Bi, Fe, and Ti ternary co-doped ZrO2 nanocomposites as a mass spectrometry matrix for the determination of bisphenol A and tetrabromobisphenol A in tea.

Bi, Fe, and Ti ternary co-doped ZrO2 (BFT-ZrO2) nanocomposites have been prepared by a sol-gel process and used as both adsorbent and matrix for the enrichment and determination of small molecules by surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF MS). The BFT-ZrO2 nanocomposites not only can selectively enrich a wide variety of low-mass toxic pollutants but can also be used as an excellent matrix to enhance the laser desorption/ionization efficiency with low background noise and uniform co-crystalline film. Low limits of detection (LODs) (0.1 pg mL-1 for bisphenol A (BPA), 2 pg mL-1 for tetrabromobisphenol A (TBBPA), 0.1 pg mL-1 for alizarin (AZ), 0.001 pg mL-1for bisphenol S (BPS), 0.01 pg mL-1 for indigo blue (ID), 0.01 pg mL-1 for pentachlorophenol (PCP), 100 pg mL-1 for estradiol (E2), 0.001 pg mL-1 for cetyltrimethylammonium bromide (CTAB), 0.1 pg mL-1 for crystal violet (CV), 1 pg mL-1 for malachite green (MG), 0.01 pg mL-1 for rhodamine B (RhB), and 0.01 pg mL-1 for perfluorooctane sulfonate (PFOS) were achieved. The relative standard deviations (RSDs) of shot-to-shot are 9.4-24% and of sample-to-sample 5.2-17%. The BFT-ZrO2 matrix was successfully applied to the determination of TBBPA and BPA in tea samples. This method shows a new strategy for determination of toxic compounds in tea. Graphical abstract.

Reduced titania nanosheets as an effective visible-light germicide.

Two-dimensional reduced titania nanosheets (RTNs), synthesized by a solvothermal method, reveal significant visible light-activated germicidal activity. XRD, XPS, EPR, TEM and Raman show successful reduction of anatase TiO2, resulting in Ti3+ formation as well as an increase in the concentration of {001} facets. The RTNs possess a bandgap energy of approximately 2.86 eV, and demonstrate strong absorption over the visible spectrum. Under simulated solar light (λ = 320-780 nm, 70 mW cm-2) the RTNs are found to completely inactivate Escherichia coli bacteria within 1 h. Our study indicates the RTNs have significant potential for ameliorating antibiotic-resistant bacteria in clinical settings under ambient lighting conditions.

Cobalt-doped nanoporous carbon as SALDI-TOF-MS adsorbent and matrix for quantification of cetyltrimethylammonium bromide, Rhodamine B and Malachite Green at sub-ppt levels.

Cobalt-doped nanoporous carbon (Co-NPC) with dodecahedral shape was pyrolytically synthesized and applied as a sorbent and matrix for the enrichment and analysis of small molecules by surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS). Extremely low detection limits were accomplished for cetyltrimethylammonium bromide (1 fg·mL-1), and Rhodamine B (1 fg·mL-1) in water, and Malachite Green and its metabolite in fish blood and fish extracts (pg·mL-1 concentrations). Graphical abstract Schematic representation of cobalt-doped nanoporous carbons (Co-NPCs) applied as SALDI matrix for analysis of toxic contaminants in fish and receipt papers. The Co-NPCs have a high desorption/ionization efficiency and low limit of detection.

Eu,Sm,Mn-Doped CaS Nanoparticles with 59.3% Upconversion-Luminescence Quantum Yield: Enabling Ultrasensitive and Facile Smartphone-Based Sulfite Detection.

Eu,Sm,Mn-doped CaS (ESM-CaS) nanoparticles demonstrate a remarkable upconversion luminescence (UCL) efficiency with a quantum yield of nearly 60%, enabling many new applications and devices. We describe an ESM-CaS nanoparticle-based paper test strip for one-shot quantitative measurement of sulfite concentration using a smartphone-based reader. The integrated UCL-based sulfite detection system features high sensitivity and facile operation without the need for separation and pretreatment. Moreover, the design principles are general in nature and so can be tailored for the detection and quantification of a variety of other analytes.

Novel Olefin-Linked Covalent Organic Framework with Multifunctional Group Modification for the Fluorescence/Smartphone Detection of Uranyl Ion.

