Variable-Angle Surface Spectroscopy Reveals the Water Structure in the Stern Layer at Charged Aqueous Interfaces.

At charged aqueous interfaces, the second-order nonlinear optical response originates from water molecules within the diffuse part of the electrical double layer, which are ordered by the surface field and from water that additionally experiences chemical and physical interactions with the surface in the Stern layer. These two environments can either reinforce or diminish the overall signal and can be disentangled by varying the coherence length of their interaction with external laser fields. Here, we demonstrate a method in which the angle of incidence is varied to afford a significant change in the coherence length. When this technique was applied to the silica-water interface, it was observed that water molecules in the Stern and diffuse layers direct their hydrogen atoms toward the mineral surface at a low ionic strength and neutral pH. A decrease in the signal with increasing ionic strength is attributed to hydrated cation adsorption that competes with free water for deprotonated silanol sites.

Graphene oxide based crosslinker for simultaneous enhancement of mechanical toughness and self-healing capability of conventional hydrogels.

Extraordinary self-healing efficiency is rarely observed in mechanically strong hydrogels, which often limits the applications of hydrogels in biomedical engineering. We have presented an approach to utilize a special type of graphene oxide-based crosslinker (GOBC) for the simultaneous improvement of toughness and self-healing properties of conventional hydrogels. The GOBC has been prepared from graphene oxide (GO) by surface oxidation and further introduction of vinyl groups. It has been designed in such a way that the crosslinker is able to form both covalent bonds and noncovalent interactions with the polymer chains of hydrogels. To demonstrate the efficacy of GOBC, it was incorporated in a conventional polyacrylamide (PAM) and polyacrylic acid (PAA) hydrogel matrix, and the mechanical and self-healing properties of the prepared hydrogels were investigated. In PAM-GOBC hydrogels, it has been observed that the mechanical properties such as tensile strength, Young's modulus, and toughness are significantly improved by the incorporation of GOBC without compromising the self-healing efficiency. The PAM-GOBC hydrogel with a modulus of about 0.446 MPa exhibited about 70% stress healing efficiency after 40 h. Whereas, under the same conditions a PAM hydrogel with commonly used crosslinker N,N'-methylene-bis(acrylamide) of approximately the same modulus demonstrated no self-healing at all. Similar improvement of self-healing properties and toughness in PAA-GOBC hydrogel has also been observed which demonstrated the universality of the crosslinker. This crosslinker-based approach to improve the self-healing properties is expected to offer the possibility of the application of commonly used hydrogels in many different sectors, particularly in developing artificial tissues.

Synthesis, characterization, and comparative assessment of antimicrobial properties and cytotoxicity of graphene-, silver-, and zinc-based nanomaterials.

Zinc oxide (ZnO) and graphene oxide (GO) nanoparticles, silver/zinc zeolite (Ag/Zn-Ze), and graphene oxide-silver (GO-Ag) nanocomposites were synthesized and characterized with X-ray powder Diffraction, Field Emission Scanning Electron Microscope and Fourier Transform-Infrared Spectroscopy. The antibacterial efficacy of these nanoparticles was evaluated against E. coli. by shake flask method and plate culture method for different concentrations. For 105 cells/mL initial bacterial concentration, minimum inhibitory concentration (MIC) were <160, <320, <320, and >1280 µg/mL, and antibacterial concentration at which 50% cells are inhibited (IC50) were 47, 90, 78, and 250 µg/mL for Ag/Zn-Ze, GO, GO-Ag, and ZnO, respectively. Therefore, the shake flask method showed that for all nanoparticle concentrations, Ag/Zn-Ze, and GO-Ag exhibited greater inhibition efficacy, which was also highly dependent on initial bacterial concentration. However, in case of the plate culture method, similar range of inhibition capacity was found for Ag/Zn-Ze, GO-Ag, and ZnO, whereas GO showed lower potency to inhibit E. coli. In addition, GO-Ag nanocomposite exhibited more efficacy than Ag/Zn-Ze when the antibacterial surface was prepared with those. However, Ag/Zn-Ze showed no toxicity on Vero cells, whereas GO-Ag exhibited severe toxicity at higher concentrations. This study establishes GO-Ag and Ag/Zn-Ze as potent antimicrobial agents; however, their application dosage should carefully be chosen based on cytotoxic effects of GO-Ag in case of any possible physiological interaction.

