Highly sensitive plasmonic paper substrate fabricated via amphiphilic polymer self-assembly in microdroplet for detection of emerging pharmaceutical pollutants.

We report an innovative and facile approach to fabricating an ultrasensitive plasmonic paper substrate for surface-enhanced Raman spectroscopy (SERS). The approach exploits the self-assembling capability of poly(styrene-b-2-vinyl pyridine) block copolymers to form a thin film at the air-liquid interface within the single microdroplet scale for the first time and the subsequent in situ growth of silver nanoparticles (AgNPs). The concentration of the block copolymer was found to play an essential role in stabilizing the droplets during the mass transfer phase and formation of silver nanoparticles, thus influencing the SERS signals. SEM analysis of the morphology of the plasmonic paper substrates revealed the formation of spherical AgNPs evenly distributed across the surface of the formed copolymer film with a size distribution of 47.5 nm. The resultant enhancement factor was calculated to be 1.2 × 107, and the detection limit of rhodamine 6G was as low as 48.9 pM. The nanohybridized plasmonic paper was successfully applied to detect two emerging pollutants-sildenafil and flibanserin-with LODs as low as 1.48 nM and 3.45 nM, respectively. Thus, this study offers new prospects for designing an affordable and readily available, yet highly sensitive, paper-based SERS substrate with the potential for development as a lab-on-a-chip device.

Smartphone-based paper strip assay for putrescine and spermidine detection using hybrid organic-inorganic perovskite with Eu3+ complex.

A new method utilizing fluorescent ratiometry is proposed for detecting putrescine and spermidine. The method involves the use of a fluorescent probe comprising a 2D halide perovskite synthesized from octadecylamine-iodine and PbI2via a grinding-sonicating technique, along with a Eu3+-complex. Upon excitation at 290 nm, the probe fluoresces at two distinguishable wavelengths. The addition of putrescine and spermidine significantly decreases the emission of the 2D halide perovskite at 496 nm, while the emission of the Eu3+-complex at 618 nm remains stable. The color changes of the probe depend on the concentration of putrescine and spermidine, and the assay offers linearity over a wide concentration range (30-4000 ng mL-1), a low detection limit (4 ng mL-1 for putrescine, and 7 ng mL-1 for spermidine), and a quick response time. Furthermore, a portable device based on a smartphone can be used to record the color change of the paper test strip using the prepared fluorescent materials. The fluorescence quenching mechanism of the probe is explained as dynamic quenching.

Triplex glycan quantification by metabolic labeling with isotopically labeled glucose in yeast.

Mass spectrometry-based approaches encompass a powerful collection of tools for the analysis biological molecules, including glycans and glycoconjugates. Unlike most traditional bioanalytical methods focusing on these molecules, mass spectrometry is especially suited for multiplexing, by utilizing stable-isotope labeling. Indeed, stable isotope-based multiplexing can be regarded as the gold-standard approach in reducing noise and uncertainty in quantitative mass spectrometry and quantitative analyses generally. The increasing sophistication and depth of biological questions being asked continue to challenge the practitioners of mass spectrometry method development. To understand the biological relevance of glycans, many stable isotope labeling-based mass spectrometry methods have been developed. Based on the duplex MILPIG (metabolic isotope labeling of polysaccharides with isotopic glucose), we establish here a novel triplex isotope labeling method using baker's yeast as the model system. Two differentially isotope-labeled glucoses (medium: 1-13C1 and heavy: 1,2-13C2), in addition to natural abundance glucose (light), were successfully used to label each monosaccharide ring in N-linked glycans in three different cell culture conditions, that, after sample mixing, resulted in a predictable triplet spectrum amenable for relative quantitation. We demonstrate excellent accuracy and precision of relative quantitation for a 1:1:1 mixture of glycans labeled in such a fashion. In addition, we applied triplex MILPIG to interrogate differential N-glycan profiles in tunicamycin-treated and control yeast cells and show that different N-glycans respond differently to tunicamycin.

Silver-based SERS substrates fabricated using a 3D printed microfluidic device.

