Boron Adsorption Kinetics of Microcrystalline Cellulose and Polymer Resin.

Tailoring boron-polysaccharide interactions is an important strategy for developing functional soft materials such as hydrogels, fire retardants, and sorbents for environmental remediation, for example, using lignocellulosic biomass. For such applications to be realized, it is paramount to understand the adsorption kinetics of borate anions on cellulose and their local structures. Here, the kinetic aspects of boron adsorption by microcrystalline cellulose, lignin, and polymeric resin are investigated and compared. Borate anions interact with the vicinal diols in the glucopyranoside moieties of cellulose to yield chemisorbed boron chelate complexes. In contrast to cellulose, technical lignin contains fewer cis-vicinal diols, and it does not have a tendency to form such chelate complexes upon treatment with the aqueous boric acid solution. The formation kinetics and stability of these chelate complexes strongly depend on nanoscale structures, as well as reaction conditions such as pH and concentration of the sorbate and sorbent. Specifically, insights into the distinct boron adsorption sites were obtained by solid-state one-dimensional (1D) 11B magic-angle spinning NMR and the local structures and intermolecular interactions in the vicinities of boron chelate complexes are elucidated by analyzing two-dimensional (2D) 1H-13C and 11B-1H heteronuclear correlation NMR spectra. The total boron adsorption capacity of cellulose is estimated to be in the 1.3-3.0 mg range per gram of sorbent, which is lower than the boron adsorption capacity of a polystyrene-based resin, ∼17.2 mg of boron per gram of Amberlite IRA 743. Our study demonstrates that the local backbone and side chain flexibility as well as the structures of polyol groups play a significant role in determining the kinetic and thermodynamic stability of chelate complexes, yielding to different boron adsorption capabilities of lignocellulosic polymers.

Optimizing silver nanowire dimensions by the modification of polyol synthesis for the fabrication of transparent conducting films.

Transparent conducting films (TCFs) made by the assembly/deposition of silver nanowires (Ag NWs) are widely used to manufacture flexible electronics such as touch screens, heaters, displays, and organic light-emitting diodes. Controlling the dimensions (length and diameter) of the nanowires is key in obtaining TCFs with the desired optoelectronic properties, namely sheet resistance and optical transparency. This work describes a combined experimental and theoretical investigation on the optimization of the NW dimensions to fabricate high-quality TCFs. Ag NWs of different dimensions are synthesized by the modified polyol method and the average diameter and length of the wires are tailored over a wide range, 35-150 nm and 12-130µm respectively, by controlling the synthesis parameters such as reaction conditions, stabilizing agents, and growth promoters. The synthesized NWs are spin coated on glass substrates to form TCFs. Comparing the films with different lengths, but identical diameters, enabled the quantification of the effect of length on the optoelectronic properties of the TCFs. Similarly, the effect of NW diameter is also studied. A non-uniformity factor is defined to evaluate the uniformity of the TCF and the transmittance of the NW network is shown to be inversely proportional to its area coverage. The sheet conductance versus the normalized number density is plotted for the different concentrations of NWs to extract a conductivity exponent that agrees well with the theoretical predictions. For thin film networks, the relation between the transmittance and sheet resistance provides the percolative figure of merit (FoM) as a fitting parameter. A large FoM is desirable for a good-performing TCF and the synthesis conditions to achieve this are optimized.

Dual Nanomechanics in Anisotropic Porous Covalent Organic Framework Janus-Type Thin Films.

Empowered by crystalline ordered structures and homogeneous fabrication techniques, covalent organic frameworks (COFs) have been realized with uniform morphologies and isotropic properties. However, such homogeneity often hinders various surface-dependent properties observed in asymmetric nanostructures. The challenge remains to induce heterogeneity in COFs by creating an asymmetric superstructure such as a Janus thin film. In this regard, we propose a versatile yet straightforward interfacial layer-grafting strategy to fabricate free-standing Janus-type COF-graphene thin films. Herein, two-dimensional graphene sheets were utilized as the suitable grafter due to the possibility of noncovalent interactions between the layers. The versatility of the approach was demonstrated by fabricating two distinct Janus-type films, with the COF surface interwoven with nanofibers and nanospheres. The Janus-type films showcase opposing surface morphologies originating from graphene sheets and COF nanofibers or nanospheres, preserving the porosity (552-600 m2 g-1). The unique surface chemistries of the constituent layers further endow the films with orthogonal mechanical properties, as confirmed by the nanoindentation technique. Interestingly, the graphene sheets favor the Janus-type assembly of COF nanofibers over the nanospheres. This is reflected in the better nanomechanical properties of COFfiber-graphene films (Egraphene = 300-1200 MPa; ECOF = 15-60 MPa) compared to the COFsphere-graphene films (Egraphene = 11-14 MPa; ECOF = 2-5 MPa). These results indicate a direct relationship between the mechanical properties and homo/heterogeneity of Janus-type COF films.