Algae Adhesion onto Silicone is Sensitive to Environment-Induced Surface Restructuring.

Resistance to algae contamination is an important characteristic of insulators used in overhead power distribution in coastal environments. It is therefore important to understand the parameters governing algae adhesion onto polymer insulator materials such as silicone. Flow cell-based shear experiments were conducted in order to characterize the adhesion strength of algae onto polydimethylsiloxane surfaces, comparing fresh polymer substrates with those that have been soaked in water and saline solutions for 1 month. Both freshwater algae and seawater species could withstand considerably less drag force and were therefore more easily removed when the polymer was soaked in salt water. The polymer surface was found to be unaltered in terms of its roughness, contact angle, and lack of water uptake; no macroscopic surface characterization was therefore able to account for the differences in cell adhesion strength resulting from the soaking treatment. Surface-specific nonlinear vibrational spectroscopy, however, revealed subtle differences in the orientation of surface methyl groups that resulted from the water and saline exposure.

Implementing an integrated multi-technology platform for drug checking: Social, scientific, and technological considerations.

The illicit drug overdose crisis in North America continues to devastate communities with fentanyl detected in the majority of illicit drug overdose deaths. The COVID-19 pandemic has heightened concerns of even greater unpredictability in the drug supplies and unprecedented rates of overdoses. Portable drug-checking technologies are increasingly being integrated within overdose prevention strategies. These emerging responses are raising new questions about which technologies to pursue and what service models can respond to the current risks and contexts. In what has been referred to as the epicenter of the overdose crisis in Canada, a multi-technology platform for drug checking is being piloted in community settings using a suite of chemical analytical methods to provide real-time harm reduction. These include infrared absorption, Raman scattering, gas chromatography with mass spectrometry, and antibody-based test strips. In this Perspective, we illustrate some advantages and challenges of using multiple techniques for the analysis of the same sample, and provide an example of a data analysis and visualization platform that can unify the presentation of the results and enable deeper analysis of the results. We also highlight the implementation of a various service models that co-exist in a research setting, with particular emphasis on the way that drug checking technicians and harm reduction workers interact with service users. Finally, we provide a description of the challenges associated with data interpretation and the communication of results to a diverse audience.

Silica Surface Charge Enhancement at Elevated Temperatures Revealed by Interfacial Water Signals.

The structure of water adjacent to silica is sensitive to the degree of deprotonation of surface silanol groups. As a result, close inspection of signals originating from these water molecules can be used to reveal the surface charge density. We have used nonlinear vibrational spectroscopy of the water O-H stretching band over a temperature range of 10-75 °C to account for the increase in surface potential from deprotonation. We demonstrate that the behavior at the silica surface is a balance between increasing surface charge and a decreasing contribution of water molecules aligned by the surface charge. Together with a model that accounts for two different types of silanol sites, we use our data to report the changes in enthalpy and entropy for deprotonation at each site. This is the first experimental determination of these thermodynamic parameters for hydrated silanol groups at the silica surface, critical to a wide range of geochemical and technological applications.

Mechanically tough and highly stretchable poly(acrylic acid) hydrogel cross-linked by 2D graphene oxide.

