Multi-function adsorbent-photocatalyst MXene-TiO2 composites for removal of enrofloxacin antibiotic from water.

MXenes, a new family of two-dimensional transition metal carbides or nitrides, have attracted tremendous attention for various applications due to their unique properties such as good electrical conductivity, hydrophilicity, and ion intercalability. In this work, Ti3C2 MXene, or MX, is converted to MX-TiO2 composites using a simple and rapid microwave hydrothermal treatment in HCl/NaCl mixture solution that induces formation of fine TiO2 particles on the MX parent structure and imparts photocatalytic activity to the resulting MX-TiO2 composites. The composites were used for enrofloxacin (ENR), a frequently found contaminating antibiotic, removal from water. The relative amount of the MX and TiO2 can be controlled by controlling the hydrothermal temperature resulting in composites with tunable adsorption/photocatalytic properties. NaCl addition was found to play important role as composites synthesized without NaCl could not adsorb enrofloxacin well. Adding NaCl into the hydrothermal treatment causes sodium ions to be simultaneously intercalated into the composite structure, improving ENR adsorption greatly from 1 to 6 mg ENR/g composite. It also slows down the MX to TiO2 conversion leading to a smaller and more uniform distribution of TiO2 particles on the structure. MX-TiO2/NaCl composites, which have sodium intercalated in their structures, showed both higher ENR adsorption and photocatalytic activity than composites without NaCl despite the latter having higher TiO2 content. Adsorbed ENR on the composites can be efficiently degraded by free radicals generated from the photoexcited TiO2 particles, leading to high photocatalytic degradation efficiency. This demonstrates the synergetic effect between adsorption and photocatalytic degradation of the synthesized compounds.

Voltammetric biosensor for coronavirus spike protein using magnetic bead and screen-printed electrode for point-of-care diagnostics.

The rapid spread of the novel human coronavirus 2019 (COVID-19) and its morbidity have created an urgent need for rapid and sensitive diagnostics. The real-time polymerase chain reaction is the gold standard for detecting the coronavirus in various types of biological specimens. However, this technique is time consuming, labor intensive, and expensive. Screen-printed electrodes (SPEs) can be used as point-of-care devices because of their low cost, sensitivity, selectivity, and ability to be miniaturized. The ability to detect the spike protein of COVID-19 in serum, urine, and saliva was developed using SPE aided by magnetic beads (MBs) and a portable potentiostat. The antibody-peroxidase-loaded MBs were the captured and catalytic units for the electrochemical assays. The MBs enable simple washing and homogenous deposition on the working electrode using a magnet. The assembly of the immunological MBs and the electrochemical system increases the measuring sensitivity and speed. The physical and electrochemical properties of the layer-by-layer modified MBs were systematically characterized. The performance of these immunosensors was evaluated using spike protein in the range 3.12-200 ng mL-1. We achieved a limit of detection of 0.20, 0.31, and 0.54 ng mL-1 in human saliva, urine, and serum, respectively. A facile electrochemical method to detect COVID-19 spike protein was developed for quick point-of-care testing.

Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers.

We report Tn ← T1 spectra and extinction coefficients, ε, and other properties as functions of chain length for a series of fluorene oligomers, oFn, and polymers, pFn, with n = 2-84 repeat units. We find that ε increases with length, peaking at 159 400 M-1 cm-1 for oF3 and then decreases for longer chains. ε does not scale with 1/n or e-n to reach a constant value at long length, as predicted by the commonly applied oligomer extrapolation approximation, although spectral shifts, oscillator strengths, and transition dipole moments do reach limiting values for chains near 10 units long. While computations describe the triplet in oF2 and oF3 as having similar geometries with a single flattened dihedral angle between units, computations and simulations suggest that in longer oligomers motion along the chains of the short 2-3 unit, the long T1 state is probably the source of the unusual changes in ε. These occur because hopping along the chain is sufficiently fast that the dihedrals between fluorene units cannot fully relax. At a length near 10 units, hopping and dihedral angle changes produce a steady state distribution of geometries with only small changes from the ground state, which persist for longer chains. Additional decreases in ε from pF28 to pF84 are plausibly due to a small number of chain defects which result in loss of triplets.