The detection of harmful chemicals in the environment and for food safety is a crucial requirement. While traditional techniques such as GC-MS and HPLC provide high sensitivity, they are expensive, time-consuming, and require skilled labor. Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical tool for detecting ultralow concentrations of chemical compounds and biomolecules. We present a reproducible method for producing Ag nanoparticles that can be used to create highly sensitive SERS substrates. A microfluidic device was employed to confine the precursor reagents within the droplets, resulting in Ag nanoparticles of uniform shape and size. The study investigates the effects of various synthesis conditions on the size distribution, dispersity, and localized surface plasmon resonance wavelength of the Ag nanoparticles. To create the SERS substrate, the as-synthesized Ag nanoparticles were assembled into a monolayer on a liquid/air interface and deposited onto a porous silicon array prepared through a metal-assisted chemical etching approach. By using the developed microfluidic device, enhancement factors of the Raman signal for rhodamine B (at 10-9 M) and melamine (at 10-7 M) of 8.59 × 106 and 8.21 × 103, respectively, were obtained. The detection limits for rhodamine B and melamine were estimated to be 1.94 × 10-10 M and 2.8 × 10-8 M with relative standard deviation values of 3.4% and 4.6%, respectively. The developed SERS substrate exhibits exceptional analytical performance and has the potential to be a valuable analytical tool for monitoring environmental contaminants.

Straightforward smartphone assay for quantifying tannic acid in beverages based on colour change of Eu3+/polyethyleneimine complex.

Tannic acid (TA)-a natural product-is a polyphenol derivative that occurs in certain kinds of beverages. A large amount of TA could give rise to an unpleasant flavour and could negatively affect the human body by causing stomach irritation, abdominal pain, nausea, vomiting, and even death. Thus, the need exists for a simple TA detection procedure that meets specific criteria such as on-site analysis, portability, and affordability. Herein, we present a new TA assay, which is based on the fluorescent quenching effect of an efficient fluorophore, and which comprises a smartphone-integrated homemade reader system. The fluorescent polyethyleneimine-derivatised polymer (FP), a strong emitter at 510 nm, was synthesised with the aid of a facile sonication method. In the presence of Eu3+ ions, TA quenches the fluorescence of the FP via electrostatic interaction. A smartphone was used to capture an image of the FP undergoing fluorescence for conversion to RGB values. The blue channel was chosen for further analysis because it offered the highest R2-value compared to the red and green channels. We verified these results using a commercial spectrofluorometer and calculated the limit of detection of this assay as 87 nM and 20 nM for the homemade reader and spectrofluorometer, respectively. The detection range for TA with the proposed assay is 0.16-66.66 µM. The application of the proposed method to real beverage samples for TA detection demonstrates its analytical applicability.

Turn Off-On Fluorescent CO2 Gas Detection Based on Amine-Functionalized Imidazole-Based Poly(ionic liquid).

Poly(ionic liquids) (PILs) have been widely used for CO2 capture because their characteristics resemble those of an ionic liquid, yet they have properties typically associated with polymers. We studied the application of the amine-functionalized poly(vinylimidazole)-based PIL (PVIm-NH2) as a chemosensor. The PVIm-NH2 was successfully prepared by a facile and low-cost method and was characterized by several analytical techniques: proton nuclear magnetic resonance (1H NMR), Fourier transform infrared (FT-IR) spectroscopy, gel permeation chromatography (GPC), and spectrofluorometry. The ability of PVIm-NH2 to detect CO2 gas was evaluated in the presence of triethylamine (TEA). Under optimized conditions, the detection limit was calculated to be 2.86 × 10-3 M with R 2 = 0.9906. Moreover, theoretical and experimental studies suggested a plausible mechanism whereby PVIm-NH2 generates N-heterocyclic carbenes (NHCs) in the presence of TEA, which further reacts with CO2 gas in aqueous media to form a carboxylic acid. Analysis of PVIm-NH2 before and after the addition of TEA using the 1H NMR technique showed the disappearance of the proton peak, thus suggesting a successful generation of NHC. Further analysis via 13C NMR revealed the reaction of CO2 and NHC to form a carboxylic acid group. Finally, we demonstrated that PIL is a promising candidate as a chemosensor through diverse structural modifications.

Upconversion Nanomaterials in Bioimaging and Biosensor Applications and Their Biological Response.