The mechanical performances of hydrogels are greatly influenced by the functionality of cross-linkers and their covalent and non-covalent interactions with the polymer chains. Conventional chemical cross-linkers fail to meet the demand of large toughness and high extensibility for their immediate applications as artificial tissues like ligaments, blood vessels, and cardiac muscles in human or animal bodies. Herein, we synthesized a new graphene oxide-based two-dimensional (2D) cross-linker (GOBC) and exploited the functionality of the cross-linker for the enhancement of toughness and stretchability of a poly(acrylic acid) (PAA) hydrogel. The 2D nanosheets of GO were modified in such a way that they could provide multifunctional sites for both physical and chemical bonding with the polymer chains. Carboxylic acid groups at the surfaces of the GO sheets were coupled with the acrylate functional groups for covalent cross-linking, while the other oxygen-containing functional groups are responsible for physical cross-linking with polymers. The GOBC had been successfully incorporated into the PAA hydrogel and the mechanical properties of the GOBC cross-linked PAA hydrogel (PAA-GOBC) were investigated at various compositions of cross-linker. Seven times enhancement in both toughness and elongation at break has been achieved without compromising on the modulus for the as-synthesized PAA-GOBC compared to the conventional N,N'-methylenebis(acrylamide) (MBA) cross-linked PAA hydrogel. This facile and efficient way of GO modification is expected to lead the development of a high-performance nanocomposite for cutting-edge applications in biomedical engineering.

Bi-functional silica nanoparticles for simultaneous enhancement of mechanical strength and swelling capacity of hydrogels.

A combination of strong load-bearing capacity and high swelling degree is desired in hydrogels for many applications including drug delivery, tissue engineering, and biomedical engineering. However, a compromising relationship exists between these two most important characteristics of hydrogels. Improving both of these important properties simultaneously in a single hydrogel material is still beyond the satisfactory limit. Herein, we report a novel approach to address this problem by introducing a silica-based bi-functional 3D crosslinker. Our bi-functional silica nanoparticles (BF-Si NPs) possess amine groups that are able to offer pseudo-crosslinking effects induced by inter-cohesive bonding, and acrylate groups that can form conventional covalent crosslinking in the same hydrogel. We fabricated polyacrylic acid (PAc-Si) and polyacrylamide (PAm-Si) hydrogels using our BF-Si NPs via free radical polymerization to demonstrate this concept. Incorporation of the BF-Si crosslinkers into the hydrogels has resulted in a large enhancement in the mechanical properties compared to conventional hydrogel crosslinked with N,N'-methylene bisacrylamide (MBA). For instance, tensile strength and the toughness increased by more than 6 times and 10 times, respectively, upon replacing MBA with BF-Si in polyacrylamide hydrogel. Moreover, the hydrogels crosslinked with BF-Si exhibited a remarkably elevated level of swelling capacity in the aqueous medium. Our facile yet smart strategy of employing the 3D bi-functional crosslinker for combining high swelling degree and strong mechanical properties in the same hydrogels can be extended to the fabrication of many similar acrylate or vinyl polymer hydrogels.

Magnetic nanocomposite based on polyacrylic acid and carboxylated cellulose nanocrystal for the removal of cationic dye.

The development of safe and cost-effective methods for the treatment of dye polluted wastewater has been a great concern among researchers. Herein, we developed a nanocomposite (M3D-PAA-CCN) based on polyacrylic acid (PAA) crosslinked with magnetic 3D crosslinkers (M3D) and carboxylated cellulose nanocrystals (CCN), for the removal of cationic dyes from aqueous solutions. Acrylic-functionalized Fe3O4 nanoparticles were covalently linked to the polymer chains via the form of the 3D crosslinker to introduce magnetic properties into the as-synthesized nanocomposite. The addition of highly dispersive CCN reduced the gel-like properties of the nanocomposite and instead incorporated a diffusive nature, which was more desirable for adsorbents. The surface morphology of the nanocomposite was analyzed by FESEM and the size of the nanocomposite particles was found to be in the range of 60-90 nm. The chemical functionalities and compositions were determined by XPS, FTIR, and EDX analyses whereas TGA confirmed the thermal stability of M3D-PAA-CCN. The maximum adsorption capacity of the M3D-PAA-CCN (332 mg g-1) was measured higher than that of M3D-PAA (114 mg g-1) to a cationic methylene blue (MB) dye indicating the significant contribution of CCN. The adsorption capacity of the as-synthesized M3D-PAA-CCN was found to be highly pH-dependent and the adsorption capacity increased with the increase of pH owing to the greater negative charge as indicated by the higher zeta potential. The adsorption kinetics of MB on the composites was found to follow the pseudo-second-order model. The adsorption capacity was also investigated as a function of concentration to figure out the adsorption mechanism using Langmuir and Freundlich isotherm models. The Langmuir model fitted the adsorption process better as suggested by the relatively smaller nonlinear chi-square value obtained from the fitting parameters.

