Magneto- and opto-stimuli responsive nanofibers as a controlled drug delivery system.

The drawbacks of conventional drug administration include repeated administration, non-specific biodistribution in the body's systems, the long-term unsustainability of drug molecules, and high global cytotoxicity, posing a challenge for the efficient treatment of chronic diseases that require varying drug dosages over time for optimal therapeutic efficacy. Most controlled-release methods encapsulate drug molecules in biodegradable materials that dissolve over time to release the drug, making it difficult to deliver drugs on a schedule. To address these limitations, we developed a magneto-, opto-stimuli responsive drug delivery system based on functionalized electrospun nanofibers loaded with superparamagnetic iron oxide nanoparticles (SPIONs). We exploited the Néel relaxation effect of SPIONs, where heat generated from vibrating SPIONs under exogenously applied magnetic fields or laser illumination induced structural changes of the thermo-sensitive nanofibers that encapsulate the particles. We showed that this structural change of nanofibers is the governing factor in controlling the release of dye molecules, used as a model drug and co-encapsulated within the nanofibers. We also showed that the degree of nanofiber structural change depends on SPION loading and duration of stimulation, demonstrating the tunability of the drug release profile. Overall, we demonstrated the potential of SPION-embedded thermoplastic nanofibers as an attractive platform for on-demand drug delivery.

Synthesis of gold nanostructures using glycine as the reducing agent.

Biological synthesis of gold nanostructures could potentially offer an environmentally friendly alternative to traditional chemical synthetic methods. During the last decades, various biomolecules, including amino acids, have been successfully used as reducing and capping agents to synthesize multi-shaped gold nanostructures. A grand challenge in this field is to increase our ability to control the size and shape of gold nanostructures formed precisely by systematic synthetic approaches based on the understanding of the mechanism for structural determination. In this study, using glycine as the model amino acid and chloroaurate (AuCl4 -) ions as the precursor solution, we report the finding that the shape of the gold nanostructures synthesized showed a strong correlation with the speciation of gold complexes determined by the pH, precursor concentration and chloride concentration of the solvent system. The gold chloro-hydroxy speciation [AuClx(OH)4-x]- (with x = 0-4) influenced the shape of the gold nanostructures formed, with gold nanoplatelets, nanotriangles, nanokites and nanoribbons observed at x = 4, 3, 2 and 1, respectively, and spherical nanoparticles observed at x = 0. Glycine was found to play a role as a reducing agent, but no significant effect on the morphology was observed, indicating the dominance of gold chloro-hydroxy speciation in the structural formation. These results collectively provide synthetic considerations to systematically synthesize non-spherical to spherical biosynthesized gold nanostructures by controlling the speciation of [AuClx(OH)4-x]-.

Controlled growth of gold nanocrystals on biogenic As-S nanotubes by galvanic displacement.

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques while alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Here, gold (Au) nanocrystals were grown on the surface of the microbiologically formed As-S nanotubes through the process of galvanic displacement. The size and organization of the synthesized Au nanocrystals were affected by the pH dependent speciation of HAuCl4 precursors as well as the initial ratio of As-S/HAuCl4. We found that as pH increased, the Au nanocrystals grown on As-S nanotubes had smaller sizes but were more likely to assemble in one-dimension along the nanotubes. At a proper initial ratio of As-S/HAuCl4, Au nanotubes were formed at pH 6.0. The mechanism of Au nanostructures formation and the synthesis process at different pHs were proposed. The resulting Au nanoparticle/As-S nanotube and Au nanotube/As-S nanotube hetero-structures may provide important properties to be used for novel nano-electronic devices.

Synthesis of hierarchical MoO2/MoS2 nanofibers for electrocatalytic hydrogen evolution.

Perpendicularly attached MoS2 nanosheets on MoO2 conductive nanofibers were synthesized by combining electrospinning, calcination, and sulfurization processes. Compared to randomly stacked MoS2 nanosheets on MoO2 nanofiber, they show greater hydrogen evolution reaction (HER) performance (i.e., onset potential of -180 mV versus normal hydrogen electrode with the Tafel slope of 59 mV dec-1). HER performance decreases with increasing MoS2 nanocrystal size.