In recent decades, upconversion nanomaterials (UCNMs) have attracted considerable research interest because of their unique optical properties, such as large anti-Stokes shifts, sharp emissions, non-photobleaching, and long lifetime. These unique properties make them ideal candidates for unified applications in biomedical fields, including drug delivery, bioimaging, biosensing, and photodynamic therapy for specific cancers. This review describes the general mechanisms of upconversion, synthesis methods, and potential applications in biology and their biological responses. Additionally, the biological toxicity of UCNMs is explained and summarized with the associated intracellular association mechanisms. Finally, the prospects and future challenges of UCNMs at the clinical level in biological applications are described, along with a summary of opportunity for biological as well as clinical applications of UCNMs.

Magnetic visible-light activated photocatalyst ZnFe2O4/BiVO4/g-C3N4 for decomposition of antibiotic lomefloxacin: Photocatalytic mechanism, degradation pathway, and toxicity assessment.

Magnetic ZnFe2O4/BiVO4/g-C3N4 (ZBC) composites were prepared via a facile hydrothermal and calcination method for the degradation of a representative antibiotics lomefloxacin (LFX) under visible light irradiation. The optimal photocatalyst ZBC-10 with a ZnFe2O4:BiVO4:g-C3N4 mass ratio of 1:8:10 performed 96.1% removal of LFX after 105 min of illumination. The excellent performance is ascribed to the effective construction of heterojunctions and its capacity to form a double Z-scheme charge transmission pathway among the hosts in ZBC-10. The composite enhanced the separation and migration of photoexcited charge carriers and the effective generation of multiple active radicals including ·OH, ·O2-, and 1O2. The LFX degradation process, identified based on an integrated HPLC-Q-TOF-MS analysis and density functional theory computation of the Fukui indices, comprised of three pathways initiated by the opening of the piperazinyl ring, separation of piperazinyl and quinoline moieties, and cleavage of the pyridine ring on the quinoline moieties. Ecotoxicological evaluation confirmed the reduced toxicity of transformation intermediates over photocatalysis. Convenient magnetic recovery, high performance, and high recyclability made ZBC-10 a promising visible-light-activated photocatalyst for practical implementation in eliminating antibiotics from wastewater.

Self-Assembly of Polystyrene-b-poly(2-vinylpyridine)/Chloroauric Acid at the Liquid/Liquid Interface.

The self-assembly of polystyrene-block-poly(2-vinylpyridine) at the liquid/liquid interface has been systematically investigated to develop a series of primary morphologies of the aggregates. The block copolymers self-assembled into large areas of nanodot arrays, parallel nanostrands, layered films, parallel nanobelts, honeycomb monolayers, and foams by reacting with chloroauric acid, depending on the molecular structure of the block copolymers and the amount of chloroauric acid. The formation of the first four ordered structures resulted from interfacial adsorption and self-assembly, and nucleation and epitaxial growth. The latter two structures were attributed to the water hole templating effect and spontaneous interfacial emulsification, respectively. This work provides insight into the self-assembly behavior of block copolymers at the interface and provides a facile approach for fabricating functional structures.

Water-stable perovskite-loaded nanogels containing antioxidant property for highly sensitive and selective detection of roxithromycin in animal-derived food products.

Luminescent inorganic lead halide perovskite nanoparticles lack stability in aqueous solutions, limiting their application to optical sensors. Here, hybrid CsPbBr3-loaded MIP nanogels were developed with enhanced stability in aqueous media. Multifunctional MIP nanogels with antioxidant function and hydrophobic cavities were synthesized from HEMA derivatives in the presence of roxithromycin as a template. The CsPbBr3 nanoparticles were loaded into pre-synthesized MIP nanogels via in-situ synthesis with a size distribution of 200 nm. The developed CsPbBr3-nanogel exhibits excellent stability to air/moisture and enhanced stability toward an aqueous solvent. The developed CsPbBr3-loaded MIP nanogels showed a selective and sensitive detection of ROX with a limit of detection calculated to be 1.7 × 10-5 µg/mL (20.6 pM). The developed CsPbBr3-loaded MIP antioxidant-nanogels were evaluated on practical application for the quantitative determination of ROX antibiotic in animal-derived food products with excellent analytical performance. The detection of ROX in animal-derived food products showed good recovery results, making them an ideal candidate for sensing ROX.