Recyclable Ag-decorated highly carbonaceous magnetic nanocomposites for the removal of organic pollutants.

Here, we report a novel fabrication of a magnetic carbon nanotube-reduced graphene oxide-silver nanocomposite for the adsorption and simultaneous catalytic reduction of two environmental pollutants. Fe3O4 nanoparticles were grown and anchored onto the multi-walled carbon nanotube (CNT) first to generate magnetic CNT (MCNT), which was further coated with polydopamine to enhance the stability of the Fe3O4 particles and introduce new functionalities on the surface. Hydrothermal treatment of the polydopamine-coated MCNT (PD-MCNT) with graphene oxide (GO) produced a highly carbonaceous reduced GO-PD-MCNT (rGO-PD-MCNT), which by itself exhibited very high adsorption capability. The catalytic property was integrated by depositing silver nanoparticles (AgNPs) on the rGO-PD-MCNT by reducing Ag(I) ions. High catalytic efficacy besides fast and efficient adsorption of the as-synthesized nanocomposites was demonstrated at variable pH during the removal of a toxic model dye, methylene blue (MB), and an aromatic nitro compound, 4-nitrophenol (4-NP). The nanocomposites were found to be magnetically separable, easily regenerable through desorption using water and ethanol, and thus highly recyclable (more than 15 cycles). The rare combination of all these properties in a single scaffold makes this nanocomposite potentially useful in a wide range of engineering and environmental applications.

A fast iris recognition system through optimum feature extraction.

With an increasing demand for stringent security systems, automated identification of individuals based on biometric methods has been a major focus of research and development over the last decade. Biometric recognition analyses unique physiological traits or behavioral characteristics, such as an iris, face, retina, voice, fingerprint, hand geometry, keystrokes or gait. The iris has a complex and unique structure that remains stable over a person's lifetime, features that have led to its increasing interest in its use for biometric recognition. In this study, we proposed a technique incorporating Principal Component Analysis (PCA) based on Discrete Wavelet Transformation (DWT) for the extraction of the optimum features of an iris and reducing the runtime needed for iris template classification. The idea of using DWT behind PCA is to reduce the resolution of the iris template. DWT converts an iris image into four frequency sub-bands. One frequency sub-band instead of four has been used for further feature extraction by using PCA. Our experimental evaluation demonstrates the efficient performance of the proposed technique.

Mussel-inspired immobilization of Au on bare and graphene-wrapped Ni nanoparticles toward highly efficient and easily recyclable catalysts.

Bimetallic nanocatalysts have been gaining huge research attention in the heterogeneous catalysis community recently owing to their tunable properties and multifunctional characteristics. In this work, we fabricated a bimetallic core-shell nanocomposite catalyst by employing a mussel-inspired strategy for immobilizing gold nanoparticles (AuNP) on the surface of nickel nanoparticles (NiNP). NiNPs obtained from the reduction of Ni(ii) were first coated with polydopamine to provide the anchoring sites towards the robust immobilization of AuNPs. The as-synthesized nanocomposite (Ni-PD-Au) exhibited outstanding catalytic activity while reducing methylene blue (MB) and 4-nitrophenol (4-NP) yielding rate constants 13.11 min-1 and 4.21 min-1, respectively, outperforming the catalytic efficiency of its monometallic counterparts and other similar reported catalysts by large margins. The superior catalytic efficiency of the Ni-PD-Au was attributed to the well-known synergistic effect, which was experimentally investigated and compared with prior reports. Similar bio-inspired immobilization of AuNPs was also applied on graphene-wrapped NiNPs (Ni-G) instead of bare NiNPs to synthesize another composite catalyst (Ni-G-PD-Au), which yet again exhibited synergistic catalytic activity. A comparative study between the two nanocomposites suggested that Ni-PD-Au excelled in catalytic activity but Ni-G-PD-Au provided noteworthy stability showing ∼100% efficiency over 17 repeated cycles. However, along with excellent synergistic performance, both nanocomposites demonstrated high magnetization and thermal stability up to 350 °C ascertaining their easy separation and sustainability for high-temperature applications, respectively.

