InP/LiNbO3 Covalent Heterointerface Construction via an Asymmetric Plasma Activation Strategy for Hybrid Integrated Quantum Systems.

Lithium niobate (LiNbO3) is emerging as an appealing candidate for integrated optical applications with enhanced complexity, owing to its inherent abundant optoelectronic properties. To compensate for the inability of LiNbO3 to generate indistinguishable single photons, the evanescent coupling heterointerface constructed between III-V compound semiconductors (e.g., InP) and LiNbO3 through plasma activation provides a feasible solution for balancing the integration efficiency and interfacial stability while achieving sub-50 nm alignment accuracy between devices, thus offering ultracompact on-chip light sources for classical optoelectronics and quantum optics. However, a challenge remains in the formation of the InP/LiNbO3 platform due to the huge mismatch in the coefficient of thermal expansion. Here, we demonstrate the InP/LiNbO3 covalent heterointerface using an asymmetric plasma activation strategy. Different plasmas are used for the activation of InP and LiNbO3 specifically, balancing the enhancement of surface functional group density with the avoidance of defect generation effectively. More importantly, combined with surface comprehensive characterizations and interface performance, we determine that the introduction of ammonia solution enables the surface hydroxyl groups to be "effective" as LiNbO3 surface relaxation increases the chance of -OH groups' contact. Therefore, a robust covalent bond network is established across the InP/LiNbO3 interface at 80 °C with an enhanced bonding strength of 9.7 MPa. Moreover, a hybrid quantum photonic chip based on the InP/LiNbO3 platform is designed to compute the coupling efficiency and the impact of misalignment on it, demonstrating the potential of extending the platform to hybrid integrated quantum systems.

Dispersion strategies of nanomaterials in polymeric inks for efficient 3D printing of soft and smart 3D structures: A systematic review.

Nanoscience-often summarized as "the future is tiny"-highlights the work of researchers advancing nanotechnology through incremental innovations. The design and innovation of new nanomaterials are vital for the development of next-generation three-dimensional (3D) printed structures characterized by low cost, high speed, and versatile capabilities, delivering exceptional performance in advanced applications. The integration of nanofillers into polymeric-based inks for 3D printing heralds a new era in additive manufacturing, allowing for the creation of custom-designed 3D objects with enhanced multifunctionality. To optimize the use of nanomaterials in 3D printing, effective disaggregation techniques and strong interfacial adhesion between nanofillers and polymer matrices are essential. This review provides an overview of the application of various types of nanomaterials used in 3D printing, focusing on their functionalization principles, dispersion strategies, and colloidal stability, as well as the methodologies for aligning nanofillers within the 3D printing framework. It discusses dispersive methods, synergistic dispersion, and in-situ growth, which have yielded smart 3D-printed structures with unique functionality for specific applications. This review also focuses on nanomaterial alignment in 3D printing, detailing methods that enhance selective deposition and orientation of nanofillers within established and customized printing techniques. By emphasizing alignment strategies, we explore their impact on the performance of 3D-printed composites and highlight potential applications that benefit from ordered nanoparticles. Through these continuing efforts, this review shows that the design and development of the new class of nanomaterials are crucial to developing the next generation of smart 3D printed architectures with versatile abilities for advanced structures with exceptional performance.

Recent Advances and Perspectives on Food-Grade Immobilisation Systems for Enzymes.

The use of enzyme immobilisation is becoming increasingly popular in beverage processing, as this method offers significant advantages, such as enhanced enzyme performance and expanded applications, while allowing for easy process termination via simple filtration. This literature review analysed approximately 120 articles, published on the Web of Science between 2000 and 2023, focused on enzyme immobilisation systems for beverage processing applications. The impact of immobilisation on enzymatic activity, including the effects on the chemical and kinetic properties, recyclability, and feasibility in continuous processes, was evaluated. Applications of these systems to beverage production, such as wine, beer, fruit juices, milk, and plant-based beverages, were examined. The immobilisation process effectively enhanced the pH and thermal stability but caused negative impacts on the kinetic properties by reducing the maximum velocity and Michaelis-Menten constant. However, it allowed for multiple reuses and facilitated continuous flow processes. The encapsulation also allowed for easy process control by simplifying the removal of the enzymes from the beverages via simple filtration, negating the need for expensive heat treatments, which could result in product quality losses.