Monitoring and purification of uranium contamination are of great importance for the rational utilization of uranium resources and maintaining the environment. In this work, an olefin-linked covalent organic framework (GC-TFPB) and its amidoxime-modified product (GC-TFPB-AO) are synthesized with 3-cyano-4,6-dimethyl-2-hydroxypyridine (GC) and 1,3,5-tris(4-formylphenyl) benzene (TFPB) by Knoevenagel condensation. GC-TFPB-AO results in specificity for rapid fluorescent/smartphone uranyl ion (UO22+) detection based on the synergistic effect of multifunctional groups (amidoxime, pyridine, and hydroxyl groups). GC-TFPB-AO features a rapid and highly sensitive detection and adsorption of UO22+ with a detection limit of 21.25 nM. In addition, it has a good recovery (100-111%) for fluorescence detection in real samples, demonstrating an excellent potential of predesigned olefin-linked fluorescent COFs in nuclear contaminated wastewater detection and removal.

A PEDOT enhanced covalent organic framework (COF) fluorescent probe for in vivo detection and imaging of Fe3.

Simple and accurate in vivo monitoring of Fe3+ is essential for gaining a better understanding of its role in physiological and pathological processes. A novel fluorescent probe was synthesized via in situ solid-state polymerization of 3,4-ethylenedioxythiophene (PEDOT) in the pore channels of a covalent organic framework (COF). The PEDOT@COF fluorescent probe exhibited an absolute quantum yield (QY) 3 times higher than COF. In the presence of Fe3+ the PEDOT@COF 475 nm fluorescence emission, 365 nm excitation, is quenched within 180 s. Fluorescence quenching is linear with Fe3+ in the concentration range of 0-960 µM, with a detection limit of 0.82 µM. The fluorescence quenching mechanism was attributed to inner filter effect (IEF), photoinduced electron transfer (PET) and static quenching (SQE) between PEDOT@COF and Fe3+. A paper strip-based detector was designed to facilitate practical applicability, and the PEDOT@COF probe successfully applied to fluorescence imaging of Fe3+ levels in vivo. This work details a tool of great promise for enabling detailed investigations into the role of Fe3+ in physiological and pathological diseases.

Eu3+-Doped Anionic Zinc-Based Organic Framework Ratio Fluorescence Sensing Platform: Supersensitive Visual Identification of Prescription Drugs.

Advanced techniques for both environmental and biological prescription drug monitoring are of ongoing interest. In this work, a fluorescent sensor based on an Eu3+-doped anionic zinc-based metal-organic framework (Eu3+@Zn-MOF) was constructed for rapid visual analysis of the prescription drug molecule demecycline (DEM), achieving both high sensitivity and selectivity. The ligand 2-amino-[1,1'-biphenyl]-4,4'-dicarboxylic acid (bpdc-NH2) not only provides stable cyan fluorescence (467 nm) for the framework through intramolecular charge transfer of bpdc-NH2 infinitesimal disturbanced by Zn2+ but also chelates Eu3+, resulting in red (617 nm) fluorescence. Through the synergy of photoinduced electron transfer and the antenna effect, a bidirectional response to DEM is achieved, enabling concentration quantification. The Eu3+@Zn-MOF platform exhibits a wide linear range (0.25-2.5 µM) to DEM and a detection limit (LOD) of 10.9 nM. Further, we integrated the DEM sensing platform into a paper-based system and utilized a smartphone for the visual detection of DEM in water samples and milk products, demonstrating the potential for large-scale, low-cost utilization of the technology.

Tracking of Intestinal Probiotics In Vivo by NIR-IIb Fluorescence Imaging.

The ability to accurately characterize microorganism distribution in the intestinal tract is helpful for understanding intrinsic mechanisms. Within the intestine, traditional optical probes used for microorganism labeling commonly suffer from a low imaging penetration depth and poor resolution. We report a novel observation tool useful for microbial research by labeling near-infrared-IIb (NIR-IIb, 1500-1700 nm) lanthanide nanomaterials NaGdF4:Yb3+,Er3+@NaGdF4,Nd3+ (Er@Nd NPs) onto the surface of Lactobacillus bulgaricus (L. bulgaricus) via EDC-NHS chemistry. We monitor microorganisms in tissue by two-photon excitation (TPE) microscopy and in vivo with NIR-IIb imaging. This dual-technique approach offers great potential for determining the distribution of transplanted bacteria in the intestinal tract with a higher spatiotemporal resolution.

Femtosecond to millisecond studies of electron transfer processes in a donor-(π-spacer)-acceptor series of organic dyes for solar cells interacting with titania nanoparticles and ordered nanotube array films.

