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.

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.

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.

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.

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.

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.

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.

Multicolor lanthanide-doped CaS and SrS near-infrared stimulated luminescent nanoparticles with bright emission: application in broad-spectrum lighting, information coding, and bio-imaging.

A series of lanthanide-doped CaS and SrS nanoparticles possessing bright fluorescence under near-infrared light (NIR) illumination and tunable emission colors are prepared and applied in light emitting, information coding, cell-labeling and in vivo imaging. The high fluorescence intensity and easily tunable emission wavelength under 980 nm light excitation make these multicolor alkaline earth sulfide nanoparticles (AES NPs) good in vivo biolabels for simultaneous differentiation of multiple organs, and other NIR-excitation-based applications.

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.

Two-dimensional TiO2 nanoflakes enable rapid SALDI-TOF-MS detection of toxic small molecules (dyes and their metabolites) in complex environments.

High surface area (136 m2 g-1) nanoporous two-dimensional TiO2 nanoflakes are applied as an adsorbent and meanwhile a matrix for toxic small molecule analysis using positive-ion surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS). The TiO2 nanoflakes enable one-step enrichment and analysis, greatly simplifying the analysis technique. Due to the high enrichment efficiency and low background noise, small molecule organic contaminants at ppt or even sub-ppt concentrations such as malachite green (10 pg/mL), leucomalachite green (10 pg/mL), cetyltrimethylammonium bromide (0.001 pg/mL), rhodamine B (0.001 pg/mL), and crystal violet (0.1 pg/mL) were detected. In addition, malachite green and its metabolite leucomalachite green at ng/mL concentrations were successfully detected from fish blood and fish extracts, and crystal violet and its homologues at ng/cm2 concentrations were detected from inks on thermal receipt papers obtained from local supermarket.

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.

The Biocompatibility of Nanoporous Acupuncture Needles.

We investigate the biocompatibility of a new class of acupuncture needles that possess a hierarchical nano/microscale porous surface topology, referred to as porous acupuncture needles (PAN). The PAN is synthesized via a facile electrochemical anodization technique by which a surface area approximately 20 times greater than a conventional acupuncture needle, of approximately the same diameter, is obtained. PAN biocompatibility is evaluated using a variety of standard tests, with results indicating that the PAN can safely be used within therapeutic practice.

Highly-luminescent Eu,Sm,Mn-doped CaS up/down conversion nano-particles: application to ultra-sensitive latent fingerprint detection and in vivo bioimaging.

Due to their unique properties, rare-earth doped upconversion luminescence (UCL) nanomaterials are of considerable scientific interest. Meanwhile, alkaline-earth sulfide materials based on a completely different electron trapping (ET) mechanism demonstrate extremely high UCL efficiencies, which are several dozens of times more than those of conventional fluoride UCL nanomaterials. However, the large particle size, easy hydrolysis, and difficulty in achieving uniform dispersion have precluded bioassay applications. Herein, we have synthesized super-bright Eu,Sm,Mn-doped CaS nanoparticles of ∼30 nm average particle size using a reverse microemulsion technique. The UCL quantum yield was up to nearly 60%. Modification of the nanoparticles with an organic layer allows their stable dispersion throughout aqueous solutions without significant loss of the fluorescence intensity. We demonstrate the application of the novel UCL materials to latent fingerprint detection, deep tissue imaging, and in vivo bioimaging.

Enhanced Therapeutic Treatment of Colorectal Cancer Using Surface-Modified Nanoporous Acupuncture Needles.

Acupuncture originated within the auspices of Oriental medicine, and today is used as an alternative method for treating various diseases and symptoms. The physiological mechanisms of acupuncture appear to involve the release of endogenous opiates and neurotransmitters, with the signals mediating through electrical stimulation of the central nervous system (CNS). Earlier we reported a nanoporous stainless steel acupuncture needle with enhanced therapeutic properties, evaluated by electrophysiological and behavioral responses in Sprague-Dawley (SD) rats. Herein, we investigate molecular changes in colorectal cancer (CRC) rats by acupuncture treatment using the nanoporous needles. Treatment at acupoint HT7 is found most effective at reducing average tumor size, ß-catenin expression levels, and the number of aberrant crypt foci in the colon endothelium. Surface modification of acupuncture needles further enhances the therapeutic effects of acupuncture treatment in CRC rats.

Hierarchical Micro/Nano-Porous Acupuncture Needles Offering Enhanced Therapeutic Properties.