Exploring the binding dynamics of covalent inhibitors within active site of PLpro in SARS-CoV-2.

In the global fight against the COVID-19 pandemic caused by the highly transmissible SARS-CoV-2 virus, the search for potent medications is paramount. With a focused investigation on the SARS-CoV-2 papain-like protease (PLpro) as a promising therapeutic target due to its pivotal role in viral replication and immune modulation, the catalytic triad of PLpro comprising Cys111, His272, and Asp286, highlights Cys111 as an intriguing nucleophilic center for potential covalent bonds with ligands. The detailed analysis of the binding site unveils crucial interactions with both hydrophobic and polar residues, demonstrating the structural insights of the cavity and deepening our understanding of its molecular landscape. The sequence of PLpro among variants of concern (Alpha, Beta, Gamma, Delta and Omicron) and the recent variant of interest, JN.1, remains conserved with no mutations at the active site. Moreover, a thorough exploration of apo, non-covalently bound, and covalently bound PLpro conformations exposes significant conformational changes in loop regions, offering invaluable insights into the intricate dynamics of ligand-protein complex formation. Employing strategic in silico medication repurposing, this study swiftly identifies potential molecules for target inhibition. Within the domain of covalent docking studies and molecular dynamics, using reported inhibitors and clinically tested molecules elucidate the formation of stable covalent bonds with the cysteine residue, laying a robust foundation for potential therapeutic applications. These details not only deepen our comprehension of PLpro inhibition but also play a pivotal role in shaping the dynamic landscape of COVID-19 treatment strategies.

Advances and Challenges in Interfacial Binding Forces for Electrocatalysts.

As a practical chemical energy conversion technology, electrocatalysis could be used in fields of energy conversion and environmental protection. In recent years, significant research efforts have been devoted to the design and development of high-performance electrocatalysts because the rational design of catalysts is crucial for enhancing electrocatalytic performance. Creating electrocatalysts by forming interactions between different components at the interface is an important means of controlling and improving performance. Therefore, several common interfacial binding forces used for synthesizing electrocatalysts was systematically summarized in this review for the first time. The discussion revolves around the crucial roles these binding forces play in various electrocatalytic reaction processes. Various characterization techniques capable of proving the existence of these interfacial binding forces was also involved in the review. Finally, some prospects and challenges for designing and researching materials through the utilization of interfacial binding forces were presented.

Synthesis of PDMS Chain Structure with Introduced Dynamic Covalent Bonding for High-Performance Rehealable Tactile Sensor Application.

In addressing the increasing demand for wearable sensing systems, the performance and lifespan of such devices must be improved by enhancing their sensitivity and healing capabilities. The present work introduces an innovative method for synthesizing a healable disulfide bond contained in a polydimethylsiloxane network (PDMS-SS) that incorporates ionic salts, which is designed to serve as a highly effective dielectric layer for capacitive tactile sensors. Within the polymer network structure, the cross-linking agent pentaerythritol tetrakis 3-mercaptopropionate (PTKPM) forms reversible disulfide bonds while simultaneously increasing polymer softness and the dielectric constant. The incorporation of dioctyl sulfosuccinate sodium salt (DOSS) significantly improves the capacitance and sensing properties by forming an electrical double-layer through interactions between the electrode charge and salt ions at the contact interface. The developed polymer material-based tactile sensor shows a strong response signal at low pressure (0.1 kPa) and maintains high sensitivity (0.175 kPa-1) over a wide pressure range (0.1-10 kPa). It also maintains the same sensitivity over 10 000 repeated applications of external pressure and is easily self-healed against mechanical deformation due to the dynamic disulfide covalent bonding, restoring ≈95% of its detection capacity.