pH-Dependent Inversion of Hofmeister Trends in the Water Structure of the Electrical Double Layer.

Specific ion effects (SIEs) are known to influence the acid/base behavior of silica and the interfacial structure of water, yet evidence of the effect of pH on SIEs is lacking. Here broadband vibrational sum frequency generation (SFG) spectroscopy was used to study SIEs on the water structure at the electrical double layer (EDL) of silica as a function of pH and monovalent cation identity from pH 2-12 at 0.5 M salt concentration. SFG results indicate a direct Hofmeister series of cation adsorption at pH 8 (Li+ < Na+ < K+ < Cs+), with an inversion in this series occurring at pH > 10. In addition, an inversion in SFG intensity trends also occurred at pH < 6, which was attributed to contributions from asymmetric cation hydration and EDL overcharging. The highly pH-dependent SIEs for silica/water have implications for EDL models that often assume pH-independent parameters.

The thermal reorganization of DNA immobilized at the silica/buffer interface: a vibrational sum frequency generation investigation.

We have monitored the interactions of DNA strands immobilized on silica at the buried solid/liquid interface using vibrational sum frequency generation. We find that the nucleobases exhibit net order even prior to hybridization for immobilized single strands. Moreover, varying the temperature of the hybridized samples leads to spectral changes from the thymine nucleobases that are consistent with duplex dissociation.

The influence of concentration on specific ion effects at the silica/water interface.

Second harmonic generation spectroscopy is a useful tool for monitoring changes in interfacial potential at buried insulator/liquid interfaces. Here we apply this technique to the silica/aqueous interface and monitor the changes in interfacial potential while varying the pH in the presence of different alkali halides at 0.1M concentration. Within the pH range explored, the bimodal distribution of acidic sites on planar silica is clearly observed, corresponding to two types of acidic SiOH groups. Comparing these data with previous work at 0.5M sheds light on whether the presence of the ions stabilizes the charged or neutral state of the surface sites. For the alkali chlorides, with the exception of NaCl, we observe that the presence of the alkali chlorides stabilize the less acidic site in the protonated (SiOH) rather than deprotonated (SiO(-)) form. This unusual influence of the cation is attributed to the combination of interactions at the interface between water, surface sites and the electrolyte. Overall, we observe that the influence of the alkali ion on the ratio of the two types of sites and their effective acid dissociation constants is minor at 0.1M, unlike that observed at 0.5M. In contrast, the influence of the anion on the cooperative dissociation of surface sites and their relative distribution is little affected upon decreasing the concentration, which indicates that these specific anion effects are prevalent in nature.

Monitoring DNA hybridization and thermal dissociation at the silica/water interface using resonantly enhanced second harmonic generation spectroscopy.