Combined experimental and simulation study of self-assembly of colloidal gold nanoparticles on silanized glass.

Understanding the kinetics of metal nanoparticle self-assembly on functionalized surfaces is key for a variety of applications. In this work, we present a combined experimental and Monte Carlo simulation analysis of the monolayer formation of Au nanoparticles (Au NPs) on a glass surface functionalized with 3-aminopropyltrimethoxysilane (APTMS). The effect of particle size on the deposition process is analyzed by a wet chemical synthesis of Au NPs with sizes ranging from 14.65 ± 1.85 to 101.81 ± 10.3 nm. The adsorption kinetics is studied by measuring the peak optical absorbance, which increases with the surface concentration of Au NPs on the glass. Also, with the increase in nanoparticle size the surface concentration is found to decrease. To understand the adsorption process, the Frumkin isotherm is used to analyse the adsorption isotherms by choosing Au NPs of three different sizes, 38.31 ± 3.55, 77.32 ± 7.14, and 101.81 ± 10.3 nm. The fitted parameters of this isotherm indicate that as the size increases the decrease in the affinity between the particles and the modified surface leads to reduced surface saturation. Correspondingly, the increased attractive interaction between the Au NPs causes agglomeration. To further interpret the experimental results, a Monte Carlo simulation was carried out to relate the adsorption kinetics with the surface coverage of the substrate. The simulations confirmed the linear relationship between the probability of NPs being adsorbed on the substrate and solution bulk concentration of the NPs. The immobilization of nanoparticles is governed by both the electrostatic interaction between the substrate and the nanoparticles and the bulk diffusion of the particles. As the diffusivity of the nanoparticles is inversely proportional to the size, the deposition decreases with particle size. The overall insight of this study helps to develop a systematic framework for the fabrication of a monolayer of Au NPs with different particle sizes for various applications.

Self assembly of nanorods on microspheres at fluid-fluid interfaces.

The potential applications of metal nanoparticles require their assembly/deposition on different solid matrices. In this work, an experimental method is demonstrated to assemble gold nanorods (AuNRs) as a ring-like structure on polystyrene (PS) microspheres at the fluid-fluid interface via dip-coating followed by solvent evaporation. The effects of AuNR concentration, size and surface charge of PS particles and size of AuNRs on the formation of AuNR ring-like structures on templated PS particles are investigated. A mechanism based on the evaporative drying of a liquid capillary bridge hinged between two PS microspheres is proposed for the formation of the ring-like structure on the PS microspheres. As the liquid evaporates from the pinning line on the PS microsphere surface, the ring-like structure is formed by the convective deposition of AuNRs. The decane-water interfacial tension dictates the position of the pinning line and thus controls the position/diameter of the ring on the PS microspheres. The ring diameter is found to be strongly affected by the template particle diameter. The generality of the experimental scheme is demonstrated by making a ring-like deposit of hematite ellipsoids on PS particles and their position is varied by changing the oil-water interfacial tension via the addition of a surfactant. The work demonstrates a simple, scalable and interface-based method of depositing both spherical and non-spherical nanoparticles on microspheres, which allows the manipulation of nanoparticles as functional components in fabricating devices.

Mechanism and modeling of poly[vinylpyrrolidone] (PVP) facilitated synthesis of silver nanoplates.