Bifunctional Sulfhydryl-Based Polyimides for Highly Active Cathodes of Li-S Batteries.

Sulfhydryl-based polyimides were synthesized by the nucleophilic ring-opening reaction of thiolactone monomers (BPDA-T, ODPA-T, BTDA-T) with polyethylenimine (PEI), and they were coated on carbon nanotubes as host materials (BPTP@CNT, ODTP@CNT, and BTTP@CNT) of the sulfur cathode. BPTP@CNT/S, ODTP@CNT/S, and BTTP@CNT/S as cathode materials not only promote the covalent bonding of sulfur and polysulfide with sulfhydryl-based polyimides but also reduce the shuttle effect of soluble polysulfide in the redox process. Moreover, sulfhydryl-based polyimides can help improve the compatibility and interfacial contact between sulfur and conductive carbon while alleviating the volume expansion of the cathode. In addition, the conductive network of carbon nanotubes improves the electronic conductivity of the cathode materials. The BTTP@CNT/S cathode showed superior stability (the initial capacity was 902 mAh g-1 at 1C, and the capacity retention rate was 88.58% after 500 cycles) and the initial capacity could reach 718 mAh g-1 when the sulfur loading was 4.8 mg cm-2 (electrolyte/sulfur ratio: 10 µL mg-1), which fully proves the feasibility of the large-scale application of sulfhydryl-based polyimide materials.

Responsive Microgels through RAFT-HDA Dynamic Covalent Bonding Chemistry.

This paper developed a method for preparing ultrasound-responsive microgels based on reversible addition fragmentation chain transfer-hetero Diels-Alder (RAFT-HAD) dynamic covalent bonding. First, a styrene cross-linked network was successfully prepared by a Diels-Alder (DA) reaction between phosphoryl dithioester and furan using double-ended diethoxyphosphoryl dithiocarbonate (BDEPDF) for RAFT reagent-mediated styrene (St) polymerization, with a double-ended dienophile linker and copolymer of furfuryl methacrylate (FMA) and St as the dienophile. Subsequently, the microgel system was constructed by the HDA reaction between phosphoryl disulfide and furan groups using the copolymer of polyethylene glycol monomethyl ether acrylate (OEGMA) and FMA as the dienophore building block and hydrophilic segment and the polystyrene pro-dienophile linker as the cross-linker and hydrophobic segment. The number of furans in the dienophile chain and the length of the dienophile linker were regulated by RAFT polymerization to investigate the effects of the single-molecule chain functional group degree, furan/dithioester ratio, and hydrophobic cross-linker length on the microgel system. The prepared microgels can achieve the reversible transformation of materials under force responsiveness, and their preparation steps are simple and adaptive to various potential applications in biomedical materials and adaptive electrical materials.

Termostable and effective immobilized invertase for sucrose determination in fruit juices.

In this study, immobilization of invertase enzyme was performed on a previously synthesized and characterized poly(N-vinylpyrrolidone-co-butylacrylate-co-N hydroxymethylacrylamide) terpolymer membranes by covalent bonding method. Glutaraldehyde(GA) was used as the crosslinker and Bovine Serum Albumin(BSA) was used as the binding agent. Optimum pH, temperature, amount of polymer, substrate concentration, amount of BSA and amount of GA values were determined for both free and immobilized enzyme. Optimum pH and temperature values were found as pH = 5.0, T = 55 °C, pH = 7.0 and T = 80 °C for free and immobilized enzyme, respectively. In particular, the optimum temperature of 80 °C for the immobilized enzyme provides its potential to be used commercially. The kinetic parameters of the free enzyme and the immobilized enzyme were determined using the well known Lineweaver-Burk method. The Vmax values for free (13.4 µM/min) and immobilized enzyme (12.2 µM/min) were found as close to each other, while the Km value of the immobilized enzyme (8.33 mM) was much lower than that of the free enzyme (29.41 mM). In reuse studies conducted with peach and orange juices, it was determined that the immobilized enzyme retained approximately 90% of its activity even after 30 reuses within 1 month.