Time-resolved emission and absorption spectroscopy are used to study the photoinduced dynamics of forward and back electron transfer processes taking place between a recently synthesized series of donor-(π-spacer)-acceptor organic dyes and semiconductor films. Results are obtained for vertically oriented titania nanotube arrays (inner diameters 36 nm and 70 nm), standard titania nanoparticles (25 nm diameter) and, as a reference, alumina nanoparticle (13 nm diameter) films. The studied dyes contain a triphenylamine group as an electron donor, cyanoacrylic acid part as an electron acceptor, and differ by the substituents in a spacer group that causes a shift of its absorption spectra. Despite a red-shift of the dye absorption band resulting in an improved response to the solar spectrum, smaller electron injection rates and smaller extinction coefficients result in reduced dye sensitized solar cell (DSSC) conversion efficiencies. For the most efficient dye, TPC1, electron injection from the hot locally excited state to titania on a time scale of about 100 fs is suggested, while from the relaxed charge transfer state it proceeds in a non-exponential way with time constants from 1 ps to 50 ps. Our results imply that the latter process involves the trap states below the conduction band edge (or the sub-bandgap tail of the acceptor states), localized close to the dye radical cation, and is accompanied by fast electron recombination to the parent dye's ground state. This process should limit the efficiency of DSSCs made using these types of organic dyes. The residual, slower recombination can be described by a stretched exponential decay with a characteristic time of 0.5 µs and a dispersion parameter of 0.33. Both the electron injection and back electron transfer dynamics are similar in titania nanoparticles and nanotubes. Variations between the two film types are only found in the time resolved emission transients, which are explained in terms of the difference in local electric fields affecting the position of the emission bands.

Nanostructured WO3/BiVO4 heterojunction films for efficient photoelectrochemical water splitting.

We report on a novel heterojunction WO(3)/BiVO(4) photoanode for photoelectrochemical water splitting. The heterojunction films are prepared by solvothermal deposition of a WO(3) nanorod-array film onto fluorine-doped tin oxide (FTO) coated glass, with subsequent deposition of a low bandgap, 2.4 eV, visible light responding BiVO(4) layer by spin-coating. The heterojunction structure offers enhanced photoconversion efficiency and increased photocorrosion stability. Compared to planar WO(3)/BiVO(4) heterojunction films, the nanorod-array films show significantly improved photoelectrochemical properties due, we believe, to the high surface area and improved separation of the photogenerated charge at the WO(3)/BiVO(4) interface. Synthesis details are discussed, with film morphologies and structures characterized by field emission scanning electron microscopy and X-ray diffraction.

Vertically aligned WO3 nanowire arrays grown directly on transparent conducting oxide coated glass: synthesis and photoelectrochemical properties.

Photocorrosion stable WO(3) nanowire arrays are synthesized by a solvothermal technique on fluorine-doped tin oxide coated glass. WO(3) morphologies of hexagonal and monoclinic structure, ranging from nanowire to nanoflake arrays, are tailored by adjusting solution composition with growth along the (001) direction. Photoelectrochemical measurements of illustrative films show incident photon-to-current conversion efficiencies higher than 60% at 400 nm with a photocurrent of 1.43 mA/cm(2) under AM 1.5G illumination. Our solvothermal film growth technique offers an exciting opportunity for growth of one-dimensional metal oxide nanostructures with practical application in photoelectrochemical energy conversion.

Rapid charge transport in dye-sensitized solar cells made from vertically aligned single-crystal rutile TiO(2) nanowires.

A rapid solvothermal approach was used to synthesize aligned 1D single-crystal rutile TiO(2) nanowire (NW) arrays on transparent conducting substrates as electrodes for dye-sensitized solar cells. The NW arrays showed a more than 200 times faster charge transport and a factor four lower defect state density than conventional rutile nanoparticle films.

Lanthanide/Cu2-xSe Nanoparticles for Bacteria-Activated NIR-II Fluorescence Imaging of Infection.

A material system enabling specific NIR-II fluorescence imaging of Gram-positive bacteria is described. The material system is based on the electrostatic binding of Cu2-xSe and vancomycin-modified NaGdF4:Nd,Yb@NaGdF4 downconversion nanoparticles (DCNPs), the fluorescence of which is weak owing to the spectral overlap of Cu2-xSe absorption with the DCNP NIR emission. The presence of Gram-positive bacteria precisely disconnects the bond between vancomycin-modified DCNPs and Cu2-xSe, thus enabling a strong fluorescent signal. In vivo studies show that the material system can be specifically activated at the site of Gram-positive bacterial infection but is essentially nonfluorescent in the area of Gram-negative bacterial infection.

An Ag2S@ZIF-Van nanosystem for NIR-II imaging of bacterial-induced inflammation and treatment of wound bacterial infection.

Bacterial diseases pose a serious threat to human health. Continued development of precise diagnostic methods and synergistic therapy techniques for combating bacteria are needed. Herein a hybrid nanosystem (Ag2S@ZIF-Van NS) was constructed by one-step self-assembly of Zn2+, vancomycin (Van) and Ag2S quantum dots (QDs). The nanosystem possesses excellent second near-infrared transparency window (NIR-II) fluorescence properties (∼1200 nm emission wavelength), good photothermal conversion properties, and biocompatibility. The material system enables precise, targeted NIR-II fluorescent imaging of bacterial inflammation in vivo as well as promoting anti-bacterial and wound healing effects.

