Gajendra S. Shekhawat

Water contamination by harmful chemicals is a growing global concern, creating a need to develop technologies that can detect a range of target compounds at the required concentrations. Here, we address this need by merging biological allosteric transcription factors with DNA-coated nanomechanical microcantilevers to detect chemicals in water with a digital readout. After proof-of-concept demonstration and optimization to detect anhydrotetracycline with the TetR transcription factor, we use the CadC transcription factor to detect Pb²⁺ and Cd²⁺ in water at concentrations down to 2 and 1 ppb, respectively, in less than 15 min. A computational model suggests this improvement in sensitivity could be achieved by the DNA-coated microcantilever surface changing the transcription factor binding properties. Our findings demonstrate a promising approach for water quality monitoring with fast, highly sensitive, digital readout.

Silver-enabled polymers, with their antimicrobial properties, could prolong the shelf life and maintain quality in packaged foods. However, there is limited understanding about how the Ag form in the polymer, food chemistry, and other factors affect the transfer (migration) of Ag from the polymer to the food under the intended conditions of use. In this study, we investigated the release of Ag from polymer composites (PCs) incorporating two different Ag-exchanged zeolites (Ag-Y), which have been explored as potential scaffolds for loading high concentrations of Ag within common polymers. We manufactured two Ag-Y films based on low-density polyethylene (LDPE): one incorporating ionic Ag (Ag⁺) and one incorporating nanoparticulate Ag (AgNPs), each with similar initial Ag concentrations. Then, we assessed the migration of Ag out of these PCs into food simulants under accelerated room temperature storage conditions. In all simulants investigated, the Ag⁺-Y/LDPE film exhibited a higher migration of Ag compared to the AgNP-Y/LDPE film, suggesting a lower fraction of readily releasable Ag in the latter material. Total Ag migration from AgNP-Y/LDPE over 10 days at 40 °C was 11.10 ± 2.05 ng cm^-2 of packaging surface area in water, 7.63 ± 1.59 ng cm^-2 in a 9 wt % aqueous sucrose solution, and 21.29 ± 1.98 ng cm^-2 in a commercial sweetened carbonated beverage (Squirt). In contrast, Ag migration from Ag⁺-Y/LDPE was measured at 49.61 ± 3.46, 57.48 ± 9.65, and 91.54 ± 5.58 ng cm^-2 in water, sucrose solution, and Squirt drink, respectively. Surface characterization techniques, including atomic force microscopy (AFM), scanning electron microscopy (SEM), and conductivity measurements, revealed the presence of exposed zeolite particles at the surface of the films, suggesting that direct interactions between Ag-exchanged zeolites and food components at the simulant-polymer interface play an important role in determining Ag migration from Ag-Y/LDPE PCs.

Water contamination is a growing global concern, creating a need to develop technologies that can detect a range of target compounds at the required thresholds. Here, we address this need by merging biological allosteric transcription factors with DNA coated nanomechanical microcantilevers to detect chemicals in water with digital readout. After proof-of-concept demonstration and optimization to detect tetracycline with the TetR transcription factor, we use the CadC transcription factor to detect Pb ²⁺ and Cd ²⁺ in water at concentrations down to 2 ppb and 1 ppb, respectively, in less than fifteen minutes. A computational model suggests this improvement in sensitivity could be achieved by the DNA coated microcantilever surface changing transcription factor binding properties. Our findings demonstrate a promising new approach for water quality monitoring with fast, highly sensitive, digital readouts.

Utilization of in situ/operando methods with broad beams and localized probes has accelerated our understanding of fluid-surface interactions in recent decades. The closed-cell microchips based on silicon nitride (SiN _x ) are widely used as “nanoscale reactors” inside the high-vacuum electron microscopes. However, the field has been stalled by the high background scattering from encapsulation (typically ~100 nanometers) that severely limits the figures of merit for in situ performance. This adverse effect is particularly notorious for gas cell as the sealing membranes dominate the overall scattering, thereby blurring any meaningful signals and limiting the resolution. Herein, we show that by adopting the back-supporting strategy, encapsulating membrane can be reduced substantially, down to ~10 nanometers while maintaining structural resiliency. The systematic gas cell work demonstrates advantages in figures of merit for hitherto the highest spatial resolution and spectral visibility. Furthermore, this strategy can be broadly adopted into other types of microchips, thus having broader impact beyond the in situ/operando fields.

New platforms for the rapid and sensitive detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) variants of concern are urgently needed. Here we report the development of a nanomechanical sensor based on the deflection of a microcantilever capable of detecting the SARS-CoV-2 spike (S) glycoprotein antigen using computationally designed multivalent minibinders immobilized on a microcantilever surface. The sensor exhibits rapid (<5 min) detection of the target antigens down to concentrations of 0.05 ng/mL (362 fM) and is more than an order of magnitude more sensitive than an antibody-based cantilever sensor. Validation of the sensor with clinical samples from 33 patients, including 9 patients infected with the Omicron (BA.1) variant observed detection of antigen from nasopharyngeal swabs with cycle threshold (Ct) values as high as 39, suggesting a limit of detection similar to that of the quantitative reverse transcription polymerase chain reaction (RT-qPCR). Our findings demonstrate the use of minibinders and nanomechanical sensors for the rapid and sensitive detection of SARS-CoV-2 and potentially other disease markers.