Dynamic Covalent Bonded Gradient Structured Actuators with Mechanical Robustness and Self-Healing Ability.

Flexible actuators with excellent adaptability and interaction safety have a wide range of application prospects in many fields. However, current flexible actuators have problems such as fragility and poor actuating ability. Here, inspired by the features of nacre structure, a gradient structured flexible actuator is proposed with mechanical robustness and self-healing ability. By introducing dynamic boronic ester bonds at the interface between MXene nanosheets and epoxy natural rubber matrix, the resulting nanocomposites with ordered micro-nano structures exhibit excellent tensile strength (25.03 MPa) and satisfactory repair efficiency (81.2%). In addition, the gradient distribution structure of MXene nanosheets endows the actuator with stable photothermal conversion capability, which can quickly respond to near-infrared light stimulation. The interlayer dynamic covalent bond crosslinking enables good response speed after multiple bending and is capable of functional self-healing after damage. This work introduces gradient structure and dynamic covalent bonding into flexible actuators, which provides a reference for the fabrication of self-healing soft robots, wearable, and other healable functional materials.

Self-Assembled Monolayers of a Fluorinated Phosphonic Acid as a Protective Coating on Aluminum.

Aluminum (Al) placed in hot water (HW) at 90 °C is roughened due to its reaction with water, forming Al hydroxide and Al oxide, as well as releasing hydrogen gas. The roughened surface is thus hydrophilic and possesses a hugely increased surface area, which can be useful in applications requiring hydrophilicity and increased surface area, such as atmospheric moisture harvesting. On the other hand, when using HW to roughen specified areas of an Al substrate, ways to protect the other areas from HW attacks are necessary. We demonstrated that self-assembled monolayers (SAMs) of a fluorinated phosphonic acid (FPA, CF3(CF2)13(CH2)2P(=O)(OH)2) derivatized on the native oxide of an Al film protected the underneath metal substrate from HW attack. The intact wettability and surface morphology of FPA-derivatized Al subjected to HW treatment were examined using contact angle measurement, and scanning electron microscopy and atomic force microscopy, respectively. Moreover, the surface and interface chemistry of FPA-derivatized Al before and after HW treatment were investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS), verifying that the FPA SAMs were intact upon HW treatment. The ToF-SIMS results therefore explained, on the molecular level, why HW treatment did not affect the underneath Al at all. FPA derivatization is thus expected to be developed as a patterning method for the formation of hydrophilic and hydrophobic areas on Al when combined with HW treatment.

Current status of development and biomedical applications of peptide-based antimicrobial hydrogels.

Microbial contamination poses a serious threat to human life and health. Through the intersection of material science and modern medicine, advanced bionic hydrogels have shown great potential for biomedical applications due to their unique bioactivity and ability to mimic the extracellular matrix environment. In particular, as a promising antimicrobial material, the synthesis and practical biomedical applications of peptide-based antimicrobial hydrogels have drawn increasing research interest. The synergistic effect of peptides and hydrogels facilitate the controlled release of antimicrobial agents and mitigation of their biotoxicity while achieving antimicrobial effects and protecting the active agents from degradation. This review reports on the progress and trends of researches in the last five years and provides a brief outlook, aiming to provide theoretical background on peptide-based antimicrobial hydrogels and make suggestions for future related work.

Experimental Evidences on Magnetism-Covalent Bonding Interplay in Structural Properties of Solids and during Chemisorption.