Simple fluorescence optosensing probe for spermine based on ciprofloxacin-Tb3+ complexation.

We developed a facile detection method of spermine based on the fluorescence (FL) quenching of the ciprofloxacin-Tb3+ complex, which shows astrong green emission. Ciprofloxacin (CP) makes efficient bondings to Tb3+ ion as a linker molecule through carboxylic and ketone groups to form a kind of lanthanide coordination polymer. The addition of spermine that competes with Tb3+ ions for the interaction with CP due to its positive charge brings about weakened coordination linkage of CP and Tb3+. The probe exhibited high sensitivity, selectivity, and good linearity in the range of 2-180 µM with a low limit of detection of 0.17 µM. Moreover, we applied this method on the paper strip test (PST), along with the integration of a smartphone and Arduino-based device. The practical reliability of the developed probe was evaluated on human serum samples with acceptable analytical results.

Large-Area Assembly of Metal-Organic Layered Ultrathin Films at the Liquid/Liquid Interface.

Two-dimensional functional metal-organic frameworks and coordination polymers have attracted much attention and have been successfully prepared in solutions and at interfaces through the coordination of ligands to metal ions. However, the preparation of large-area ultrathin ordered films is still a challenge. Here, a modified liquid/liquid interfacial epitaxial growth method has been developed. A planar liquid/liquid interface between a chloroform solution of bipyridine derivatives and pure water was constructed first, and then an aqueous solution of Eu3+ or Cu2+ ions was added dropwise into the water phase. A layered ultrathin film with the size of several hundreds of square micrometers appeared at the liquid/liquid interface after a certain time. The monitoring results showed that the formation of ultrathin films was a result of continuous epitaxial growth of the adsorbed species due to the synergistic effects of hydrophobic effects of the alkyl chains, coordination bonds between the ligands and metal ions, π-π interactions between the ligands, and the restriction of the interface on the vertical growth. This offers a way to fabricate more large-area thin films of amphiphilic molecules.

Selective dual detection of Hg2+ and TATP based on amphiphilic conjugated polythiophene-quantum dot hybrid materials.

The design of multifunctional sensors based on biocompatible hybrid materials consisting of conjugated polythiophene-quantum dots for multiple environmental pollutants is a promising strategy for the development of new monitoring technologies. Herein, we present a new approach for the "on-off-on" sensing of Hg2+ and triacetone triperoxide (TATP) based on amphiphilic polythiophene-coated CdTe QDs (PQDs, PLQY ∼78%). The emission of the PQDs is quenched by Hg2+ ions via electron transfer interactions. Based on the strong interaction between TATP and Hg2+ ions, the addition of TATP to the PQD-Hg2+ complex results in a remarkable recovery of the PQD emission. Under the optimized conditions, the PQD sensor shows a good linear response to Hg2+ and TATP with detection limits of 7.4 nM and 0.055 mg L-1, respectively. Furthermore, the "on-off-on" sensor demonstrates good biocompatibility, high stability, and excellent selectivity in the presence of other metal ions and common explosives. Importantly, the proposed method can be used to determine the level of Hg2+ and TATP in environmental water samples.

Preparation, Properties, and Microbial Impact of Tungsten (VI) Oxide and Zinc (II) Oxide Nanoparticles Enriched Polyethylene Sebacate Nanocomposites.

Nanoparticles of tungsten oxide (WO3) and zinc oxide (ZnO) enriched polyethylene sebacate (PES) nanocomposites were prepared through the coprecipitation process and condensation polymerization reaction. The obtained nano-sized particles of WO3 and ZnO, PES, and nanocomposites (WO3-PES NC and ZnO-PES NC) were investigated. The average molecular weight of the cured PES was measured by employing the gel permeation chromatography (GPC) technique. Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) spectra assured the formation of the polymeric nanocomposites.WO3 and ZnO nanoparticles supposed a condensed porous spherical phase found implanted in the polymer structure, as detected by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. These nano-scale systems achieved an electrical activity based on the conductive nanoparticles embedded matrix as a result of the ion-ion interactions. The microbial influence of the nanocomposites was examined against pathogenic bacteria; Pseudomonas aeruginosa,Escherichia coli, Staphylococcus aureus, and Bacillus subtilis, and Fungi; Aspergillus niger, and Candidaalbicans. Results exhibited that these nanocomposites have antimicrobial effects from moderate to slightly high on bacteria and high on fungi which was confirmed by a clear zone of inhibition. This study contributes to the design of reasonable composites to be under evaluation for their catalytic effect.

