ-glutamyl-cysteine) _n -glycine, are specialized peptides produced by plants and algae to mitigate toxic metal exposure, for instance in response to high levels of metals such as Cu, Cd, and Zn. Stability constants and structural characterization of metal–phytochelatin complexes are lacking. This information is required to gain mechanistic insights on the metal selectivity of phytochelatins. Here, we studied structural coordination and thermodynamic stability by performing molecular dynamics simulations of a fully hydrated phytochelatin molecule complexed with Ca²⁺, Mg²⁺, Fe²⁺, Zn²⁺, and Cu²⁺. Our results predict the following decreasing order for the thermodynamic stability of the phytochelatin complexes: Zn²⁺ ≥ Cu²⁺ ≥ Fe²⁺ > Mg²⁺ > Ca²⁺. The favorable binding energies with Zn²⁺ and Cu²⁺ over the other metal cations can be explained by shorter binding distances and greater coordination from carboxylate and keto O atoms. Conformational rearrangement of phytochelatin following metal chelation was captured by monitoring changes in the solvent-accessible volume. Accessibility of solvent molecules to the phytochelatin structure was inversely proportional to the distance between the coordinated ligands and the chelated metal. These new findings demonstrate the influence of the metal–phytochelatin structure on the metal-binding thermodynamics and the phytochelatin conformation, both of which are important to evaluate the intracellular role of phytochelatin in mediating algal response to toxic heavy metal exposure.     

Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water

• Magnetic multi-template molecularly imprinted polymer composite was synthesized. • MIP composite was used as the adsorbent for removal of tetracyclines from water. • MIP composite showed excellent adsorption selectivity toward tetracyclines. • MIP composite possessed good reusability. Antibiotic contamination of the water environment has attracted much attention from researchers because of their potential hazards to humans and ecosystems. In this study, a multi-template molecularly imprinted polymer (MIP) modified mesoporous silica coated magnetic graphene oxide (MGO@MS@MIP) was prepared by the surface imprinting method via a sol-gel process and was used for the selective, efficient and simultaneous removal of tetracyclines (TCs), including doxycycline (DC), tetracycline (TC), chlorotetracycline (CTC) and oxytetracycline (OTC) from water. The synthesized MIP composite was characterized by Fourier transform infrared spectroscopy, transmission electron microscope and thermogravimetric analysis. The adsorption properties of MGO@MS@MIP for these TCs were characterized through adsorption kinetics, isotherms and selectivity tests. The MIP composite revealed larger adsorption quantities, excellent selectivity and rapid kinetics for these four tetracyclines. The adsorption process was spontaneous and endothermic and followed the Freundlich isotherm model and the pseudo-second-order kinetic model. The MGO@MS@MIP could specifically recognize DC, TC, CTC and OTC in the presence of some chemical analogs. In addition, the sorption capacity of the MIP composite did not decrease significantly after repeated application for at least five cycles. Thus, the prepared magnetic MIP composite has great potential to contribute to the effective separation and removal of tetracyclines from water.     

石墨烯对高等植物幼苗的毒性及机理探究

随着石墨烯产品的广泛应用和潜在的环境释放,其对生态环境的影响已引起广泛关注。为探讨石墨烯对高等植物生长的影响,探究了其对黄瓜幼苗和玉米幼苗生长的影响及其致毒机理。结果表明,水培条件下,不同浓度的石墨烯(10、50、100、500、1 000和2 000 mg·L~(-1))处理植物幼苗15 d后,对植物幼苗的生长具有抑制作用。且随着处理时间和石墨烯浓度的增加,植物幼苗生长的所有指标,包括根/地上部鲜重和干重、根长、根尖数、株高和叶面积均相应降低。另外,黄瓜幼苗比玉米幼苗对石墨烯更加的敏感。进一步研究发现,石墨烯与黄瓜幼苗根部直接接触导致的物理损伤、氧化损伤,以及营养耗竭是其致毒机理。而石墨烯对玉米幼苗的致毒机理包括物理损伤和营养耗竭。本研究为石墨烯的环境风险评价提供了基础数据。     

Effects of nano carbon black and single-layer graphene oxide on settlement,survival and swimming behaviour of Amphibalanus amphitrite larvae

The effects of two carbon-based nanomaterials, nano-sized carbon black (nCB), and single-layer graphene oxide (GO) on settlement of Amphibalanus amphitrite (Cirripedia, Crustacea) cypris larvae (cyprids) were assessed after 24, 48, and 72 h of exposure. Additionally, the effects of these nanomaterials on the mortality and swimming behaviour of the nauplius larvae (nauplii) of the same organism were determined after 24 and 48 h. The data indicate that nCB is more effective as a potential antisettlement agent than single-layer GO; moreover, nCB did not show any adverse effects on the larvae. The swimming behaviour of II stage nauplii of A. amphitrite exposed to a suspension of nCB was inhibited only at very high nCB concentrations (≥0.5 mg/mL). Single-layer GO, on the contrary, showed lower antisettlement effects and was more active in altering the survival and inhibiting the swimming behaviour of the nauplii. An indication of the toxic or non-toxic mechanisms of the antisettlement properties of both of these nanomaterials is provided by the reversibility of the antisettlement activity. In conclusion, we propose nCB as an innovative antifouling nanomaterial that shows low toxicity towards the model organism (crustaceans) used in this study.     

Hair burning and liming in tanneries is a source of pollution by arsenic,lead, zinc,manganese and iron

Heavy metals in the environment may be toxic for human and animals. Tanneries are a source of pollution by heavy metals. There is little information on heavy metals pollution in tanneries, especially on metals produced by the process of hair burning and liming. Liming is the first stage of chemical treatment where animal hair or wool is removed with sodium sulphide and calcium oxide. Here we studied cow, goat, buffalo and sheep hair, conventional liming agents and liming wastewaters from several sources. Samples were acid-digested and aliquots were analysed by atomic absorption spectroscopy following APHA standard method to measure concentrations of arsenic, lead, cadmium, zinc, manganese and iron. Results show that the range of metal contents in hair or wool and liming agents are 1.3–8.2 mg/kg for arsenic, 0.02–21.8 mg/kg for lead, 17.7–121.0 mg/kg for manganese, 7.3–141.1 mg/kg for zinc and 119.6–10613.8 mg/kg for iron. Liming wastewaters contain 1.9–5.6 µg/L arsenic, 0.03–6.05 µg/L lead, 38.6–139.0 µg/L manganese, 144.0–171.5 µg/L zinc and 399.5–1069.0 µg/L iron. Cadmium was below detection limits. This is the first investigation that reveals that hair burning liming operation is a potential source of heavy metals in the environment.