Preparation of heterogeneous cation exchange membrane and its contributions in enhancing the removal of Ni2+ by capacitive deionization system.

Capacitive deionization (CDI), an emerging method to eliminate ions from water at a low cost, has garnered significant interest in recent years. This study evaluates the implication of cation exchange resin loading on the membrane via the nonsolvent-induced phase inversion method. After determining the quantity of resins efficiently loaded on the membrane, it was subsequently utilized as a cation exchange membrane in the membrane capacitive deionization (MCDI) unit to examine the performance removal of Ni2+. The results show that the amount of resins influenced the membrane structure and significantly improved the efficiency of Ni2+ removal. The sulfonic acid group show a strong intensity directly proportional to the quantity of resins based on the FTIR measurement. In conjunction with the enhanced resin amount, ion exchange capacity and water content were increased. Simultaneously, there was an observed elevation in the water contact angle and the roughness of the membrane surface with increased resin amount. In the MCDI unit, membrane M20 (20% by weight resin) was employed to elucidate its roles in the CDI unit, encompassing an examination of various concentrations and flow rates, with Ni2+ utilized as a test contaminant. The results demonstrated that using membrane M20 in the MCDI (MCDI-M20) unit consistently exhibited higher adsorption levels than the CDI unit, reaching 19.80 mg g-1 ACC in the MCDI-M20 unit, while CDI unit achieved 10.27 mg g-1 ACC at 200 mg L-1 Ni2+ concentration and a flow rate of 10 mL min-1 at 1.2 V. Additionally, Ni2+ concentrations and flow rates in CDI system had an evident impact on the duration of adsorption due to the mechanisms of ions transport on the membrane. This study suggests that employing the prepared membrane in the MCDI unit enhanced the removal of Ni2+ from the solution, contributing to sustainable development goals.

Upcycling of post-consumer polyethylene terephthalate bottles into aluminum-based metal-organic framework adsorbents for efficient orthophosphate removal.

2-Phosphonobutane-1,2,4,-tricarboxylic acid (PBTC) is an orthophosphate compound widely used as an antiscalant chemical and corrosion inhibitor in manufacturing. However, PBTC poses persistent environmental concerns due to its stability and resistance to conventional water treatment. In addressing the issues of PBTC in aquatic systems, Al-based metal-organic frameworks (MOFs) have been developed and applied as sustainable adsorbents. The materials are synthesized from terephthalic acid (TPA) linkers derived from upcycling products of post-consumer polyethylene terephthalate (PET) bottles. The PET-derived linker was prepared using alkaline hydrolysis followed by acidification and employed in forming MIL-53 (Al), with a comparative assessment against the corresponding MOFs made from commercial-grade TPA. The structures and properties of the materials were characterized with microscopic and spectroscopic methods. The synthesized adsorbents achieved a phosphate adsorption capacity of 826 mg/g at pH 5, with kinetics fitting a pseudo-second-order model and isotherm patterns aligning with Langmuir, Freundlich, and Sips models, indicative of diverse adsorption on heterogeneous surfaces. The results highlight the role of electrostatic interactions and hydrogen bonding mechanisms in PBTC adsorption. The eco-friendly materials with high adsorption performance offer an innovative route for sustainable waste management and water purification.

Synthesis and characterization of Au-decorated graphene oxide nanocomposite for magneto-electrochemical detection of SARS-CoV-2 nucleocapsid gene.