Silver triangular nanoplates (AgTNP) present unique surface plasmonic and catalytic properties depending upon the thickness and edge length. AgTNP are synthesized in a kinetically controlled growth process, by and large, using the polymer poly-vinylpyrrolidone (PVP) as a reductant. In this work, we present a systematic study to uncover the effect of the molecular weight (MW) of PVP and the PVP to silver salt (AgNO3) molar ratio ([P : S]) on the physical dimensions of AgTNP. The edge length of AgTNP shows a non-monotonic variation with respect to [P : S] for all MWs. Based on several control experiments, a kinetic mechanism is proposed and a mathematical model is developed to explain the formation of AgTNP. The elementary processes of the model include the reduction of Ag+ by the -OH group in PVP, followed by instantaneous nucleation. This phase is then followed by a slow reduction of Ag+ and growth of the nuclei to AgTNP. The model shows a reasonable agreement with experiments on the non-monotonic variation of edge length of AgTNP with respect to [P : S], as well as on the temporal evolution of the edge length.

Phospholipid stabilized gold nanorods: towards improved colloidal stability and biocompatibility.

Biocompatible and colloidally stable gold nanorods (GNRs) with well-defined plasmonic properties are essential for biomedical and theranostic applications. The as-synthesized GNRs using the seed-mediated method are stabilized by the surfactant, cetyltrimethylammonium bromide (CTAB), which is known for its cytotoxicity in many cell lines. Biocompatible GNRs synthesized using known protocols exhibit some extent of cytotoxicity and colloidal instability because of the incomplete removal of CTAB. We report a facile method for the efficient removal of CTAB molecules with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) phospholipid molecules, which are naturally present in cell membranes. The kinetics of the ligand exchange process is studied using surface-enhanced Raman scattering (SERS) and corroborated with matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. From colloidal stability studies using dynamic light scattering (DLS) and UV-Vis spectroscopy, the optimal lipid concentration and duration required for the successful ligand exchange of CTAB by DMPC are reported. Using thermogravimetric analysis, the surface concentration of DMPC on colloidally stable GNRs is found to be approximately 9 molecules per nm2. The 3-(4,5-dimethylthiozol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) and lactate dehydrogenase (LDH) assays show that the surface-modified DMPC-GNRs have significantly better biocompatibility than those of CTAB-GNRs. Studies on the ligand exchange, colloidal stability and biocompatibility of DMPC-GNRs with aspect ratios ranging from 2.2 to 4.2 demonstrate the robustness of the proposed method. The results provide insights into the important factors to be considered while designing biocompatible GNRs suitable for applications in nanomedicine.

Morphology Tuning via Linker Modulation: Metal-Free Covalent Organic Nanostructures with Exceptional Chemical Stability for Electrocatalytic Water Splitting.

The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on 1H, 13C, and 14N nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm-2 current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).

Predictors of SARS-CoV-2 transmission in congregate living settings: a multicenter prospective study.

BACKGROUND: Older adults residing in congregate living settings (CLS) such as nursing homes and independent living facilities remain at increased risk of morbidity and mortality from coronavirus disease 2019. We performed a prospective multicenter study of consecutive severe acute respiratory coronavirus virus 2 (SARS-CoV-2) exposures to identify predictors of transmission in this setting. METHODS: Consecutive resident SARS-CoV-2 exposures across 17 CLS were prospectively characterized from 1 September 2022 to 1 March 2023, including factors related to environment, source, and exposed resident. Room size, humidity, and ventilation were measured in locations where exposures occurred. Predictors were incorporated in a generalized estimating equation model adjusting for the correlation within CLS. RESULTS: Among 670 consecutive exposures to SARS-CoV-2 across 17 CLS, transmission occurred among 328 (49.0%). Increased risk was associated with nursing homes (odds ratio (OR) = 90.8; 95% CI, 7.8-1047.4), Jack and Jill rooms (OR = 2.2; 95% CI, 1.3-3.6), from source who was pre-symptomatic (OR = 11.2; 95% CI, 4.1-30.9), symptomatic (OR = 6.5; 95% CI, 1.4-29.9), or rapid antigen test positive (OR = 35.6; 95% CI, 5.6-225.6), and in the presence of secondary exposure (OR = 6.3; 95% CI, 1.6-24.0). Exposure in dining room was associated with reduced risk (OR = 0.02; 95% CI, 0.005-0.08) as was medium room size (OR = 0.3; 95% CI, 0.2-0.6). Recent vaccination of exposed resident (OR = 0.5; 95% CI, 0.3-1.0) and increased ventilation of room (OR = 0.9; 95% CI, 0.8-1.0) were marginally associated with reduced risk. CONCLUSION: Prospective assessment of SARS-CoV-2 exposures in CLS suggests that source characteristics and location of exposure are most predictive of resident transmission. These findings can inform risk assessment and further opportunities to prevent transmission in CLS.