Metabolic labeling of glycans with isotopic glucose for quantitative glycomics in yeast.

Changes in glycan levels could directly affect the biochemical properties of glycoproteins and thus influence their physiological functions. In order to decode the correlation of glycan prevalence with their physiological contribution, many mass spectrometry (MS) and stable isotope labeling-based methods have been developed for the relative quantification of glycans. In this study, we expand the quantitative glycomic toolbox with the addition of optimized Metabolic Isotope Labeling of Polysaccharides with Isotopic Glucose (MILPIG) approach in baker's yeast (Saccharomyces cerevisiae). We demonstrate that culturing baker's yeast in the presence of carbon-13 labeled glucose (1-13C1) leads to effective incorporation of carbon-13 to both N-linked and O-linked glycans. We established that metabolic incorporation of isotope-labeled glucose at a concentration of 5 mg/mL for three days is required for an accurate quantitative analysis with optimal isotopic cluster distribution of glycans. To validate the robustness of the method, we performed the analysis by 1:1 mixing of normal and isotope-labeled glycans, and obtained excellent linear calibration curves from various analytes. Finally, we quantitated the inhibitory effect of tunicamycin, a N-linked glycosylation inhibitor, to glycan expression profile in yeast.

Selective optosensing of iron(III) ions in HeLa cells using NaYF4:Yb3+/Tm3+ upconversion nanoparticles coated with polyepinephrine.

Novel polyepinephrine-modified NaYF4:Yb,Tm upconversion luminescent nanoparticles (UCNP@PEP) were prepared via the self-polymerization of epinephrine on the surfaces of the UCNPs for selective sensing of Fe3+ inside a cell and for intracellular imaging. The proposed UCNP@PEP probe is a strong blue light emitter (λmax = 474 nm) upon exposure to an excitation wavelength of 980 nm. The probe was used for detecting Fe3+ owing to the complexation reaction between UCNP@PEP and Fe3+, resulting in reduced upconversion luminescence (UCL) intensity. The proposed probe has a detection limit of 0.2 µM and a good linear range of 1-10 µM for sensing Fe3+ ions. Moreover, the UCNP@PEP probe displays high cell viability (90%) and is feasible for intracellular imaging. The ability of the probe to sense Fe3+ in a human serum sample was tested and shows promising output for diagnostic purposes. The prepared UCNP@PEP probe was characterized by using UV-visible (UV-Vis) absorption spectrometry, fluorescence (FL) spectrometry, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR).

Solvent-resistant microfluidic paper-based analytical device/spray mass spectrometry for quantitative analysis of C18 -ceramide biomarker.

We developed a highly efficient and low-cost organic solvents-resistant microfluidic paper-based analytical device (µPAD) coupled with paper spray mass spectrometry (PS-MS) for quantitative determination of C18 -ceramide as a prognostic biomarker for several diseases. Several models of µPAD patterns have been examined to select the most resistant and efficient microchannel barriers, which can provide continuous spray at ionization zone and prevent "coffee ring" effect. Moreover, the developed µPAD has enabled the analysis of low concentration of C18 -ceramide because of the maximum supply of deposited analyte through microchannel. The MS results confirmed the formation of doubly and singly charged metal ion complexes between ceramide and different metal ions. Notably, the complexation that occurs between lithium ions and C18 -ceramide showed a high relative abundance compared with other formed complexes. Taking into account the relative abundance of complex [Cer + Li]+ at 572.8 m/z, it can be considered as a stable ion and therefore be used for the analysis of C18 -ceramide at low concentrations. Complexation of C18 -ceramide and lithium confirmed with quantum chemical calculations. The proposed method represents good linearity with a regression coefficient of 0.9956 for the analysis of C18 -ceramide and reaches a limit of detection to 0.84 nM. It has been adapted successfully for practical application in human serum samples with high recovery values in range of 92%-105%. The developed µPAD-MS technique provides clear advantages by reducing the experimental steps and simplifying the operation process and enables to identify subnanomolar concentration of C18 -ceramide in human serum samples.