Fast and effective diagnosis is the first step in monitoring the current coronavirus 2 (CoV-2) pandemic. Herein, we establish a simple and sensitive electrochemical assay using magnetic nanocomposite and DNA sandwich probes to rapidly quantify the CoV-2 nucleocapsid (N) gene down to the 0.37 fM level. This assay uses a pair of specific DNA probes. The capture probe is covalently conjugated to Au-decorated magnetic reduced graphene oxide (AMrGO) nanocomposite for efficiently capturing target RNA. In contrast, the detection probe is linked to peroxidase for signal amplification. The probes target the COV-2 gene, allowing for specific magnetic separation, enzymatic signal amplification, and subsequent generation of voltammetric current with a total assay time of 45 min. The developed biosensor has high selectivity and can discriminate non-specific gene sequences. Synthetic COV-2 N-gene can be detected efficiently in serum and saliva, while 1-bp mismatch gene yielded a low response. The performance of the genosensor was good in an extensive linear range of 5 aM-50 pM. For synthetic N-gene, we achieved the detection limit of 0.37, 0.33, and 0.19 fM in human saliva, urine, and serum. This simple, selective, and sensitive genosensor could have various genetics-based biosensing and diagnostic applications.

Microwave assisted synthesis of Mn3O4 nanograins intercalated into reduced graphene oxide layers as cathode material for alternative clean power generation energy device.

Mn3O4 nanograins incorporated into reduced graphene oxide as a nanocomposite electrocatalyst have been synthesized via one-step, facile, and single-pot microwave-assisted hydrothermal technique. The nanocomposites were employed as cathode material of fuel cells for oxygen reduction reaction (ORR). The synthesized product was thoroughly studied by using important characterization, such as XRD for the structure analysis and FESEM and TEM analyses to assess the morphological structures of the material. Raman spectra were employed to study the GO, rGO bands and formation of Mn3O4@rGO nanocomposite. FTIR and UV-Vis spectroscopic analysis were used to verify the effective synthesis of the desired electrocatalyst. The Mn3O4@rGO-10% nanocomposite with 10 wt% of graphene oxide was used to alter the shiny surface of the working electrode and applied for ORR in O2 purged 0.5 M KOH electrolyte solution. The Mn3O4@rGO-10% nanocomposite electrocatalyst exhibited outstanding performance with an improved current of - 0.738 mA/cm2 and shifted overpotential values of - 0.345 V when compared to other controlled electrodes, including the conventionally used Pt/C catalyst generally used for ORR activity. The tolerance of Mn3O4@rGO-10% nanocomposite was tested by injecting a higher concentration of methanol, i.e., 0.5 M, and found unsusceptible by methanol crossover. The stability test of the synthesized electrocatalyst after 3000 s was also considered, and it demonstrated excellent current retention of 98% compared to commercially available Pt/C electrocatalyst. The synthesized nanocomposite material could be regarded as an effective and Pt-free electrocatalyst for practical ORR that meets the requirement of low cost, facile fabrication, and adequate stability.

Preparation of Water-Based Alkyl Ketene Dimer (AKD) Nanoparticles and Their Use in Superhydrophobic Treatments of Value-Added Teakwood Products.

A process for preparing emulsions of alkyl ketene dimer (AKD) nanoparticles via a nanoemulsion template (emulsion/evaporation) method has been developed. The effects of types and contents of stabilizing agents, i.e., anionic (sodium dodecyl sulfate, SDS), cationic (cetyltrimethylammonium bromide, CTAB), amphoteric (phosphatidylcholine, PC), and polymeric (poly(vinyl alcohol), PVA), on the colloidal stability and hydrodynamic size of the AKD nanoparticles are investigated. The use of 0.1 wt % anionic SDS as a stabilizer generates nanoparticles with high stability and the smallest average size of 148 ± 5 nm. The environmentally friendly water-based emulsion prepared without halogenated compounds and harsh organic solvents is then applied to enhance the hydrophobicity of teakwood products by a simple dipping process. The properties and structures of the resulting treated woods are examined by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM), and water contact angle (WCA) measurements. The treated woods show superhydrophobicity with a WCA value of 150 ± 2°, as the emulsion generates a hydrophobic layer covering the wood surfaces due to the ß-ketoester bond formation and the arrangement of AKD hydrophobic tails. The nanosized nanoparticles can penetrate the dense structure of the teakwood and form similar bonding for up to a 0.8 mm depth, generating a protective water-repellent layer in the wood structure. The emulsion has high potential for use in the commercial production of value-added teakwood products, with excellent water-resistant properties and high dimensional instability, without altering their physical appearances.