Acupuncture as a therapeutic intervention has been widely used for treatment of many pathophysiological disorders. For achieving improved therapeutic effects, relatively thick acupuncture needles have been frequently used in clinical practice with, in turn, enhanced stimulation intensity. However due to the discomforting nature of the larger-diameter acupuncture needles there is considerable interest in developing advanced acupuncture therapeutical techniques that provide more comfort with improved efficacy. So motivated, we have developed a new class of acupuncture needles, porous acupuncture needles (PANs) with hierarchical micro/nano-scale conical pores upon the surface, fabricated via a simple and well known electrochemical process, with surface area approximately 20 times greater than conventional acupuncture needles. The performance of these high-surface-area PANs is evaluated by monitoring the electrophysiological and behavioral responses from the in vivo stimulation of Shenmen (HT7) points in Wistar rats, showing PANs to be more effective in controlling electrophysiological and behavioral responses than conventional acupuncture needles. Comparative analysis of cocaine induced locomotor activity using PANs and thick acupuncture needles shows enhanced performance of PANs with significantly less pain sensation. Our work offers a unique pathway for achieving a comfortable and improved acupuncture therapeutic effect.

Towards efficient visible-light active photocatalysts: CdS/Au sensitized TiO2 nanotube arrays.

A visible-light active photocatalyst, CdS/Au/TiO2 nanotube array (NTA) photoelectrode, was prepared by electrodeposition of Au nanoparticles onto TiO2 NTA with subsequent deposition of visible-light absorbable 2.4eV band-gap CdS quantum dots using successive ion layer adsorption and reaction (SILAR). The Au nanoparticles here act as electron sinks facilitating charge carrier separation. Under AM1.5G illumination a photoconversion efficiency of 4.06% was achieved for the CdS/Au/TiO2 NTA photoelectrode, suggesting the promise of the material architecture for achieving high-performance cost-effective materials.

Hybrid Cu x O-TiO2 Heterostructured Composites for Photocatalytic CO2 Reduction into Methane Using Solar Irradiation: Sunlight into Fuel.

Photocatalytic CO2 conversion to fuel offers an exciting prospect for solar energy storage and transportation thereof. Several photocatalysts have been employed for CO2 photoreduction; the challenge of realizing a low-cost, readily synthesized photocorrosion-stable photocatalytic material that absorbs and successfully utilizes a broad portion of the solar spectrum energy is as yet unmet. Herein, a mesoporous p-type/n-type heterojunction material, Cu x O-TiO2 (x = 1, 2), is synthesized via annealing of Cu/Cu2O nanocomposites mixed with a TiO2 precursor (TiCl4). Such an experimental approach in which two materials of diverse bandgaps are coupled provides a simultaneous opportunity for greater light absorption and rapid charge separation because of the intrinsic p-n heterojunction nature of the material. As detailed herein, this heterostructured photocatalyst demonstrates an improved photocatalytic activity. With the CO2 reduction of our optimal sample (augmented light absorption, efficacious charge separation, and mesoporosity) that utilizes no metal cocatalysts, a remarkable methane yield of 221.63 ppm·g-1·h-1 is achieved.

Generation of fuel from CO2 saturated liquids using a p-Si nanowire ‖ n-TiO2 nanotube array photoelectrochemical cell.

Light-driven, electrically biased pn junction photoelectrochemical (PEC) cells immersed in an electrolyte of CO(2) saturated 1.0 M NaHCO(3) are investigated for use in generating hydrocarbon fuels. The PEC photocathode is comprised of p-type Si nanowire arrays, with and without copper sensitization, while the photoanode is comprised of n-type TiO(2) nanotube array films. Under band gap illumination, the PEC cells convert CO(2) into hydrocarbon fuels, such as methane, along with carbon monoxide and substantial rates of hydrogen generation due to water photoelectrolysis. In addition to traces of C3-C4 hydrocarbons, methane and ethylene were formed at the combined rate of 201.5 nM/cm(2)-hr at an applied potential of -1.5 V vs. Ag/AgCl. The described technique provides a unique approach, utilizing earth abundant materials, for the photocatalytic reduction of CO(2) with subsequent generation of higher order hydrocarbons and syngas constituents of carbon monoxide and hydrogen.

Fabrication of coaxial TiO2/Sb2S3 nanowire hybrids for efficient nanostructured organic-inorganic thin film photovoltaics.

We report on low-cost, all solution fabrication of efficient air-stable nanostructured thin film photovoltaics comprised of n-type Sb(2)S(3) chemically deposited onto TiO(2) nanowire array films, forming coaxial Sb(2)S(3)/TiO(2) nanowire hybrids vertically oriented from the SnO(2):F coated glass substrate, which are then intercalated with poly(3-hexylthiophene) (P3HT) for hole transport and enhanced light absorption.