The immobilization of oligonucleotide sequences onto glass supports is central to the field of biodiagnostics and molecular biology with the widespread use of DNA microarrays. However, the influence of confinement on the behavior of DNA immobilized on silica is not well understood owing to the difficulties associated with monitoring this buried interface. Second harmonic generation (SHG) is an inherently surface specific technique making it well suited to observe processes at insulator interfaces like silica. Using a universal 3-nitropyrolle nucleotide as an SHG-active label, we monitored the hybridization rate and thermal dissociation of a 15-mer of DNA immobilized at the silica/aqueous interface. The immobilized DNA exhibits hybridization rates on the minute time scale, which is much slower than hybridization kinetics in solution but on par with hybridization behavior observed at electrochemical interfaces. In contrast, the thermal dissociation temperature of the DNA immobilized on silica is on average 12 °C lower than the analogous duplex in solution, which is more significant than that observed on other surfaces like gold. We attribute the destabilizing affect of silica to its negatively charged surface at neutral pH that repels the hybridizing complementary DNA.

Specific Cation Effects on the Bimodal Acid-Base Behavior of the Silica/Water Interface.

Using nonresonant second harmonic generation spectroscopy, we have monitored the change in surface charge density of the silica/water interface over a broad pH range in the presence of different alkali chlorides. Planar silica is known to possess two types of surface sites with pKa values of ∼4 and ∼9, which are attributed to different solvation environments of the silanols. We report that varying the alkali chloride electrolyte significantly changes the effective acid dissociation constant (pKa(eff)) for the less acidic silanol groups, with the silica/NaClaq and silica/CsClaq interfaces exhibiting the lowest and highest pKa(eff) values of 8.3(1) and 10.8(1), respectively. Additionally, the relative populations of the two silanol groups are also very sensitive to the electrolyte identity. The greatest percentage of acidic silanol groups was 60(2)% for the silica/LiClaq interface in contrast to the lowest value of 20(2)% for the silica/NaClaq interface. We attribute these changes in the bimodal behavior to the influence of alkali ions on the interfacial water structure and its corresponding effect on surface acidity.

Pedestrian injury analysis with consideration of the selectivity bias in linked police-hospital data.

Evaluation of crash-related injuries by medical specialists in hospitals is believed to be more exact than rather a cursory evaluation made at the crash scene. Safety analysts sometimes reach for hospital data and use them in combination with the police crash data. One issue that needs to be addressed is the, so-called, selectivity (or selection) bias possible when data used in analysis are not coming from random sampling. If not properly addressed, this issue can lead to a considerable bias in both the model coefficient estimates and the model predictions. This paper investigates pedestrian injury severity factors using linked police-hospital data. A bivariate ordered probit model with sample selection is used to check for the presence of the selectivity bias and to account for it in the MAIS estimates on the Maximum Abbreviated Injury Scale (MAIS). The presence of the sample selection issue has been confirmed. The selectivity bias is considerable in predictions of low injury levels. The pedestrian injury analysis identified and estimated several severity factors, including pedestrian, road, and vehicle characteristics. Male and older pedestrians were found to be particularly exposed to severe injuries. Rural roads and high-speed urban roads appear to be more dangerous for pedestrians, particularly when crossing such roads. Crossing a road between intersections was found to be particularly dangerous behavior. The size and weight of the vehicle involved in a pedestrian crash were also found to have an effect on the pedestrian injury level. The relevant safety countermeasures that may improve pedestrian safety have been proposed.

Orthogonally reactive SAMs as a general platform for bifunctional silica surfaces.

We report the synthesis and self-assembly of azide and amine trimethoxysilanes that result in mixed monolayers on silica. The amine and azide functional groups can be independently reacted with acid chlorides and terminal alkynes, respectively. Consequently, these orthogonally reactive monolayers represent a general starting point for making bifunctional surfaces. Using X-ray photoelectron spectroscopy, we determined the azide/amine surface ratio as well as the reactivity of the azide and amine functional groups in the mixed self-assembled monolayer (SAM). Significantly, the surface azide/amine ratio was much lower than the azide/amine ratio in the self-assembly mixture. After determining the self-assembly mixture composition that would afford 1:1 azide-amine mixed monolayers, we demonstrated their subsequent functionalization. The resulting bifunctional surface has a similar functional group ratio to the azide/amine precursor SAM demonstrating the generality of this approach.