Viral-templated gold/polypyrrole nanopeapods for an ammonia gas sensor.

One-dimensional gold/polypyrrole (Au/PPy) nanopeapods were fabricated using a viral template: M13 bacteriophage. The genetically modified filamentous virus displayed gold-binding peptides along its length, allowing selective attachment of gold nanoparticles (Au NPs) under ambient conditions. A PPy shell was electropolymerized on the viral-templated Au NP chains forming nanopeapod structures. The PPy shell morphology and thickness were controlled through electrodeposition potential and time, resulting in an ultra-thin conductive polymer shell of 17.4 ± 3.3 nm. A post-electrodeposition acid treatment was used to modify the electrical properties of these hybrid materials. The electrical resistance of the nanopeapods was monitored at each assembly step. Chemiresistive ammonia (NH3) gas sensors were developed from networks of the hybrid Au/PPy nanostructures. Room temperature sensing performance was evaluated from 5 to 50 ppmv and a mixture of reversible and irreversible chemiresistive behavior was observed. A sensitivity of 0.30%/ppmv was found for NH3 concentrations of 10 ppmv or less, and a lowest detection limit (LDL) of 0.007 ppmv was calculated. Furthermore, acid-treated devices exhibited an enhanced sensitivity of 1.26%/ppmv within the same concentration range and a calculated LDL of 0.005 ppmv.

Synthesis of gold structures by gold-binding peptide governed by concentration of gold ion and peptide.

Although biological synthesis methods for the production of gold structures by microorganisms, plant extracts, proteins, and peptide have recently been introduced, there have been few reports pertaining to controlling their size and morphology. The gold ion and peptide concentrations affected on the size and uniformity of gold plates by a gold-binding peptide Midas-11. The higher concentration of gold ions produced a larger size of gold structures reached 125.5 µm, but an increased amount of Midas-11 produced a smaller size of gold platelets and increased the yield percentage of polygonal gold particles rather than platelets. The mechanisms governing factors controlling the production of gold structures were primarily related to nucleation and growth. These results indicate that the synthesis of gold architectures can be controlled by newly isolated and substituted peptides under different reaction conditions.

Thermochemical hydrogen sensor based on chalcogenide nanowire arrays.

The hydrogen gas-sensing properties have been investigated of two types of thermochemical hydrogen (TCH) sensors composed of thermoelectric layers based on chalcogenide nanowire arrays and anodic aluminum oxide (AAO) templates. The monomorphic-type TCH sensor, which had only Bi2Te3 nanowire arrays, showed an output signal of 23.7 µV in response to 5 vol% hydrogen gas at room temperature, whereas an output signal of 215 µV was obtained from an n-p junction-type TCH sensor made of connected Bi2Te3 and Sb2Te3 nanowire arrays in an AAO template. Despite its small deposition area, the output signal of the n-p sensor was more than nine times that of the monomorphic sensor. This observation can be explained by the difference in electrical connections (parallel and serial conversions) in the TCH sensor between each type of nanowire array. Also, our n-p sensor had a wide detection range for hydrogen gas (from 400 ppm to 45 vol%) and a fast response time of 1.3 s at room temperature without requiring external power.

Tailored synthesis of photoactive TiO 2 nanofibers and Au/TiO 2 nanofiber composites: structure and reactivity optimization for water treatment applications.