Theory, instrumentation and applications of magnetoelastic resonance sensors: a review.

Thick-film magnetoelastic sensors vibrate mechanically in response to a time varying magnetic excitation field. The mechanical vibrations of the magnetostrictive magnetoelastic material launch, in turn, a magnetic field by which the sensor can be monitored. Magnetic field telemetry enables contact-less, remote-query operation that has enabled many practical uses of the sensor platform. This paper builds upon a review paper we published in Sensors in 2002 (Grimes, C.A.; et al. Sensors 2002, 2, 294-313), presenting a comprehensive review on the theory, operating principles, instrumentation and key applications of magnetoelastic sensing technology.

High-efficiency Förster resonance energy transfer in solid-state dye sensitized solar cells.

Solid-state dye-sensitized solar cells (SS-DSCs) offer the potential to make low cost solar power a reality, however their photoconversion efficiency must first be increased. The dyes used are commonly narrow band with high absorption coefficients, while conventional photovoltaic operation requires proper band edge alignment significantly limiting the dyes and charge transporting materials that can be used in combination. We demonstrate a significant enhancement in the light harvesting and photocurrent generation of SS-DSCs due to Förster resonance energy transfer (FRET). TiO(2) nanotube array films are sensitized with red/near IR absorbing SQ-1 acceptor dye, subsequently intercalated with Spiro-OMeTAD blended with a visible light absorbing DCM-pyran donor dye. The calculated Förster radius is 6.1 nm. The donor molecules contribute a FRET-based maximum IPCE of 25% with a corresponding excitation transfer efficiency of approximately 67.5%.

Ta3N5 nanotube arrays for visible light water photoelectrolysis.

Tantalum nitride (Ta3N5) has a band gap of approximately 2.07 eV, suitable for collecting more than 45% of the incident solar spectrum energy. We describe a simple method for scale fabrication of highly oriented Ta3N5 nanotube array films, by anodization of tantalum foil to achieve vertically oriented tantalum oxide nanotube arrays followed by a 700 degrees C ammonia anneal for sample crystallization and nitridation. The thin walled amorphous nanotube array structure enables transformation from tantalum oxide to Ta3N5 to occur at relatively low temperatures, while high-temperature annealing related structural aggregation that commonly occurs in particle films is avoided. In 1 M KOH solution, under AM 1.5 illumination with 0.5 V dc bias typical sample (nanotube length approximately 240 nm, wall thickness approximately 7 nm) visible light incident photon conversion efficiencies (IPCE) as high as 5.3% were obtained. The enhanced visible light activity in combination with the ordered one-dimensional nanoarchitecture makes Ta3N5 nanotube arrays films a promising candidate for visible light water photoelectrolysis.

Whole genome expression analysis reveals differential effects of TiO2 nanotubes on vascular cells.

The response of primary human endothelial (ECs) and vascular smooth muscle cells (VSMCs) to TiO2 nanotube arrays is studied through gene expression analysis. Microarrays revealed that nanotubes enhanced EC proliferation and motility, decreased VSMC proliferation, and decreased expression of molecules involved in inflammation and coagulation in both cell types. Networks generated from significantly affected genes suggest that cells may be sensing nanotopographical cues via pathways previously implicated in sensing shear stress.

Self-assembled TiO(2) nanotube arrays by anodization of titanium in diethylene glycol: approach to extended pore widening.

We report on the formation of titanium dioxide nanotube arrays having the largest known pore size, approximately 350 nm diameter. The nanotube arrays are synthesized by Ti foil anodization in a diethylene glycol electrolyte containing low (0.5-2%) concentrations of hydrofluoric acid. The large pore size nanotube arrays are achieved with extended anodization durations of approximately 120 h, with the anodization duration showing a more significant effect on pore diameter than the anodization voltage. It appears that the combined effects of hydrofluoric acid content and anodization duration determine the lateral etching rate of the nanotubes, leading to the larger pore size nanotubes.

Molecular design of near-IR harvesting unsymmetrical squaraine dyes.

The functionalized unsymmetrical benzothiazole squaraine organic sensitizers 5-carboxy-2-({3-[(3-hexylbenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (hereafter named as SK-11) and 5-carboxy-2-({3-[(3-hexyl-5-methoxybenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (coded as SK-12) are designed and developed to observe an intense and wider absorption band in the red/NIR wavelength region. DFT/TDDFT calculations have been performed on the two unsymmetrical squaraine sensitizers to gain insight into their electronic and optical properties. The utility of these dyes in solid state dye sensitized solar cells (SS-DSSCs) is demonstrated.