Valence electrons are one of the main players in solid catalysts and in catalytic reactions, since they are involved in several correlated phenomena like chemical bonding, magnetism, chemisorption, and bond activation. This is particularly true in the case of solid catalysts containing d-transition metals, which exhibit a wide range of magnetic phenomena, from paramagnetism to collective behaviour. Indeed, the electrons of the outer d-shells are, on one hand, involved in the formation of bonds within the structure of a catalyst and on its surface, and, on the other, they are accountable for the magnetic properties of the material. For this reason, the relationship between magnetism and heterogeneous catalysis has been a source of great interest since the mid-20th century. The subject has gained a lot of attention in the last decade, thanks to the orbital engineering of quantum spin-exchange interactions and to the widespread application of external magnetic fields as boosting tools in several catalytic reactions. The topic is discussed here through experimental examples and evidences of the interplay between magnetism and covalent bonding in the structure of solids and during the chemisorption process. Covalent bonding is discussed since it represents one of the strongest contributions to bonds encountered in materials.

Covalent conjugation of Inca peanut albumin and polyphenols with different phenolic hydroxyl numbers through laccase catalysis to improve functional properties.

BACKGROUND: Enzymatic crosslinking is a method that can be used to modify Inca peanut albumin (IPA) using polyphenols, and provides desirable functionalities; however, the effect of polyphenol structures on conjugate properties is unclear. In this study, we selected four polyphenols with different numbers of phenolic hydroxyl groups [para-hydroxybenzoic acid (HBA), protocatechuic acid (PCA), gallic acid (GA), and epigallocatechin gallate (EGCG)] for covalent modification of IPA by enzymatic crosslinking, and explored the structure-function changes of the IPA-polyphenol conjugates. RESULTS: Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis showed that laccase successfully promoted covalent crosslinking of IPA with polyphenols, with the order of degree of conjugation as EGCG > GA > PCA > HBA, the IPA-EGCG conjugate showed the highest polyphenol binding equivalents (98.35 g kg-1 protein), and a significant reduction in the content of free amino, sulfhydryl, and tyrosine group. The oxidation of polyphenols by laccase forms quinone or semiquinone radicals that are covalently crosslinked to the reactive groups of IPA, leading to significant changes in the secondary and tertiary structures of IPA, with spherical structures transforming into dense lamellar structures. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging ability and emulsification stability of IPA-EGCG conjugates improved by almost 6-fold and 2.7-fold, respectively, compared with those of unmodified IPA. CONCLUSION: These data suggest that the higher the number of polyphenol hydroxyl groups, the higher the degree of IPA-polyphenol conjugation; additionally, enzymatic crosslinking can significantly improve the functional properties of IPA. © 2024 Society of Chemical Industry.

Analysis of the Unusual Chemical Bonds and Dipole Moments of AeF- (Ae=Be-Ba): A Lesson in Covalent Bonding.

Quantum chemical calculations of the anions AeF- (Ae=Be-Ba) have been carried out using ab initio methods at the CCSD(T)/def2-TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge- and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F- donate electronic charge into the vacant spx(σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae F-. The heavier Ae atoms Ca, Sr, Ba use their vacant (n-1)d AOs as acceptor orbitals which enables them to form a second σ donor bond with F- that leads to quadruply bonded Ae F- (Ae=Ca-Ba). The presentation of molecular orbitals or charge distribution using only one isodensity value may give misleading information about the overall nature of the orbital or charge distribution. Better insights are given by contour line diagrams. The ELF calculations provide monosynaptic and disynaptic basins of AeF- which nicely agree with the analysis of the occupied molecular orbitals and with the charge density difference maps. A particular feature of the covalent bonds in AeF- concerns the inductive interaction of F- with the soft valence electrons in the (n)s valence orbitals of Ae. The polarization of the (n)s2 electrons induces a (n)spx hybridized lone-pair orbital at atom Ae, which yields a large dipole moment with the negative end at Ae. The concomitant formation of a vacant (n)spx AO of atom Ae, which overlaps with the occupied 2p(σ) AO of F-, leads to a strong covalent σ bond.