Titanium dioxide (TiO2) nanofibers with tailored structure and composition were synthesized by electrospinning to optimize photocatalytic treatment efficiency. Nanofibers of controlled diameter (30-210 nm), crystal structure (anatase, rutile, mixed phases), and grain size (20-50 nm) were developed along with composite nanofibers with either surface-deposited or bulk-integrated Au nanoparticle cocatalysts. Their reactivity was then examined in batch suspensions toward model (phenol) and emerging (pharmaceuticals, personal care products) pollutants across various water qualities. Optimized TiO2 nanofibers meet or exceed the performance of traditional nanoparticulate photocatalysts (e.g., Aeroxide P25) with the greatest reactivity enhancements arising from (i) decreasing diameter (i.e., increasing surface area), (ii) mixed phase composition [74/26 (±0.5) % anatase/rutile], and (iii) small amounts (1.5 wt %) of surface-deposited, more so than bulk-integrated, Au nanoparticles. Surface Au deposition consistently enhanced photoactivity by 5- to 10-fold across our micropollutant suite independent of their solution concentration, behavior that we attribute to higher photocatalytic efficiency from improved charge separation. However, the practical value of Au/TiO2 nanofibers was limited by their greater degree of inhibition by solution-phase radical scavengers and higher rate of reactivity loss from surface fouling in nonidealized matrixes (e.g., partially treated surface water). Ultimately, unmodified TiO2 nanofibers appear most promising for use as reactive filtration materials because their performance was less influenced by water quality, although future efforts must increase the strength of TiO2 nanofiber mats to realize such applications.

Highly sensitive hydrogen sulfide (H2S) gas sensors from viral-templated nanocrystalline gold nanowires.

A facile, site-specific viral-templated assembly method was used to fabricate sensitive hydrogen sulfide (H2S) gas sensors at room temperature. A gold-binding M13 bacteriophage served to organize gold nanoparticles into linear arrays which were used as seeds for subsequent nanowire formation through electroless deposition. Nanowire widths and densities within the sensors were modified by electroless deposition time and phage concentration, respectively, to tune device resistance. Chemiresistive H2S gas sensors with superior room temperature sensing performance were produced with sensitivity of 654%/ppm(v), theoretical lowest detection limit of 2 ppb(v), and 70% recovery within 9 min for 0.025 ppm(v). The role of the viral template and associated gold-binding peptide was elucidated by removing organics using a short O2 plasma treatment followed by an ethanol dip. The template and gold-binding peptide were crucial to electrical and sensor performance. Without surface organics, the resistance fell by several orders of magnitude, the sensitivity dropped by more than a factor of 100 to 6%/ppm(v), the lower limit of detection increased, and no recovery was detected with dry air flow. Viral templates provide a novel, alternative fabrication route for highly sensitive, nanostructured H2S gas sensors.

Polyaniline/poly(ε-caprolactone) composite electrospun nanofiber-based gas sensors: optimization of sensing properties by dopants and doping concentration.

Electrospinning was utilized to synthesize a polyaniline (PANI)/poly(ε-caprolactone) (PCL) composite in the form of nanofibers to examine its gas sensing performance. Electrical conductivity of the composite nanofibers was tailored by secondary doping with protonic acids including hydrochloride (HCl) or camphorsulfonic acid (HCSA). FT-IR and diffuse reflectance UV-vis spectroscopy were utilized to examine doping-dependent changes in the chemical structure and the protonation state of the nanofibers, respectively. The oxidation and protonation state of the composite nanofibers were shown to strongly depend on the doping agent and duration, demonstrating a simple way of controlling the electrical conductivity of the composite. PANI/PCL electrospun nanofibers having various electrical conductivities via varying dopants and doping concentrations, were configured to chemiresistors for sensing various analytes, including water vapor, NH3, and NO2. Secondary doping with Cl(-) and CSA differentially affected sensing behaviors by having distinctive optimal sensitivities. Biphasic sensitivity with respect to electrical conductivity was observed, demonstrating a facile method to enhance gas sensitivity by optimizing secondary doping. A balance between Debye length of the nanofibers and overall charge conduction may play an important role for modulating such an optimal sensitivity.

Achieving One Part Per Billion Hydrogen Sulfide (H2S) Level Detection through Optimizing Composition and Crystallinity of Gold-Decorated Tungsten Trioxide (Au-WO3) Nanofibers.

