Nirupam Aich

Effects of Chloride and Ionic Strength on Physical Morphology, Dissolution, and Bacterial Toxicity of Silver Nanoparticles

In this study, we comprehensively evaluate chloride- and ionic-strength-mediated changes in the physical morphology, dissolution, and bacterial toxicity of silver nanoparticles (AgNPs), which are one of the most-used nanomaterials. The findings isolate the impact of ionic strength from that of chloride concentration. As ionic strength increases, AgNP aggregation likewise increases (such that the hydrodynamic radius [HR] increases), fractal dimension (Df) strongly decreases (providing increased available surface relative to suspensions with higher Df), and the release of Ag(aq) increases. With increased Ag(+) in solution, Escherichia coli demonstrates reduced tolerance to AgNP exposure (i.e., toxicity increases) under higher ionic strength conditions. As chloride concentration increases, aggregates are formed (HR increases) but are dominated by AgCl(0)(s) bridging of AgNPs; relatedly, Df increases. Furthermore, AgNP dissolution strongly increases under increased chloride conditions, but the dominant, theoretical, equilibrium aqueous silver species shift to negatively charged AgClx((x-1)-) species, which appear to be less toxic to E. coli. Thus, E. coli demonstrates increased tolerance to AgNP exposure under higher chloride conditions (i.e., toxicity decreases). Expression measurements of katE, a gene involved in catalase production to alleviate oxidative stress, support oxidative stress in E. coli as a result of Ag(+) exposure. Overall, our work indicates that the environmental impacts of AgNPs must be evaluated under relevant water chemistry conditions.

Emergent Properties and Toxicological Considerations for Nanohybrid Materials in Aquatic Systems

Conjugation of multiple nanomaterials has become the focus of recent materials development. This new material class is commonly known as nanohybrids or “horizon nanomaterials”. Conjugation of metal/metal oxides with carbonaceous nanomaterials and overcoating or doping of one metal with another have been pursued to enhance material performance and/or incorporate multifunctionality into nano-enabled devices and processes. Nanohybrids are already at use in commercialized energy, electronics and medical products, which warrant immediate attention for their safety evaluation. These conjugated ensembles likely present a new set of physicochemical properties that are unique to their individual component attributes, hence increasing uncertainty in their risk evaluation. Established toxicological testing strategies and enumerated underlying mechanisms will thus need to be re-evaluated for the assessment of these horizon materials. This review will present a critical discussion on the altered physicochemical properties of nanohybrids and analyze the validity of existing nanotoxicology data against these unique properties. The article will also propose strategies to evaluate the conjugate materials’ safety to help undertake future toxicological research on the nanohybrid material class.

A critical review of nanohybrids: synthesis, applications and environmental implications

Environmental context Recent developments in nanotechnology have focussed towards innovation and usage of multifunctional and superior hybrid nanomaterials. Possible exposure of these novel nanohybrids can lead to unpredicted environmental fate, transport, transformation and toxicity scenarios. Environmentally relevant emerging properties and potential environmental implications of these newer materials need to be systematically studied to prevent harmful effects towards the aquatic environment and ecology. Abstract Nanomaterial synthesis and modification for applications have progressed to a great extent in the last decades. Manipulation of the physicochemical properties of a material at the nanoscale has been extensively performed to produce materials for novel applications. Controlling the size, shape, surface functionality, etc. has been key to successful implementation of nanomaterials in multidimensional usage for electronics, optics, biomedicine, drug delivery and green fuel technology. Recently, a focus has been on the conjugation of two or more nanomaterials to achieve increased multifunctionality as well as creating opportunities for next generation materials with enhanced performance. With incremental production and potential usage of such nanohybrids come the concerns about their ecological and environmental effects, which will be dictated by their not-yet-understood physicochemical properties. While environmental implication studies concerning the single materials are yet to give an integrated mechanistic understanding and predictability of their environmental fate and transport, the importance of studying the novel nanohybrids with their multi-dimensional and complex behaviour in environmental and biological exposure systems are immense. This article critically reviews the literature of nanohybrids and identifies potential environmental uncertainties of these emerging ‘horizon materials’.