Stabilizing Lithium-Metal Host Anodes by Covalently Binding MgF2 Nanodots to Honeycomb Carbon Nanofibers.

Constructing lithiophilic carbon hosts has been regarded as an effective strategy for inhibiting Li dendrite formation and mitigating the volume expansion of Li metal anodes. However, the limitation of lithiophilic carbon hosts by conventional surface decoration methods over long-term cycling hinders their practical application. In this work, a robust host composed of ultrafine MgF2 nanodots covalently bonded to honeycomb carbon nanofibers (MgF2/HCNFs) is created through an in situ solid-state reaction. The composite exhibits ultralight weight, excellent lithiophilicity, and structural stability, contributing to a significantly enhanced energy efficiency and lifespan of the battery. Specifically, the strong covalent bond not only prevents MgF2 nanodots from migrating and aggregating but also enhances the binding energy between Mg and Li during the molten Li infusion process. This allows for the effective and stable regulation of repeated Li plating/stripping. As a result, the MgF2/HCNF-Li electrode delivers a high Coulombic efficiency of 97% after 200 cycles, cycling stably for more than 2000 h. Furthermore, the full cells with a LiFePO4 cathode achieve a capacity retention of 85% after 500 cycles at 0.5C. This work provides a strategy to guide dendrite-free Li deposition patterns toward the development of high-performance Li metal batteries.

Exploring a Ni-N4 Active Site-Based Conjugated Microporous Polymer Z-Scheme Heterojunction Through Covalent Bonding for Visible Light-Driven Photocatalytic CO2 Conversion in Pure Water.

Designing photocatalysts with efficient charge transport and abundant active sites for photocatalytic CO2 reduction in pure water is considered a potential approach. Herein, a nickel-phthalocyanine containing Ni-N4 active sites-based conjugated microporous polymer (NiPc-CMP), offering highly dispersed metal active sites, satisfactory CO2 adsorption capability, and excellent light harvesting properties, is engineered as a photocatalyst. By virtue of the covalently bonded bridge, an atomic-scale interface between the NiPc-CMP/Bi2 WO6 Z-scheme heterojunction with strong chemical interactions is obtained. The interface creates directional charge transport highways and retains a high redox potential, thereby enhancing the photoexcited charge carrier separation and photocatalytic efficiency. Consequently, the optimal NiPc-CMP/Bi2 WO6 (NCB-3) achieves efficient photocatalytic CO2 reduction performance in pure water under visible-light irradiation without any sacrificial agent or photosensitizer, affording a CO generation rate of 325.9 µmol g-1 with CO selectivity of 93% in 8 h, outperforming those of Bi2 WO6 and NiPc-CMP, individually. Experimental and theoretical calculations reveal the promotion of interfacial photoinduced electron separation and the role of Ni-N4 active sites in photocatalytic reactions. This study presents a high-performance CMP-based Z-scheme heterojunction with an effective interfacial charge-transfer route and rich metal active sites for photocatalytic CO2 conversion.

Synergistic pervaporation dehydration of ethanol/water mixture: Exploring the potential of a covalently designed hybrid membrane structure of polyacrylic acid grafted carbon nitride and polyvinyl alcohol.

