On-Water Surface Synthesis of Vinylene-Linked Cationic Two-Dimensional Polymer Films as the Anion-Selective Electrode Coating.

Vinylene-linked two-dimensional polymers (V-2DPs) and their layer-stacked covalent organic frameworks (V-2D COFs) featuring high in-plane π-conjugation and robust frameworks have emerged as promising candidates for energy-related applications. However, current synthetic approaches are restricted to producing V-2D COF powders that lack processability, impeding their integration into devices, particularly within membrane technologies reliant upon thin films. Herein, we report the novel on-water surface synthesis of vinylene-linked cationic 2DPs films (V-C2DP-1 and V-C2DP-2) via Knoevenagel polycondensation, which serve as the anion-selective electrode coating for highly-reversible and durable zinc-based dual-ion batteries (ZDIBs). Model reactions and theoretical modeling revealed the enhanced reactivity and reversibility of the Knoevenagel reaction on the water surface. On this basis, we demonstrated the on-water surface 2D polycondensation towards V-C2DPs films that show large lateral size, tunable thickness, and high chemical stability. Representatively, V-C2DP-1 presents as a fully crystalline and face-on oriented film with in-plane lattice parameters of a=b≈43.3 Å. Profiting from its well-defined cationic sites, oriented 1D channels, and stable frameworks, V-C2DP-1 film possesses superior bis(trifluoromethanesulfonyl)imide anion (TFSI-)-transport selectivity (transference, t_=0.85) for graphite cathode in high-voltage ZDIBs, thus triggering additional TFSI--intercalation stage and promoting its specific capacity (from ~83 to 124 mAh g-1) and cycling life (>1000 cycles, 95 % capacity retention).

Toward Smart Sensing by MXene.

The Internet of Things era has promoted enormous research on sensors, communications, data fusion, and actuators. Among them, sensors are a prerequisite for acquiring the environmental information for delivering to an artificial data center to make decisions. The MXene-based sensors have aroused tremendous interest because of their extraordinary performances. In this review, the electrical, electronic, and optical properties of MXenes are first introduced. Next, the MXene-based sensors are discussed according to the sensing mechanisms such as electronic, electrochemical, and optical methods. Initially, biosensors are introduced based on chemiresistors and field-effect transistors. Besides, the wearable pressure sensor is demonstrated with piezoresistive devices. Third, the electrochemical methods include amperometry and electrochemiluminescence as examples. In addition, the optical approaches refer to surface plasmonic resonance and fluorescence resonance energy transfer. Moreover, the prospects are delivered of multimodal data fusion toward complicated human-like senses. Eventually, future opportunities for MXene research are conveyed in the new material discovery, structure design, and proof-of-concept devices.

Photocatalytic degradation of methylene blue at nanostructured ZnO thin films.

The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l-1MB solution, 540 minUV irradiation), the rate constantkof MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10-9(mol·l-1·min-1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB.

Sequence-controlled chiral induced spin selectivity effect in ds-DNA.

In this research, we explore sequence-dependent chiral-induced spin selectivity (CISS) in double-stranded (ds)-DNA using time-correlated single-photon counting and electrochemical impedance spectroscopy supplemented by tight-binding calculations of the phenomenon for the first time. The average lifetime of the photo-excited electrons in a Quantum Dot-DNA system is influenced by the CISS effect generated by the DNA molecule, and the difference in average time decay of electrons was found to be 345 ps for opposite polarity ("UP" and "DOWN") of spins due to the CISS effect. Moreover, the yield of spin-polarized electrons due to the CISS effect was reduced by more than 35% from perfect DNA to DNA with point mutations. Remarkably, by employing a tight binding method combined with Green's function formalism for transport, simulations of the process support the observed experimental trends. Our results provide a basic understanding of the sequence-specific spin-dependent electron transfer through ds-DNA. These results would help to build spin-based next-generation DNA sensors.

Spin-phonon coupling in a double-stranded model of DNA.

