Graphene-Infused Sustainable Rubber-Based Triboelectric Nanogenerator For Real-Time Human Motion Monitoring.

Triboelectric nanogenerators (TENG) are promising alternatives for clean energy harvesting. However, the material utilization in the development of TENG relies majorly on polymers derived from non-renewable resources. Therefore, minimizing the carbon footprint associated with such TENG development demands a shift toward usage of sustainable materials. This study pioneers using natural rubber (NR) as a sustainable alternative in TENG development. Infusing graphene in NR, its dielectric constant and tribonegativity are optimized, yielding a remarkable enhancement. The optimized sample exhibits a dielectric constant of 411 (at 103 Hz) and a contact potential difference (CPD) value of 1.85 V. In contrast, the pristine NR sample showed values of 6 and 3.06 V for the dielectric constant and CPD. Simulation and experimental studies fine-tune the TENG's performance, demonstrating excellent agreement between theoretical predictions and practical studies. Sensors developed via stencil printing technique possess a remarkably low layer thickness of 270 µm, and boast a power density of 420 mW m-2, a staggering 250% increase over conventional NR. Moreover, the material is pressure sensitive, enabling precise real-time human motion detection, including finger contact, finger bending, neck bending, and arm bending. This versatile sensor offers wireless monitoring, empowering healthcare monitoring based on the Internet of Things.

Elastomeric Ionic Hydrogel-Based Flexible Moisture-Electric Generator for Next-Generation Wearable Electronics.

Rapid consumption of traditional energy resources creates utmost research interest in developing self-sufficient electrical devices to progress next-generation electronics to a level up. To address the global energy crisis, moisture-electric generators (MEGs) are proving to be an emerging technology in this field, capable of powering wearable electronics by harvesting energy from abundantly available ambient moisture without any requirement for external/additional energy. Recent advances in MEGs generally utilize an inorganic, metal, or petroleum-based polymeric material as an active material, which may produce sufficient current but lacks the flexibility and stretchability required for wearable electronics. Herein, we prepared an elastomer-based ionic hydrogel as an active material, and an MEG was fabricated by placing the ionic hydrogel on a PET sheet with two copper tapes on both sides of the hydrogel. The preparation of the hydrogel was thoroughly optimized and characterized in terms of spectroscopic analysis, swelling, water retention, and mechanical and rheological studies. The highly stretchable (350%) fabricated MEG is capable of producing a short-circuit current (JSC) of 16.1 µA/cm2, an open-circuit voltage (VOC) of 0.24 V, and a power density of 3.86 µW/cm2. The synergistic effect of the ion concentration gradient and the redox reaction on electrodes can be considered MEG's working principle. Apart from the current generation, this device is also used as a self-powered electronic sensor to monitor different physical activities by measuring breathing patterns. This prepared device is also capable of sensing the proximity of a hand. Therefore, our low-cost, easily fabricable, sustainable MEG device can be a potential aspirant for next-generation self-powered wearable electronics in healthcare applications.

Tetradentate Ligand's Chameleon-Like Behavior Offers Recognition of Specific Lanthanides.

The surging demand for high-purity individual lanthanides necessitates the development of novel and exceptionally selective separation strategies. At the heart of these separation systems is an organic compound that, based on its structural features, selectively recognizes the lighter or heavier lanthanides in the trivalent lanthanide (Ln) series. This work emphasizes the significant implications resulting from modifying the donor group configuration within an N,O-based tetradentate ligand and the changes in the solvation environment of Ln ions in the process of separating Lns, with the unique ability to achieve peak selectivity in the light, medium, and heavy Ln regions. The structural rigidity of the bis-lactam-1,10-phenanthroline ligand enforces size-based selectivity, displaying an exceptional affinity for Lns having larger ionic radii such as La. Modifying the ligand by eliminating one preorganization element (phenanthroline → bipyridine) results in the fast formation of complexes with light Lns, but, in the span of hours, the peak selectivity shifts toward middle Ln (Sm), resulting in time-resolved separation. As expected, at low nitric acid concentrations, the neutral tetradentate ligand complexes with Ln3+ ions. However, the change in extraction mechanism is observed at high nitric acid concentrations, leading to the formation and preferential extraction of anionic heavy Ln species, [Ln(NO3)x+3]x-, that self-assemble with two ligands that have undergone protonation, forming intricate supramolecular architectures. The tetradentate ligand that is structurally balanced with restrictive and unrestrictive motifs demonstrates unique, controllable selectivity for light, middle, and heavy Lns, underscoring the pivotal role of solvation and ion interactions within the first and second coordination spheres.

Supramolecular Complexation-Enhanced CO2 Chemisorption in Amine-Derived Sorbents.