Polyacrylic acid (PAA) grafted CN sheet (P-g-CN) was synthesized to enhance the dispersive properties of carbon nitride (CN) in the membrane. A successful PAA grafting to the CN was confirmed from FTIR, TGA, and Zeta potential and XRD analyses. The A PVA membrane embedded P-g-CN, including a covalently constructed polymer-filler network, was developed to separate ethanol-water mixtures using pervaporation (PV). XPS study has confirmed a covalent attachment of P-g-CN sheets to the PVA matrix. Thereby, a defect-free membrane matrix was observed in the FESEM analysis. A 10 wt% loaded PVA-P-g-CN10 composite membrane was compared to the pristine PVA membrane, demonstrating improved PV dehydration performance. The flux decreased from 0.21 kg/m2h of pristine PVA membrane to 0.17 kg/m2h of PVA-P-g-CN10 membrane, while the separation factor improved from 49 to 176 in a 90/10 wt % ethanol/water feed at 40 °C. This improvement can be attributed to the selective diffusion of water through the P-g-CN interlayer spacing and tiny triangular nanopores in the s-triazine network, along with their dispersibility in the PVA matrix, resulting in well-ordered membrane morphology. Furthermore, PVA-P-g-CN10 exhibited higher water permeance (43.31-86.07 GPU) than ethanol (1.18-10.47 GPU) as the feed temperature increased from 30 to 70 °C, suggesting P-g-CN successfully inhibits swelling in the feed solution through proper interaction with PVA. In a long-term PV test lasting 250 h, the PVA-P-g-CN10 membrane displayed excellent structural stability and maintained its performance.

Structural Control of Plasmon Resonance in Molecularly Linked Metal Oxide Nanocrystal Gel Assemblies.

Nanocrystal gels exhibit collective optical phenomena based on interactions among their constituent building blocks. However, their inherently disordered structures have made it challenging to understand, predict, or design properties such as optical absorption spectra that are sensitive to the coupling between the plasmon resonances of the individual nanocrystals. Here, we bring indium tin oxide nanocrystal gels under chemical control and show that their infrared absorption can be predicted and systematically tuned by selecting the nanocrystal sizes and compositions and molecular structures of the link-mediating surface ligands. Thermoreversible assemblies with metal-terpyridine links form reproducible gel architectures, enabling us to derive a plasmon ruler that governs the spectral shifts upon gelation, predicated on the nanocrystal and ligand compositions. This empirical guide is validated using large-scale, many-bodied simulations to compute the optical spectra of gels with varied structural parameters. Based on the derived plasmon ruler, we design and demonstrate a nanocrystal mixture whose spectrum exhibits distinctive line narrowing upon assembly.

Laser-Induced MXene-Functionalized Graphene Nanoarchitectonics-Based Microsupercapacitor for Health Monitoring Application.

Microsupercapacitors (micro-SCs) with mechanical flexibility have the potential to complement or even replace microbatteries in the portable electronics sector, particularly for portable biomonitoring devices. The real-time biomonitoring of the human body's physical status using lightweight, flexible, and wearable micro-SCs is important to consider, but the main limitation is, however, the low energy density of micro-SCs as compared to microbatteries. Here using a temporally and spatially controlled picosecond pulsed laser, we developed high-energy-density micro-SCs integrated with a force sensing device to monitor a human body's radial artery pulses. The photochemically synthesized spherical laser-induced MXene (Ti3C2Tx)-derived oxide nanoparticles uniformly attached to laser-induced graphene (LIG) act as active electrode materials for micro-SCs. The molecular dynamics simulations and detailed spectroscopic analysis reveal the synergistic interfacial interaction mechanism of Ti-O-C covalent bonding between MXene and LIG. The incorporation of MXene nanosheets improves the graphene sheet alignment and ion transport while minimizing self-restacking. Furthermore, the micro-SCs based on a nano-MXene-LIG hybrid demonstrate high mechanical flexibility, durability, ultrahigh energy density (21.16 × 10-3 mWh cm-2), and excellent capacitance (∼100 mF cm-2 @ 10 mV s-1) with long cycle life (91% retention after 10 000 cycles). Such a single-step roll-to-roll highly reproducible manufacturing technique using a picosecond pulsed laser to induce MXene-derived spherical oxide nanoparticles (size of quantum dots) attached uniformly to laser-induced graphene for biomedical device fabrication is expected to find a wide range of applications.