Preparation and characterization of stable aqueous higher-order fullerenes

Stable aqueous suspensions of nC₆₀ and individual higher fullerenes, i.e. C₇₀, C₇₆ and C₈₄, are prepared by a calorimetric modification of a commonly used liquid-liquid extraction technique. The energy requirement for synthesis of higher fullerenes has been guided by molecular-scale interaction energy calculations. Solubilized fullerenes show crystalline behavior by exhibiting lattice fringes in high resolution transmission electron microscopy images. The fullerene colloidal suspensions thus prepared are stable with a narrow distribution of cluster radii (42.7 ± 0.8 nm, 46.0 ± 14.0 nm, 60 ± 3.2 nm and 56.3 ± 1.1 nm for nC₆₀, nC₇₀, nC₇₆ and nC₈₄, respectively) as measured by time-resolved dynamic light scattering. The ζ-potential values for all fullerene samples showed negative surface potentials with similar magnitude ( - 38.6 ± 5.8 mV, - 39.1 ± 4.2 mV, - 38.9 ± 5.8 mV and - 41.7 ± 5.1 mV for nC₆₀, nC₇₀, nC₇₆ and nC₈₄, respectively), which provide electrostatic stability to the colloidal clusters. This energy-based modified solubilization technique to produce stable aqueous fullerenes will likely aid in future studies focusing on better applicability, determination of colloidal properties, and understanding of environmental fate, transport and toxicity of higher-order fullerenes.

Mechanistic lessons learned from studies of planktonic bacteria with metallic nanomaterials: implications for interactions between nanomaterials and biofilm bacteria

Metal and metal-oxide nanoparticles (NPs) are used in numerous applications and have high likelihood of entering engineered and natural environmental systems. Careful assessment of the interaction of these NPs with bacteria, particularly biofilm bacteria, is necessary. This perspective discusses mechanisms of NP interaction with bacteria and identifies challenges in understanding NP–biofilm interaction, considering fundamental material attributes and inherent complexities of biofilm structure. The current literature is reviewed, both for planktonic bacteria and biofilms; future challenges and complexities are identified, both in light of the literature and a dataset on the toxicity of silver NPs toward planktonic and biofilm bacteria. This perspective aims to highlight the complexities in such studies and emphasizes the need for systematic evaluation of NP–biofilm interaction.

Preparation of non-aggregating aqueous fullerenes in highly saline solutions with a biocompatible non-ionic polymer.

Size-tunable stable aqueous fullerenes were prepared with different concentrations of biocompatible block-copolymer pluronic (PA) F-127, ranging from 0.001% to 1% (w/v). Size uniformity increased with the increase in PA concentration, yielding optimum 58.8 ± 5.6 and 61.8 ± 5.6 nm nC₆₀s and nC₇₀s, respectively (0.10%w/v PA), as observed using a dynamic light scattering technique. Fullerene aqueous suspensions also manifested enhanced stability in saline solution, Dulbeccos modified Eagle medium (DMEM), and Roswell Park Memorial Institute (RPMI) culture medium. Transmission electron microscopy was performed to elaborate on the morphology and size specificity of fullerene clusters. Physicochemical characterizations of the suspended fullerenes were performed through UV-vis spectroscopy and electrophoretic mobility measurements. PA molecules showed size restriction by encasement, as observed via molecular dynamics simulations. Such solubilization with controllable size and non-aggregating behavior can facilitate application enhancement and mechanistic environmental and toxicological studies of size-specific fullerenes.