As a common environmental pollutant and an important breath biomarker for several diseases, it is essential to develop a hydrogen sulfide gas sensor with a low-ppb level detection limit to prevent harmful gas exposure and allow early diagnoses of diseases in low-resource settings. Gold doped/decorated tungsten trioxide (Au-WO3) nanofibers with various compositions and crystallinities were synthesized to optimize H2S-sensing performance. Systematically experimental results demonstrated the ability to detect 1 ppb H2S with a response value (Rair/Rgas) of 2.01 using a 5 at % Au-WO3 nanofibers with average grain sizes of around 15 nm. Additionally, energy barrier difference of sensing materials in air and nitrogen (ΔEb) and power law exponent (n) were determined to be 0.36 eV and 0.7, respectively, at 450 °C indicating that O- is predominately ionic oxygen species and adsorption of O- significantly altered the Schottky barrier between the grain. Such quantitative analysis provides a comprehensive understanding of H2S detection mechanism.

Fabrication of DNA-templated Te and Bi2Te3 nanowires by galvanic displacement.

This paper demonstrates the use of galvanic displacement to form continuous tellurium-based nanowires on DNA templates, enabling the conversion of metals, which can be deposited site-specifically, into other materials needed for device fabrication. Specifically, galvanic displacement reaction of copper and nickel nanowires is used to fabricate tellurium and bismuth telluride nanowires on λ-DNA templates. The method is simple, rapid, highly selective, and applicable to a number of different materials. In this study, continuous Ni and Cu nanowires are formed on DNA templates by seeding with Ag followed by electroless plating of the desired metal. These wires are then displaced by a galvanic displacement reaction where either Te or Bi2Te3 is deposited from an acidic solution containing HTeO2(+) ions or a combination of HTeO2(+) and Bi(3+) ions, and the metal wire is simultaneously dissolved due to oxidation. Both tellurium and bismuth telluride wires can be formed from nickel templates. In contrast, copper templates only form tellurium nanowires under the conditions considered. Therefore, the composition of the metal being displaced can be used to influence the chemistry of the resulting nanowire. Galvanic displacement of metals deposited on DNA templates has the potential to enable site-specific fabrication of a variety of materials and, thereby, make an important contribution to the advancement of useful devices via self-assembled nanotemplates.

Metal nanoparticles and DNA co-functionalized single-walled carbon nanotube gas sensors.

Metal/DNA/SWNT hybrid nanostructure-based gas sensor arrays were fabricated by means of ink jet printing of metal ion chelated DNA/SWNTs on microfabricated electrodes, followed by electroless deposition to reduce metal ions to metal. DNA served as a dispersing agent to effectively solubilize pristine SWNTs in water and as metal ion chelating centers for the formation of nanoparticles. Noble metals including palladium, platinum, and gold were used because the high binding affinity toward specific analytes enhances the selectivity and sensitivity. The sensitivity and selectivity of the gas sensors toward various gases such as H2, H2S, NH3, and NO2 were determined at room temperature. Sensing results indicated the enhancement of the sensitivity and selectivity toward certain analytes by functionalizing with different metal nanoparticles (e.g., Pd/DNA/SWNTs for H2 and H2S). The combined responses give a unique pattern or signature for each analyte by which the system can identify and quantify an individual gas.

Simple fabrication of an electrospun polystyrene microfiber filter that meets N95 filtering facepiece respirator filtration and breathability standards.