Sudden, "step" electron capture by conjugated polymers.

Data showing significant time-resolution-limited "step" capture of electrons following radiolysis by 7 - 10 ps electron pulses in a series of different length and different concentration conjugated polyfluorene polymers in tetrahydrofuran (THF) are presented. At the highest concentration, ∼48 mM in repeat units for lengths from 20 to 133 fluorenes, ∼30% of the electrons formed during pulse radiolysis were captured in the step, with a constant efficiency per repeat unit. Step capture per repeat unit (q = 6.9 M(-1)) is 60% of the presolvated electron capture efficiency previously reported for biphenyl in THF, giving capture per polymer molecule 12-80 times larger than that for biphenyl at the same concentration. This increase in capture efficiency is large compared to the rate constant per repeat unit for diffusion-limited electron attachment to the same molecules, which is 13% of that of a single unit of fluorene. Plausible mechanisms of this fast capture are explored. It is shown that both capture of quasi-free and localized presolvated electrons can adequately explain the observations. The large yield of radical anions at low concentration of polyfluorene enables observation of subsequent chemistry on the picosecond time scale in these systems, which would otherwise been limited by diffusional attachment to the nanosecond regime.

Toward designed singlet fission: electronic states and photophysics of 1,3-diphenylisobenzofuran.

Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1(+*)) and anion (1(-*)), we report the UV-visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, S(1) --> S(x) and sensitized T(1) --> T(x), and single exponential lifetimes, tau(F) = approximately 5.3 ns and tau(T) = approximately 200 micros, are reported. The spectra and lifetimes of S(1) --> S(0) fluorescence and sensitized T(1) --> T(x) absorption of 1 were obtained in a series of solvents, as was the fluorescence quantum yield, Phi(F) = 0.95-0.99. No phosphorescence has been detected. The first triplet excitation energy of solid 1 (11,400 cm(-1)) was obtained by electron energy loss spectroscopy, in agreement with previously reported solution values. The fluorescence excitation spectrum suggests an onset of a nonradiative channel at approximately 37,000 cm(-1). Excitation energies and relative transition intensities are in agreement with those of ab initio (CC2) calculations after an empirical 3000 cm(-1) adjustment of the initial state energy to correct differentially for a better quality description of the initial relative to the terminal state of an absorption transition. The interpretation of the MCD spectrum used the semiempirical PPP method, whose results for the S(0) --> S(x) spectrum require no empirical adjustment and are otherwise nearly identical with the CC2 results in all respects including the detailed nature of the electronic excitation. The ground state geometry of 1 was also calculated by the MP2, B3LYP, and CAS methods. The calculations provided a prediction of changes of molecular geometry upon excitation or ionization and permitted an interpretation of the spectra in terms of molecular orbitals involved. Computations suggest that 1 can exist as two nearly isoenergetic conformers of C(2) or C(s) symmetry. Linear dichroism measurements in stretched polyethylene provide evidence for their existence and show that they orient to different degrees, permitting a separation of their spectra in the region of the purely polarized first absorption band. Their excitation energies are nearly identical, but the Franck-Condon envelopes of their first transition differ to a surprising degree.

Electronic structures of interfacial states formed at polymeric semiconductor heterojunctions.

Heterojunctions between organic semiconductors are central to the operation of light-emitting and photovoltaic diodes, providing respectively for electron-hole capture and separation. However, relatively little is known about the character of electronic excitations stable at the heterojunction. We have developed molecular models to study such interfacial excited electronic excitations that form at the heterojunction between model polymer donor and polymer acceptor systems: poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine) (PFB) with poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), and poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) with F8BT. We find that for stable ground-state geometries the excited state has a strong charge-transfer character. Furthermore, when partly covalent, modelled radiative lifetimes (approximately 10(-7) s) and off-chain axis polarization (30 degrees) match observed 'exciplex' emission. Additionally for the PFB:F8BT blend, geometries with fully ionic character are also found, thus accounting for the low electroluminescence efficiency of this system.