A supramolecular complexation approach is developed to improve the CO2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. The reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO2 capacity and diminished energy consumption in sorbent regeneration are achieved.

Vibrational, optical, and photocatalytic properties of ZnO/layered carbon nanocomposite synthesized by ball milling.

ZnO/layered carbon nanocomposites with varied sizes of ZnO nanoparticles (NPs) were synthesized by mechanical milling of mixture of ZnO NPs and carbon NPs. The NP size of ZnO was controlled with average particle sizes about 19.33, 21.87, 24.21, and 27.89 nm by varying the concentrations of carbon NPs viz 0, 2, 5, and 10 weight percent, respectively, in the mixture. Presence of carbon with ZnO in the form of composite also resulted in the enhanced shift of the band gap of ZnO due to the optical transitions in the impurity states or presence of carbon as compared to the ZnO size change alone. Additionally, the enhancement of absorbance in the visible region with an increase in carbon content was observed. Such an increase in absorbance can enhance the photocatalytic activity of ZnO NPs. Raman bands for ZnO NPs also were found to shift faster in the presence of layered carbon. The quenching of visible photoluminescence emission of ZnO NPs with an increase in concentration of carbon NPs in the composite indicated the phenomenon associated with transfer of electrons from ZnO to layered carbon helping the separation of photo-generated electrons and holes in ZnO and can lead to enhancement of the photocatalytic activity of ZnO NPs. In the photocatalytic studies, it was observed that the degradation of methylene blue (MB) dye was significantly enhanced by the increase of content of layered carbon in the nanocomposite. The sample containing 10% carbon showed the highest adsorption in dark conditions which was up to 60% of the starting strength and this was further enhanced to 88% in the presence of UV radiation. Enhanced adsorption of MB dye and the effective separation of electron-hole pairs due to charge transfer were believed to be the main causes behind such kind of improvement in the photocatalytic effects.

Observation of a promethium complex in solution.

Lanthanide rare-earth metals are ubiquitous in modern technologies1-5, but we know little about chemistry of the 61st element, promethium (Pm)6, a lanthanide that is highly radioactive and inaccessible. Despite its importance7,8, Pm has been conspicuously absent from the experimental studies of lanthanides, impeding our full comprehension of the so-called lanthanide contraction phenomenon: a fundamental aspect of the periodic table that is quoted in general chemistry textbooks. Here we demonstrate a stable chelation of the 147Pm radionuclide (half-life of 2.62 years) in aqueous solution by the newly synthesized organic diglycolamide ligand. The resulting homoleptic PmIII complex is studied using synchrotron X-ray absorption spectroscopy and quantum chemical calculations to establish the coordination structure and a bond distance of promethium. These fundamental insights allow a complete structural investigation of a full set of isostructural lanthanide complexes, ultimately capturing the lanthanide contraction in solution solely on the basis of experimental observations. Our results show accelerated shortening of bonds at the beginning of the lanthanide series, which can be correlated to the separation trends shown by diglycolamides9-11. The characterization of the radioactive PmIII complex in an aqueous environment deepens our understanding of intra-lanthanide behaviour12-15 and the chemistry and separation of the f-block elements16.

Structural Insight on Supramolecular Polyion Salts: Inositol Hexaphosphate Enclosed in Cationic Macrocyclic Clusters.

Supramolecular macrocyclic forces have been used to trap phytate, myo-inositol-1,2,3,4,5,6-hexakisphosphate, a key bioanion with multiple roles in metabolic processes. Due to the complex chemistry of six multivalent phosphates surrounding the small, cyclic inositol framework, crystallographic information of simple phytate salts has been elusive. This report represents a combined crystallographic, theoretical, and solution binding investigation of a supramolecular macrocyclic complex of phytate. Together, the results provide significant insight to phytate's intramolecular and intermolecular interactions at the microenvironment level. The macrocycle-phytate aggregates consist of phytate anionic pairs, each partly sandwiched by two 24-membered, amide/amine-based cationic macrocycles. The phytate ion pairs hold the tetrameric macrocyclic array together by six strong intermolecular hydrogen bonds. Both phytates crystallize in 1a5e phosphate conformations (one axial (P2) and five equatorial phosphates). Solution NMR binding studies in 1 : 1 DMSO-d6 : D2 O indicate 2 : 1 macrocycle:phytate associations, suggesting that the sandwich-like nature of the complex holds together in solution. DFT studies indicate the likely occurrence of dynamic intramolecular interchange of phosphate protons, as well as important roles for the axial (P2) phosphate in both intramolecular and intermolecular hydrogen bonding interactions.

Tunable, reversible resistive switching behavior of PVA-zirconia nanocomposite films and validation of the trap-assisted switching mechanism by the selective application of external bias voltages.