We address the electron-spin-phonon coupling in an effective model Hamiltonian for DNA to assess its role in spin transfer involved in the Chiral-Induced Spin Selectivity (CISS) effect. The envelope function approach is used to describe semiclassical electron transfer in a tight-binding model of DNA at half filling in the presence of intrinsic spin-orbit coupling. Spin-phonon coupling arises from the orbital-configuration dependence of the spin-orbit interaction. We find spin-phonon coupling only for the acoustic modes, while the optical modes exhibit electron-phonon interaction without coupling to spin. We derive an effective Hamiltonian whose eigenstates carry spin currents that are protected by spin-inactive stretching optical modes. As optical phonons interact more strongly than acoustic phonons, side buckling and tilting optical base modes will be more strongly associated with decoherence, which allows for the two terminal spin filtering effects found in CISS.

Sensors for in situ monitoring of oral and dental health parameters in saliva.

OBJECTIVES: The oral cavity is an easily accessible unique environment and open system which is influenced by the oral fluids, microbiota, and nutrition. Little is known about the kinetics and dynamics of metabolic processes at the intraoral surfaces. Real-time monitoring of salivary biomarkers, e.g., glucose, lactate, fluoride, calcium, phosphate, and pH with intraoral sensors is therefore of major interest. The aim of this review is to overview the existing literature for intraoral saliva sensors. MATERIALS AND METHODS: A comprehensive literature search was performed to review the most relevant studies on intraoral saliva sensor technology. RESULTS: There is limited literature about the in situ saliva monitoring of salivary biomarkers. Bioadhesion and biofouling processes at the intraoral surfaces limit the performances of the sensors. Real-time, long-term, and continuous intraoral measurement of salivary metabolites remains challenging and needs further investigation as only few well-functioning sensors have been developed until today. Until now, there is no sensor that measures reliably beyond hours for any analyte other than glucose. CONCLUSIONS: Saliva's complex and dynamic structure as well as bioadhesion are key challenges and should be addressed in the future developments. Consequently, more studies that focus particularly on biofouling processes and interferential effects of the salivary matrix components on sensor surfaces are required. CLINICAL RELEVANCE: By monitoring fluids in the oral cavity, as the entrance to the digestive system, extensive information can be obtained regarding the effects of foods and preventive agents on the oral microbiota and the tooth surfaces. This may lead to a better understanding of strategies to modulate oral and general health.

Dithienylethene-Based Single Molecular Photothermal Linear Actuator.

By employing a mechanically controllable break junction technique, we have realized an ideal single molecular linear actuator based on dithienylethene (DTE) based molecular architecture, which undergoes reversible photothermal isomerization when subjected to UV irradiation under ambient conditions. As a result, open form (compressed, UV OFF) and closed form (elongated, UV ON) of dithienylethene-based molecular junctions are achieved. Interestingly, the mechanical actuation is achieved without changing the conductance of the molecular junction around the Fermi level over several cycles, which is an essential property required for an ideal single molecular actuator. Our study demonstrates a unique example of achieving a perfect balance between tunneling width and barrier height change upon photothermal isomerization, resulting in no change in conductance but a change in the molecular length, which results in mechanical actuation at the single molecular level.

Control of Crystallinity of Vinylene-Linked Two-Dimensional Conjugated Polymers by Rational Monomer Design.

The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp2 -carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylene-quinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylene-vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C-C single bond formation.

An effective formaldehyde gas sensor based on oxygen-rich three-dimensional graphene.

Three-dimensional (3D) graphene with a high specific surface area and excellent electrical conductivity holds extraordinary potential for molecular gas sensing. Gas molecules adsorbed onto graphene serve as electron donors, leading to an increase in conductivity. However, several challenges remain for 3D graphene-based gas sensors, such as slow response and long recovery time. Therefore, research interest remains in the promotion of the sensitivity of molecular gas detection. In this study, we fabricate oxygen plasma-treated 3D graphene for the high-performance gas sensing of formaldehyde. We synthesize large-area, high-quality, 3D graphene over Ni foam by chemical vapor deposition and obtain freestanding 3D graphene foam after Ni etching. We compare three types of strategies-non-treatment, oxygen plasma, and etching in HNO3solution-for the posttreatment of 3D graphene. Eventually, the strategy for oxygen plasma-treated 3D graphene exceeds expectations, which may highlight the general gas sensing based on chemiresistors.