Mechanical stability of hybrid organic-inorganic perovskites (HOIPs) is essential to achieve long-term durable HOIP-based devices. While HOIPs in two-dimensional (2D) form offer numerous options in the structure and composition to tune their mechanical properties, little is known about the structure/mechanical-properties relationship in this family of materials. Here we investigated a series of 2D lead-halide HOIPs by nano-indentation to explore the impact of critical factors controlling the properties of both the organic and inorganic layers on the materials’ out-of-plane mechanical performance. We find that the lead-halide bond in the inorganic framework can significantly influence the mechanical properties of 2D Ruddlesden-Popper (RP) HOIPs with n = 1. Like 3D HOIPs, stronger lead-halide bond strength leads to higher Young’s modulus in these 2D HOIPs, i.e., E_⊥^Cl>E_⊥^Br>E_⊥^I. In contrast, the hardness of 2D RP HOIPs follows a trend of H_Br^2D>H_Cl^2D>H_I^2D, which is different from that found in 3D HOIPs, probably due to the combined effects from the Pb-X bond strength and inorganic framework structural change (e.g., symmetry and distortion). We further show that the interface between the organic layers in 2D HOIPs can be an effective route to engineer the materials’ mechanical properties. Replacing the weak CH3-CH3 Van der Waals forces by covalent bonds or phenyl-phenyl interactions in the interface can lead to a much stiffer and harder 2D HOIPs. Finally, we discover that the mechanical performance of 2D HOIPs with linear aliphatic diammonium spacer molecules is affected by the two basic structural parameters, i.e., the thicknesses of the organic and inorganic layers, in a similar way compared to that of 2D RP HOIPs with linear aliphatic monoammonium spacer molecules. Thinner organic layer and thicker inorganic layer can result in 2D HOIPs with larger elastic modulus and hardness values. Our results offer intriguing insights into the structure-property relationship of 2D HOIPs from a mechanical perspective, providing guidelines and inspirations to achieve materials design with required mechanical properties for applications.

Optically actuated silicon structures reveal rapid calcium signal propagation in biofilms.

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure-property relationships at the molecular level remains a challenge in chemistry and materials science. Here, we describe the single crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer—a self-complementary building block possessing a preorganized conformation. A single-crystal-to-single-crystal photopolymerization was revealed unambiguously by in-situ single-crystal X-ray diffraction analysis, which was also employed to follow the progression of molecular structure from the monomer, to a partially polymerized intermediate, and, finally, to the polymer itself. Collinear polymer chains are held together tightly by multiple Coulombic interactions involving counterions to form two-dimensional lamellar sheets (1 nm in height) with subnanometer pores (5 Å). The polymer is extremely stable under 254 nm irradiation and high temperature (above 500 K). The extraordinary mechanical strength and environmental stability—in combination with its impressive proton conductivity (~ 3×10 –4 S cm –1)—endows the polymer with potential applications as a robust proton-conducting material. By marrying supramolecular chemistry with macromolecular science, the outcome represents a major step towards the controlled synthesis of single-crystalline polyelectrolyte materials with perfect tacticity.

The power conversion efficiency (PCE) of halide perovskite solar cells is now comparable to commercial solar cells. These solar cells are generally based on multi-cation mixed-halide perovskite absorbers with non-ideal bandgaps of 1.5 to 1.6 eV. The PCE should be able to rise further if the solar cells could use narrower-bandgap absorbers (1.2-1.4 eV). Reducing the Pb content of the semiconductors without sacrificing performance is also a significant driver in the perovskite solar cell research. Here, we demonstrate that mixed Pb/Sn-based perovskites containing the oversized ethylenediammonium (en) dication, {en}FA0.5MA0.5Sn0.5Pb0.5I3 (FA=formamidinium, MA=methylammonium), can exhibit ideal bandgaps of 1.27 to 1.38 eV, suitable for the assembly of single-junction solar cells with higher efficiencies. The use of en dication creates a three-dimensional (3D) hollow inorganic perovskite structure, which was verified through crystal density measurements and single crystal X-ray diffraction structural analysis as well as nuclear magnetic resonance measurements. The {en}FA0.5MA0.5Sn0.5Pb0.5I3 structure has massive Pb/Sn vacancies and much higher chemical stability than the same structure without en and vacancies. This new property reduces the dark current and carrier trap density and increases the carrier lifetime of the Pb/Sn-based perovskite films. Therefore, solar cells using {en}FA0.5MA0.5Sn0.5Pb0.5I3 light absorbers have substantially enhanced air stability and around 20% improvement in efficiency. After overlaying a thin MABr top layer, the {5% en}FA0.5MA0.5Sn0.5Pb0.5I3 material gives an optimized PCE of 17.04%. The results highlight the strong promise of 3D hollow mixed Pb/Sn perovskites in achieving ideal-bandgap materials with higher chemical stability and lower Pb content for high-performance single-junction solar cells or multi-junction solar cells serving as bottom cells.