Flexible, free-standing polyvinyl alcohol (PVA)-zirconia (mean particle size ∼24 nm) nanocomposite films have been synthesized and their performance as a potential next-generation resistive switching device material has been assessed in this report. The nanocomposite films switch from a high resistive state (HRS) to a low resistive state (LRS) at the SET potential and from LRS to HRS at the RESET potential within the voltage window of 5 V. The origination of trap-assisted SET/RESET potentials has been experimentally validated by analyzing the experimental data and invoking various theoretical models. The impregnation of zirconium dioxide (ZrO2) nanoparticles considerably enhances the interfacial charges facilitated by the formation of dangling bonds. The current (I)-voltage (V) characteristics elucidate how the alteration of free volumetric space in the nanocomposites can modify the SET-RESET potential. This leads to tunable SET/RESET potential, good resistance ratio (∼80), and extensive cycling ability of these PVA-ZrO2 organic flexible nanocomposite films. Herein, we have also investigated the effect of applying external bias voltage (equal to the RESET potential) for possible energy bandgap modification and polymer chain orientation. The impedance spectra differ considerably when the sample is subjected to SET, RESET, and zero voltage bias. The observations have been correlated with the UV-vis absorption spectra and electrical studies. The adopted analysis method and obtained results can open up new avenues for designing and analyzing resistive switching-based random-access memory devices.

Hydrophilic and hydrophobic carboxamide pincers as anion hosts.

Hydrophobic and hydrophilic, monotopic and ditopic carboxamide pincer hosts containing ethyl, hexyl, 2-hydroxyethyl and 2-hydroxyethyl ethyl ether pendant arms were synthesized. Solubility trends indicated that solubilities in water or hydrocarbon solvents varied depending on the nature of the pendant arms. Binding constants for hydrophilic pincers were larger in general than their hydrophobic analogs. Significant synergistic binding effects for the ditopic hosts were not observed.

Snapshots of "crystalline" salt-water solutions of inositol hexaphosphate conformers.

Supramolecular insight to intra- and inter-ionic interactions in two inositol hexaphosphate conformers as a function of pH was enabled by NMR and crystallographic studies. These findings also shed light on the complex interactive roles of extended salt-water arrays through the crystal "solution" lattice.

Supramolecular traps for highly phosphorylated inositol sources of phosphorus.

Structurally elusive inositol hexakisphosphates have been trapped in host-guest sandwiches between two picolinamide macrocycles that remain intact in solution, aided by hydrogen bonds and electrostatic interactions. This first report of macrocyclic complexes of inositol hexakisphosphates provides structural insight to significant biosources of phosphorus that impact the global phosphorus cycle.

Characterizing Hydrogen-Bond Interactions in Pyrazinetetracarboxamide Complexes: Insights from Experimental and Quantum Topological Analyses.

Experimental and topological analyses of dipalladium(II) complexes with pyrazinetetracarboxamide ligands containing tetraethyl (1), tetrahexyl (2), and tetrakis(2-hydroxyethyl) ethyl ether (3) are described. The presence of two very short O---O distances between adjacent amide carbonyl groups in the pincer complexes revealed two protons, which necessitated two additional anions to satisfy charge requirements. The results of the crystal structures indicate carbonyl O---O separations approaching that of low barrier hydrogen bonds, ranging from 2.413(5) to 2.430(3) Å. Solution studies and quantum topological analyses, the latter including electron localization function, noncovalent interaction, and Bader's quantum theory of atoms in molecules, were carried out to probe the nature of the short hydrogen bonds and the influence of the ligand environment on their strength. Findings indicated that the ligand field, and, in particular, the counterion at the fourth coordination site, may play a subtle role in determining the degree of covalent association of the bridging protons with one or the other carbonyl groups.

AIEE Active Donor-Acceptor-Donor-Based Hexaphenylbenzene Probe for Recognition of Aliphatic and Aromatic Amines.

In the present investigation, an intramolecular charge transfer (ICT) and aggregation induced emission enhancement (AIEE) active donor-acceptor-donor (D-A-D) system 5 having fumaronitrile as the acceptor and hexaphenylbenzene (HPB) as the donor moieties joined through rotatable phenyl rings has been designed and synthesized that is highly emissive in the solid state and exhibits stimuli-responsive reversible piezochromic behavior upon grinding and heating. Because of its AIEE characteristics, HPB derivative 5 undergoes aggregation to form fluorescent aggregates in mixed aqueous media that exhibit ratiometric fluorescence response toward aliphatic amines (primary/secondary/tertiary) and turn-off response toward aromatic amines and hence differentiates between them. Further, the solution-coated portable paper strips of derivative 5 showed pronounced and sensitive response toward aromatic and aliphatic amines with a detection limit in the range of picogram and nanogram level, respectively.