Combination of Knoevenagel Polycondensation and Water-Assisted Dynamic Michael-Addition-Elimination for the Synthesis of Vinylene-Linked 2D Covalent Organic Frameworks.

Vinylene-linked two-dimensional conjugated covalent organic frameworks (V-2D-COFs), belonging to the class of two-dimensional conjugated polymers, have attracted increasing attention due to their extended π-conjugation over the 2D backbones associated with high chemical stability. The Knoevenagel polycondensation has been demonstrated as a robust synthetic method to provide cyano (CN)-substituted V-2D-COFs with unique optoelectronic, magnetic, and redox properties. Despite the successful synthesis, it remains elusive for the relevant polymerization mechanism, which leads to relatively low crystallinity and poor reproducibility. In this work, we demonstrate the novel synthesis of CN-substituted V-2D-COFs via the combination of Knoevenagel polycondensation and water-assisted dynamic Michael-addition-elimination, abbreviated as KMAE polymerization. The existence of C=C bond exchange between two diphenylacrylonitriles (M1 and M6) is firstly confirmed via in situ high-temperature NMR spectroscopy study of model reactions. Notably, the intermediate M4 synthesized via Michael-addition can proceed the Michael-elimination quantitatively, leading to an efficient C=C bond exchange, unambiguously confirming the dynamic nature of Michael-addition-elimination. Furthermore, the addition of water can significantly promote the reaction rate of Michael-addition-elimination for highly efficient C=C bond exchange within 5 mins. As a result, the KMAE polymerization provides a highly efficient strategy for the synthesis of CN-substituted V-2D-COFs with high crystallinity, as demonstrated by four examples of V-2D-COF-TFPB-PDAN, V-2D-COF-TFPT-PDAN, V-2D-COF-TFPB-BDAN, and V-2D-COF-HATN-BDAN, based on the simulated and experimental powder X-ray diffraction (PXRD) patterns as well as N2 -adsorption-desorption measurements. Moreover, high-resolution transmission electron microscopy (HR-TEM) analysis shows crystalline domain sizes ranging from 20 to 100 nm for the newly synthesized V-2D-COFs.

Vinylene-Linked 2D Conjugated Covalent Organic Frameworks by Wittig Reactions.

Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high (E)-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs2 CO3 ) to obtain more stable intermediates and elevating the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm2  V-1 s-1 , as revealed by non-contact terahertz (THz) spectroscopy.

On-Surface Formation of Cyano-Vinylene Linked Chains by Knoevenagel Condensation.

The rapid development of on-surface synthesis provides a unique approach toward the formation of carbon-based nanostructures with designed properties. Herein, we present the on-surface formation of CN-substituted phenylene vinylene chains on the Au(111) surface, thermally induced by annealing the substrate stepwise at temperatures between 220 °C and 240 °C. The reaction is investigated by scanning tunneling microscopy and density functional theory. Supported by the calculated reaction pathway, we assign the observed chain formation to a Knoevenagel condensation between an aldehyde and a methylene nitrile substituent.

Determining the Diffusion Coefficient of Lithium Insertion Cathodes from GITT measurements: Theoretical Analysis for low Temperatures*.