Implementation of point-of-care molecular testing for respiratory viruses in congregate living settings.

OBJECTIVE: To implement and evaluate a point-of-care (POC) molecular testing platform for respiratory viruses in congregate living settings (CLS). DESIGN: Prospective quality improvement study. SETTING: Seven CLS, including three nursing homes and four independent-living facilities. PARTICIPANTS: Residents of CLS. METHODS: A POC platform for COVID-19, influenza A and B, and respiratory syncytial virus was implemented at participating CLS from December 1, 2022 to April 15, 2023. Residents with respiratory symptoms underwent paired testing, with respiratory specimens tested first with the POC platform and then delivered to an off-site laboratory for multiplex respiratory virus panel (MRVP) polymerase chain reaction (PCR) as per standard protocol. Turn-around time and diagnostic accuracy of the POC platform were compared against MRVP PCR. In an exploratory analysis, time to outbreak declaration among participating CLS was compared against a convenience sample of 19 CLS that did not use the POC platform. RESULTS: A total of 290 specimens that underwent paired testing were included. Turn-around time to result was significantly shorter with the POC platform compared to MRVP PCR, with median difference of 36.2 hours (interquartile range 21.8-46.4 hours). The POC platform had excellent diagnostic accuracy compared to MRVP PCR, with area under the curve statistic of .96. Time to outbreak declaration was shorter in CLS that used the POC platform compared to CLS that did not. CONCLUSION: Rapid POC testing platforms for respiratory viruses can be implemented in CLS, with high diagnostic accuracy, expedited turn-around times, and shorter time to outbreak declaration.

Influenza outbreak management tabletop exercise for congregate living settings.

We conducted a tabletop exercise on influenza outbreak preparedness that engaged a large group of congregate living settings (CLS), with improvements in self-reported knowledge and readiness. This proactive approach to responding to communicable disease threats has potential to build infection prevention and control capacity beyond COVID-19 in the CLS sector.

Room Temperature Curable Copper Nanowire-Based Transparent Heater.

Copper nanowires (Cu NWs) are a promising alternative to silver NWs to develop transparent conducting films (TCFs) due to their comparable electrical conductivity and relative abundance. Postsynthetic modifications of the ink and high-temperature postannealing processes for obtaining conducting films are significant challenges that need to be addressed before commercial deployment of these materials. In this work, we have developed an annealing-free (room temperature curable) TCF with Cu NW ink that requires minimal postsynthetic modifications. Organic acid pretreated Cu NW ink is used for spin-coating to obtain a TCF with a sheet resistance of 9.4 Ω/sq. and optical transparency of 67.4% at 550 nm. For oxidation protection, the Cu NW TCF is encapsulated with polydimethylsiloxane (PDMS). The encapsulated film is tested as a transparent heater at various voltages and shows good repeatability. These results demonstrate the potential of Cu NW-based TCFs as a replacement for Ag-NW based TCFs for a variety of optoelectronic applications, such as transparent heaters, touch screens, and photovoltaics.

Porous covalent organic nanotubes and their assembly in loops and toroids.

Carbon nanotubes, and synthetic organic nanotubes more generally, have in recent decades been widely explored for application in electronic devices, energy storage, catalysis and biosensors. Despite noteworthy progress made in the synthesis of nanotubular architectures with well-defined lengths and diameters, purely covalently bonded organic nanotubes have remained somewhat challenging to prepare. Here we report the synthesis of covalently bonded porous organic nanotubes (CONTs) by Schiff base reaction between a tetratopic amine-functionalized triptycene and a linear dialdehyde. The spatial orientation of the functional groups promotes the growth of the framework in one dimension, and the strong covalent bonds between carbon, nitrogen and oxygen impart the resulting CONTs with high thermal and chemical stability. Upon ultrasonication, the CONTs form intertwined structures that go on to coil and form toroidal superstructures. Computational studies give some insight into the effect of the solvent in this assembly process.