Hexaphenylbenzene-Stabilized Luminescent Silver Nanoclusters: A Potential Catalytic System for the Cycloaddition of Terminal Alkynes with Isocyanides.

A hexaphenylbenzene (HPB)-based derivative bearing thiol groups has been designed and synthesized that undergoes aggregation-induced emission enhancement in mixed aqueous media to form rodlike fluorescent aggregates. These rodlike aggregates behave as a "not quenched" probe for the detection of silver ions and further act as reactors and stabilizers for reducing-agent-free preparation of blue luminescent silver nanoclusters at room temperature. The utilization of fluorescent supramolecular aggregates for the preparation of Ag NCs in mixed aqueous media is unprecedented in the literature. Moreover, the wet chemical method that we are reporting in the present paper for the preparation of luminescent silver nanoclusters is better than the other methods reported in the literature. Further, these in situ generated Ag NCs showed exceptional catalytic activity in the preparation of pyrroles involving cocyclization of isocyanides and terminal alkynes. Interestingly, the catalytic efficiency of in situ generated Ag NCs was found to be better than the other catalytic systems reported in the literature.

Aggregates of a hetero-oligophenylene derivative as reactors for the generation of palladium nanoparticles: a potential catalyst in the Sonogashira coupling reaction under aerial conditions.

The utilization of Pd nanoparticles stabilized by aggregates of hetero-oligophenylene derivative 3 as an excellent catalyst in a copper/amine free Sonogashira coupling reaction under aerial conditions at room temperature has been demonstrated.

A hexaphenylbenzene based AIEE active two photon probe for the detection of hydrogen sulfide with tunable self-assembly in aqueous media and application in live cell imaging.

Supramolecular aggregates of hexaphenylbenzene derivative exhibit aggregation induced emission enhancement and modulation of self-assembled architecture from spherical to flower-like assembly in the presence of H2S. Furthermore, probe displays higher photostability, low toxicity and bright green fluorescence in two-photon microscopy (TPM) imaging for the detection of H2S in live HeLa cells.

One-pot multicomponent synthesis of tetrahydropyridines promoted by luminescent ZnO nanoparticles supported by the aggregates of 6,6-dicyanopentafulvene.

Pot-shaped fluorescent aggregates of 6,6-dicyanopentafulvene derivative serve as reactors and stabilizers for the preparation of luminescent ZnO nanoparticles, which exhibit high catalytic efficiency in one-pot multicomponent synthesis of tetrahydropyridines.

A hexaphenylbenzene based AIEE active probe for the preparation of ferromagnetic α-Fe2O3 nanoparticles: facile synthesis and catalytic applications.

Fluorescent aggregates formed by self-assembly of a hexaphenylbenzene based derivative serve as a reactor and a stabilizer for the formation of ferromagnetic iron oxide (α-Fe2O3) nanoparticles in aqueous medium at room temperature. These α-Fe2O3 nanoparticles showed excellent catalytic activity in palladium, copper and amine free Sonogashira cross coupling reactions and also in photocatalytic degradation of rhodamine B dye.

Hexaphenylbenzene-based fluorescent aggregates for ratiometric detection of cyanide ions at nanomolar level: set-reset memorized sequential logic device.

A hexaphenylbenzene-based receptor 3 has been synthesized that forms a fluorescent spherical aggregate in mixed aqueous media due to its aggregation-induced emission enhancement attributes. These fluorescent spherical aggregates show ratiometric response toward cyanide ions via nucleophilic addition and undergo deaggregation to form smaller nanoaggregates. In addition, the solution-coated paper strips of 3 can detect cyanide ions in the range of ∼2.6 ng/cm(2), thus, providing a simple, portable, and low-cost method for detection of cyanide ions in aqueous media. Receptor 3 also behaves as a set-reset memorized sequential logic circuit with chemical inputs of CN(-) ions and trifluoroacetic acid or H(+) (pH ≤ 3).

Mercury assisted fluorescent supramolecular assembly of hexaphenylbenzene derivative for femtogram detection of picric acid.

Aggregates of hexaphenylbenzene derivatives 3, having pyrene groups form network of fluorescent nanofibres in presence of mercury ions. Further, fluorescent nanofibres of 3-Hg(2+) supramolecular ensemble exhibit sensitive and pronounced response towards the picric acid. In addition, the solution coated paper strips of 3-Hg(2+) supramolecular ensemble can detect picric acid in the range of 2.29 fg/cm(2), thus, providing a simple, portable and low cost method for detection of picric acid in solution and in contact mode.