Accurate knowledge of transport properties of Li-insertion materials in application-relevant temperature ranges is of crucial importance for the targeted optimization of Li-ion batteries (LIBs). Galvanostatic intermittent titration technique (GITT) is a widely applied method to determine Li-ion diffusion coefficients of electrode materials. The well-known calculation formulas based on Weppner's and Huggins' approach, imply a square-root time dependence of the potential during a GITT pulse. Charging the electrochemical double layer capacitance at the beginning of a GITT pulse usually takes less than one second. However, at lower temperatures down to -40 °C, the double layer charging time strongly increases due to an increase of the charge transfer resistance. The charging time can become comparable with the pulse duration, impeding the conventional GITT diffusion analysis. We propose a model to describe the potential change during a galvanostatic current pulse, which includes an initial, relatively long-lasting double layer charging, and analyze the accuracy of the lithium diffusion coefficient, derived by using the Weppner-Huggins method within a suitably chosen time interval of the pulse. Effects leading to an inaccurate determination of the diffusion coefficient are discussed and suggestions to improve GITT analyses at low temperature are derived.

Impact of surface charge on the motion of light-activated Janus micromotors.

Control over micromotors' motion is of high relevance for lab-on-a-chip and biomedical engineering, wherein such particles encounter complex microenvironments. Here, we introduce an efficient way to influence Janus micromotors' direction of motion and speed by modifying their surface properties and those of their immediate surroundings. We fabricated light-responsive Janus micromotors with positive and negative surface charge, both driven by ionic self-diffusiophoresis. These were used to observe direction-of-motion reversal in proximity to glass substrates for which we varied the surface charge. Quantitative analysis allowed us to extract the dependence of the particle velocity on the surface charge density of the substrate. This constitutes the first quantitative demonstration of the substrate's surface charge on the motility of the light-activated diffusiophoretic motors in water. We provide qualitative understanding of these observations in terms of osmotic flow along the substrate generated through the ions released by the propulsion mechanism. Our results constitute a crucial step in moving toward practical application of self-phoretic artificial micromotors.

Role of Exchange Interactions in the Magnetic Response and Intermolecular Recognition of Chiral Molecules.

The physical origin of the so-called chirality-induced spin selectivity (CISS) effect has puzzled experimental and theoretical researchers over the past few years. Early experiments were interpreted in terms of unconventional spin-orbit interactions mediated by the helical geometry. However, more recent experimental studies have clearly revealed that electronic exchange interactions also play a key role in the magnetic response of chiral molecules in singlet states. In this investigation, we use spin-polarized closed-shell density functional theory calculations to address the influence of exchange contributions to the interaction between helical molecules as well as of helical molecules with magnetized substrates. We show that exchange effects result in differences in the interaction properties with magnetized surfaces, shedding light into the possible origin of two recent important experimental results: enantiomer separation and magnetic exchange force microscopy with AFM tips functionalized with helical peptides.

Nanocytometer for smart analysis of peripheral blood and acute myeloid leukemia: a pilot study.

We realize an ultracompact nanocytometer for real-time impedimetric detection and classification of subpopulations of living cells. Nanoscopic nanowires in a microfluidic channel act as nanocapacitors and measure in real time the change of the amplitude and phase of the output voltage and, thus, the electrical properties of living cells. We perform the cell classification in the human peripheral blood (PBMC) and demonstrate for the first time the possibility to discriminate monocytes and subpopulations of lymphocytes in a label-free format. Further, we demonstrate that the PBMC of acute myeloid leukemia and healthy samples grant the label free identification of the disease. Using the algorithm based on machine learning, we generated specific data patterns to discriminate healthy donors and leukemia patients. Such a solution has the potential to improve the traditional diagnostics approaches with respect to the overall cost and time effort, in a label-free format, and restrictions of the complex data analysis.

Interactions of Long-Chain Polyamines with Silica Studied by Molecular Dynamics Simulations and Solid-State NMR Spectroscopy.