Length and time-dependent rates in diffusion-controlled reactions with conjugated polymers.

Rate constants for diffusion-controlled reactions of solvated electrons with conjugated fluorene oligomers (oF) and polymers (pF) were measured in liquid tetrahydrofuran (THF). Preparative gel permeation chromatography (GPC) was used to separate the polyfluorenes into fractions having narrowed distributions of lengths. Both oF and pF's were used in determinations of the attachment rate constants k(inf) as a function of length, where k(inf) refers to the rate coefficients at long times where they are indeed constant. The results find that in going from oF(1) to pF(133), k(inf) increases by a factor of 16, which is much smaller than that of the 133-fold increase in length. The extent of this increase and its change with length are in excellent agreement with published theoretical models that describe diffusion to long thin objects as either prolate spheroids or one-dimensional arrays of spheres. As the concentration of polymer was increased, the effects of large transient terms in the rate constant were observed. As predicted by the Smoluchowski diffusion equation, with modifications by more contemporary theorists, these transient effects are larger and persist to longer times for the larger molecules. For the longest molecule, pF(133), k(t) increases by more than a decade at short times. In that case, the "transient term" becomes dominant and the rate coefficient is approximately proportional to the square of the effective reaction radius in contrast to the linear dependence usual for diffusional reactions. The size of these transient effects and their quantitative confirmation are unprecedented.

Optoelectronic and charge transport properties at organic-organic semiconductor interfaces: comparison between polyfluorene-based polymer blend and copolymer.

We report detailed studies of optoelectronic and charge transport properties at the organic-organic semiconductor interfaces formed between polymer chains (interchain) and within a polymer chain (intrachain). These interfaces are fabricated using poly(9,9-di-n-octylfluorene-alt-N-(4-butylphenyl)diphenylamine) (TFB [f8-tfb]) (electron-donor) and poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT [f8-bt]) (electron-acceptor) conjugated polymers, by blending them together or by covalently attaching them via a main polymer backbone (copolymer). For optoelectronic properties, when a bulky and twisted tfb molecule is incorporated into a rigid F8BT conjugated backbone, it disturbs the conjugation of F8BT polymer, leading to a blue-shift in the lowest absorption transition. However, by acting as an effective electron donor, it assists the formation of an intrachain singlet exciton that has a strong charge-transfer character, leading to a red-shifted and longer-lived emission than that of F8BT. An extremely efficient and fast energy transfer from tfb donor to bt acceptor is observed in the copolymer (<1 ps) compared to transfer from TFB to F8BT in the blend (tens of ps). This efficient energy transfer in the copolymer is found to be associated with its low fluorescence efficiency (40-45% vs 60-65% for blend) because of the migration of radiative singlet excitons to low-energy states such as triplet and exciplex states that are nonemissive or weakly emissive. The presence of molecular-scale tfb-f8-bt interfaces in the copolymer, however, does not hinder an efficient transport of charge carriers at high drive voltages. Instead, it provides a better balance of charge carriers inside the device, which leads to slower decay of the device efficiency and thus more stable light-emitting diodes with increasing voltage than the blend devices. These distinctive optoelectronic and charge transport properties observed at different organic-organic semiconductor interfaces will provide useful input for the design rules of conjugated polymers required for improved molecular electronics.

Exciton regeneration at polymeric semiconductor heterojunctions.

Control of the band-edge offsets at heterojunctions between organic semiconductors allows efficient operation of either photovoltaic or light-emitting diodes. We investigate systems where the exciton is marginally stable against charge separation and show via E-field-dependent time-resolved photoluminescence spectroscopy that excitons that have undergone charge separation at a heterojunction can be efficiently regenerated. This is because the charge transfer produces a geminate electron-hole pair (separation 2.2-3.1 nm) which may collapse into an exciplex and then endothermically (E(A)=100-200 meV) back transfer towards the exciton.