Triboluminescence for distributed damage assessment in cement-based materials

Triboluminescent materials are promising in the field of structural health monitoring for real-time crack detection and related damage assessment. This study presents a simple, but novel, image processing protocol to detect and quantify luminescence from crack formation in cement-based matrices. Mortar cubes of 2″× 2″ (5.1 cm × 5.1 cm) were loaded in compression with an external coating of manganese-doped zinc sulfide (ZnS:Mn) triboluminescent material. The concentration of triboluminescent material and rate of loading were varied to evaluate luminescence response. A digital single lens reflex camera was employed to capture luminescence from the resulting cracks, which formed and propagated during failure. The images were then analyzed with an image processor, and total luminescence/pixel along the cracks was quantified. Results show that overall luminescence increases with the increase in triboluminescent concentration as well as with the rate of loading. This article presents a novel method that can be applied to monitor crack formation in cement-based materials, providing reliable accuracy in luminescence quantification.

Aggregation Kinetics of Higher-Order Fullerene Clusters in Aquatic Systems

The aggregation kinetics of nC60 and higher-order fullerene (HOF) clusters, i.e., nC70, nC76, and nC84, was systematically studied under a wide range of mono- (NaCl) and divalent (CaCl2) electrolytes and using time-resolved dynamic light scattering. Suwanee River Humic Acid (SRHA) was also used to determine the effect of natural macromolecules on nHOF aggregation. An increase in electrolyte concentration resulted in electrical double-layer compression of the negatively charged fullerene clusters, and the nC60s and nHOFs alike displayed classical Derjaguin-Landau-Verwey-Overbeek (DLVO) type interaction. The critical coagulation concentration (CCC) displayed a strong negative correlation with the carbon number in fullerenes and was estimated as 220, 150, 100, and 70 mM NaCl and 10, 12, 6, and 7.5 mM CaCl2 for nC60, nC70, nC76, and nC84, respectively. The aggregation mechanism (i.e., van der Waals interaction domination) was enumerated via molecular dynamics simulation and modified DLVO model. The presence of SRHA (2.5 mg TOC/L) profoundly influenced the aggregation behavior by stabilizing all fullerene clusters, even at a 100 mM NaCl concentration. The results from this study can be utilized to predict aggregation kinetics of nHOF clusters other than the ones studied here. The scaling factor for van der Waals interaction can also be used to model nHOF cluster interaction.

Detection of crack formation and stress distribution for carbon fiber–reinforced polymer specimens through triboluminescent-based imaging

This article demonstrates the ability of surface-coated triboluminescent materials to detect damage in carbon fiber–reinforced polymer specimens. An experimental protocol was developed to test the efficiency of the triboluminescent-based diagnostic method using carbon fiber–reinforced polymer coupons under combined bending–compression conditions. Luminescence, emitted from the triboluminescent coatings under quasi-static loading, was detected by capturing digital images. We employed image processing software to quantify change in luminescence as a function of triboluminescent concentration. We observed that 10%, 20%, and 30% triboluminescent coating resulted in 25.3, 27.9, and 40.4 (arbitrary units) total luminescence, respectively, which shows a positive correlation of triboluminescent concentration with luminescence. Finite element simulation was also performed to understand the stress and strain distribution and to aid in understanding and correlating light emission regions on the carbon fiber–reinforced polymer coupons under bending deformation. This work represents a step toward the development of a robust technology that employs triboluminescent materials for early damage detection, consistent with theoretical predictions of damage occurrence.

Graphene Nanoreinforcement for Cement Composites

This paper reports on research aimed at investigating the reinforcing effects of graphene nanoplatelets (GNPs) in cement composites. Nanoreinforced cement mortar cubes were prepared using surfactant-coated GNPs. The dispersion and embedment of GNPs in the cement matrix were verified based on evidence from compression strength tests and scanning electron microscopic imaging. Results from fracture mechanics tests on notched beams were then used to evaluate the effect of incorporating well-dispersed, surfactant-coated GNPs on the flexural strength and stiffness of cement paste. 3D digital image correlation measurements were used to study the morphology and evolution of the fracture process zone in plain and GNP-reinforced cement paste.