The investigation of molecular interactions between silica phases and organic components is crucial for elucidating the main steps involved in the biosilica mineralization process. In this respect, the structural characterization of the organic/inorganic interface is particularly useful for a deeper understanding of the dominant mechanisms of biomineralization. In this work, we have investigated the interaction of selectively 13C- and 15N-labeled atoms of organic long-chain polyamines (LCPAs) with 29Si-labeled atoms of a silica layer at the molecular level. In particular, silica/LCPA nanocomposites were analyzed by solid-state NMR spectroscopy in combination with all-atom molecular dynamics simulations. Solid-state NMR experiments allow the determination of 29Si-15N and 29Si-13C internuclear distances, providing the parameters for direct verification of atomistic simulations. Our results elucidate the relevant molecular conformations as well as the nature of the interaction between the LCPA and a silica substrate. Specifically, distances and second moments suggest a picture compatible with (i) LCPA completely embedded in the silica phase and (ii) the charged amino groups located in close vicinity of silanol groups.

Comparative Studies of Light-Responsive Swimmers: Janus Nanorods versus Spherical Particles.

The shape of objects has a strong influence on their dynamics. Here, we present comparative studies of two different motile objects, spherical Ag/AgCl Janus particles and polystyrene Janus nanorods, that move due to an ionic self-diffusiophoretic propulsion mechanism when exposed to blue light. In this paper, we propose a method to fabricate Janus rodlike particles with high aspect ratios and hemispherical tip shapes. The inherent asymmetry due to the ratio between capped and uncapped parts of the particles as well as the shape anistropy of Janus nanorods enables imaging and quantification of rotational dynamics. The dynamics of microswimmers are compared in terms of velocities and diffusion coefficients. We observe that despite a small amount of the Ag/AgCl reagent on the surface of rodlike objects, these new Janus micromotors reveal high motility in pure water. While the velocities of spherical particles reach 4.2 µm/s, the single rodlike swimmers reach 1.1 µm/s, and clusters reach 1.6 µm/s. The effect of suppressed rotational diffusion is discussed as one of the reasons for the increased velocities. These Janus micro- and nanomotors hold the promise for application in light-controlled propulsion transport.

Anisotropic Exclusion Effect between Photocatalytic Ag/AgCl Janus Particles and Passive Beads in a Dense Colloidal Matrix.

Synthetic nano- and micromotors interact with each other and their surroundings in a complex manner. Here, we report on the anisotropy of active-passive particle interaction in a soft matter system containing an immobile yet photochemical Ag/AgCl-based Janus particle embedded in a dense matrix of passive beads in pure water. The asymmetry in the chemical gradient around the Janus particle, triggered upon visible light illumination, distorts the isotropy of the surrounding electric potential and results in the repulsion of adjacent passive beads to a certain distance away from the Janus particle. This exclusion effect is found to be anisotropic with larger distances to passive beads in front of the Ag/AgCl cap of the Janus particle. We provide insight into this phenomenon by performing the angular analysis of the radii of exclusion and tracking their time evolution at the level of a single bead. Our study provides a novel fundamental insight into the collective behavior of a complex mixture of active and passive particles and is relevant for various application scenarios, e.g., particle transport at micro- and nanoscale and local chemical sensing.

Modification of titanium implants using biofunctional nanodiamonds for enhanced antimicrobial properties.

The present study describes a novel antimicrobial surface using anodic oxidation of titanium and biofunctional detonation nanodiamonds (ND). ND have been loaded with antibiotics (amoxicillin or ampicillin) using poly(diallyldimethylammonium chloride) (PDDA). Successful conjugation with PDDA was determined by dynamic light scattering, which showed increase in the hydrodynamic diameter of ND agglomerates and shift of zeta potential towards positive values. The surface loading of amoxicillin was determined using UV-vis spectroscopy and the maximum of 44% surface loading was obtained. Biofunctional ND were immobilized by anodic oxidation within a titanium oxide layer, which was confirmed by scanning electron microscopy. The in vitro antimicrobial properties of ND suspensions were examined using Kirby-Bauer test with E. coli. Modified titanium surfaces comprising biofunctional ND were evaluated with E. coli inoculum by live/dead assay staining. Both biofunctional ND suspensions and modified titanium surfaces presented inhibition of bacteria growth and increase in bacteria lethality.