During the global spread of COVID-19, high demand and limited availability of melt-blown filtration material led to a manufacturing backlog of N95 Filtering Facepiece Respirators (FFRs). This shortfall prompted the search for alternative filter materials that could be quickly mass produced while meeting N95 FFR filtration and breathability performance standards. Here, an unsupported, nonwoven layer of uncharged polystyrene (PS) microfibers was produced via electrospinning that achieves N95 performance standards based on physical parameters (e.g., filter thickness) alone. PS microfibers 3-6 µm in diameter and deposited in an ~5 mm thick filter layer are favorable for use in FFRs, achieving high filtration efficiencies (≥97.5%) and low pressure drops (≤15 mm H2O). The PS microfiber filter demonstrates durability upon disinfection with hydroxyl radicals (•OH), maintaining high filtration efficiencies and low pressure drops over six rounds of disinfection. Additionally, the PS microfibers exhibit antibacterial activity (1-log removal of E. coli) and can be modified readily through integration of silver nanoparticles (AgNPs) during electrospinning to enhance their activity (≥3-log removal at 25 wt% AgNP integration). Because of their tunable performance, potential reusability with disinfection, and antimicrobial properties, these electrospun PS microfibers may represent a suitable, alternative filter material for use in N95 FFRs.

Single-walled carbon nanotubes based chemicapacitive sensors.

Carboxylated single-walled carbon nanotubes (SWNTs) based chemicapacitive gas sensors were fabricated by AC dielectrophoretically aligning SWNTs across microfabricated gold electrodes with controlled density/device resistance. Two different sensing configurations (i.e., horizontal/in-plane and vertical/out-of-plane) were utilized to compare their sensing performance. Upon exposure to water vapor at room temperature, the response (R = [(C--C0)/C0] x 100%) increased with an increase in water vapor concentration similar to that of resistance response. In horizontal configuration, the response was increased with an increase in device resistance which might be attributed to preferentially alignment of semiconducting SWNTs during initial phase of alignment. However, the response was independent of device resistance in vertical/out-of-plane configuration which indicated that the sensing mechanism is based on the change of dielectric constant of gate and atmosphere.

Non-destructive characterization of bone mineral content by machine learning-assisted electrochemical impedance spectroscopy.

Continuous quantitative monitoring of the change in mineral content during the bone healing process is crucial for efficient clinical treatment. Current radiography-based modalities, however, pose various technological, medical, and economical challenges such as low sensitivity, radiation exposure risk, and high cost/instrument accessibility. In this regard, an analytical approach utilizing electrochemical impedance spectroscopy (EIS) assisted by machine learning algorithms is developed to quantitatively characterize the physico-electrochemical properties of the bone, in response to the changes in the bone mineral contents. The system is designed and validated following the process of impedance data measurement, equivalent circuit model designing, machine learning algorithm optimization, and data training and testing. Overall, the systematic machine learning-based classification utilizing the combination of EIS measurements and electrical circuit modeling offers a means to accurately monitor the status of the bone healing process.

Nitrous Oxide Is No Laughing Matter: A Historical Review of Nitrous Oxide Gas-Sensing Capabilities Highlighting the Need for Further Exploration.

Nitrous oxide (N2O), also known as laughing gas, is arguably one of the most detrimental greenhouse gases while concurrently being overlooked by the public. Specifically, N2O is ∼300 times more damaging than its better-known counterpart carbon dioxide (CO2) and has a longer-lived lifetime in the atmosphere than CO2. There exist both natural and anthropogenic sources of N2O, and thus, for a better understanding of sources, capture, and decomposition, it is pivotal to identify N2O within the nitrogen biosphere. This review covers the past and current low-cost N2O gas-sensing technologies, focusing specifically on low-cost metal oxide semiconductors (MOSs), chemiresistive and electrochemical sensors that can provide spatial and temporal monitoring of N2O emissions from various sources. Additionally, compositional modifications to MOsS using metal-organic frameworks (MOFs) are discussed, potentially facilitating new awareness and efforts for increased sensing performance and functionality in N2O detection.

Multiplexed Anodic Stripping Voltammetry Detection of Heavy Metals in Water Using Nanocomposites Modified Screen-Printed Electrodes Integrated With a 3D-Printed Flow Cell.

In this study, we present multiplexed anodic stripping voltammetry (ASV) detection of heavy metal ions (HMIs)-As(III), Cd(II), and Pb(II)-using a homemade electrochemical cell consisting of dual working, reference and counter screen-printed electrodes (SPE) on polyimide substrate integrated with a 3D-printed flow cell. Working and counter electrodes were fabricated by the screen-printing of graphite paste while the Ag/AgCl paste was screen-printed as a reference electrode (Ag/AgCl quasi-reference electrode). The working electrodes were modified with (BiO)2CO3-reduced graphene oxide (rGO)-Nafion [(BiO)2CO3-rGO-Nafion] and Fe3O4 magnetic nanoparticles (Fe3O4MNPs) decorated Au nanoparticles (AuNPs)-ionic liquid (IL) (Fe3O4-Au-IL) nanocomposites separately to enhance HMIs sensing. Electrochemical detection was achieved using square wave ASV technique. The desired structure of the flow electrochemical cell was optimized by the computational fluid dynamic (CFD). Different experimental parameters for stripping analysis of HMIs were optimized including deposition time, deposition potential and flow rate. The linear range of calibration curves with the sensing nanocomposites modified SPE for the three metal ions was from 0-50 µg/L. The limits of detection (S/N = 3) were estimated to be 2.4 µg/L for As(III), 1.2 µg/L for Pb(II) and 0.8 µg/L for Cd(II). Furthermore, the homemade flow anodic stripping sensor platform was used to detect HMIs in simulated river water with a 95-101% recovery, indicating high selectivity and accuracy and great potential for applicability even in complex matrices.

Recent advances and remaining barriers to the development of electrospun nanofiber and nanofiber composites for point-of-use and point-of-entry water treatment systems.

In this review, we focus on electrospun nanofibers as a promising material alternative for the niche application of decentralized, point-of-use (POU) and point-of-entry (POE) water treatment systems. We focus our review on prior work with various formulations of electrospun materials, including nanofibers of carbon, pure metal oxides, functionalized polymers, and polymer-metal oxide composites, that exhibit analogous performance to media (e.g., activated carbon, ion exchange resins) commonly used in commercially available, certified POU/POE devices for contaminants including organic pollutants, metals (e.g., lead) and persistent oxyanions (e.g., nitrate). We then analyze the relevant strengths and remaining research and development opportunities of the relevant literature based on an evaluation framework that considers (i) performance comparison to commercial analogs; (ii) appropriate pollutant targets for POU/POE applications; (iii) testing in flow-through systems consistent with POU/POE applications; (iv) consideration of water quality effects; and (v) evaluation of material strength and longevity. We also identify several emerging issues in decentralized water treatment where nanofiber-based POU/POE devices could help meet existing needs including their use for treatment of uranium, disinfection, and in electrochemical treatment systems. To date, research has demonstrated promising material performance toward relevant targets for POU/POE applications, using appropriate aquatic matrices and considering material stability. To fully realize their promise as an emerging treatment technology, our analysis of the available literature reveals the need for more work that benchmarks nanofiber performance against established commercial analogs, as well as fabrication and performance validation at scales and under conditions simulating POU/POE water treatment.

Effects of NH4 +/citrate complexing agent ratio on Ni-Mo and Ni-Mo-O electrodeposits from ammonium citrate baths.

To understand the effect of complexing agents (i.e., ammonium and citrate) in nickel-molybdenum electrodeposition, calculation of the concentration of various Ni and Mo species as a function of pH and initial concentration of metal ions and complexing agents was performed. In addition, linear sweep voltammetry and Hull cell experiments were systematically investigated to understand the effect of current density and ammonium-to-citrate ratio to film compositions, morphology, and crystallinity. The results indicated that Ni(NH3)3 2+ played a critical role in induced co-deposition mechanism of Ni-Mo alloys, which involved the reduced Ni and absorbed H atoms. Microstructure analysis of deposits indicated that the transition from smooth laminarly grown amorphous Ni-Mo-O composites to columnar and nanocrystalline metallic Ni-Mo alloys with a globular structure as the ammonium-to-citrate molar ratio increases. The highest Mo content of alloys was as high as 19 at%, and up to 70 at% O was present in the composites.