Novel "turn on-off" paper sensor based on nonionic conjugated polythiophene-coated CdTe QDs for efficient visual detection of cholinesterase activity.

An increasing number of patients are living with Alzheimer's disease (AD); thus, the need for a method to detect AD early and sensitively has become urgent, and the demand for an intelligent analytical platform is growing year by year. Abnormal levels of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) are known to be indicative of AD. In this work, a novel conjugated polythiophene (CP) compound was successfully combined with CdTe quantum dots (QDs) to improve their selectivity and sensitivity. The QDs successfully enabled the detection of low concentrations of AChE by turning on the fluorescence of the CdTe/CP via the interaction between CP and thiocholine produced by ATCh hydrolysis and aggregation induced emission enhancement (AIEE). Under optimal conditions, we reached a low detection limit of 0.14 U L-1, which is 7.9 times lower than that of pristine QDs. More importantly, an efficient, inexpensive, and disposable paper-based platform, which allows the efficient visual detection of AChE activity via the color variation of CdTe/CP, was designed. Moreover, the accuracy of the method was demonstrated by conducting a recovery test in human serum, in which the recoveries reached 107% and 110%, proving that CdTe/CP has considerable potential to be used for analyzing real biological samples. The advantages of this method are its simplicity, fast detection capability, affordability, and the fact that it can be used for on-site detection of AChE activity. Furthermore, it has certain guiding significance for detecting AD.

Dual emission nonionic molecular imprinting conjugated polythiophenes-based paper devices and their nanofibers for point-of-care biomarkers detection.

Enzyme-based assays have been extensively used for the early diagnosis of disease-related biomarkers. However, these assays are time-consuming, resource-intensive, and infrastructure-dependent, which renders them unsuitable and impractical for use in resource-constrained areas. Thus, there is a strong demand for a biocompatible and potentially generalizable sensor that can rapidly detect cancer biomarkers at ultralow concentration. Herein, an enzyme-free, cost-efficient, and easy-to-use assay based on a novel approach that entails fluorescent molecularly imprinting conjugated polythiophenes (FMICPs) for cancer biomarkers detection is developed. The promising conjugated polythiophenes structure, with a PLQY as high as 55%, provides a straightforward, and affordable method for free-enzyme signal generation. More importantly, the feasibility of integrating printed-paper technology with a sensitive and cost-effective smartphone and portable prototype testing device that could be utilized for rapid point-of-care (POC) cancer diagnostics is successfully introduced. Significantly, the unique structure of FMICP nanofibers (FMICP NFs) displays superior performance with enhanced sensitivity that is 80 times higher than that of pristine FMICP. This assay could lower the limits of detection to 15 fg mL-1 and 3.5 fg mL-1 for α-fetoprotein (AFP) and carcinoembryonic antigen (CEA), respectively, which are three orders of magnitude exceeding that of the standard enzyme-based assay. Moreover, the developed sensors are successfully applied to the fast diagnosis of AFP in liver cancer patients and the FMICP and FMICP NFs results are in excellent agreement with those of clinical ELISA.

Highly sensitive and selective optosensing of quercetin based on novel complexation with yttrium ions.

A simple and fast method was developed for the determination of quercetin. The concentration of quercetin can be determined based on the fluorescence emission resulting from the coordinative interactions between quercetin and the yttrium ion (Y3+). Notably, a portable platform to quantitatively analyze quercetin was constructed. This platform incorporates our custom-built homemade reader based on a photodiode, and Arduino hardware, which accepts a paper ribbon on which Y3+ is deposited as an input. In addition, the color change of the paper ribbon was identified using a smartphone via the hue values of the photographs. The limits of detection for quercetin using spectroscopy, a smartphone, and a custom-built reader were calculated to be 27, 110, and 129 nM, respectively. The use of a custom-built device and a smartphone for detecting quercetin via fluorescence from the prepared paper ribbon reduces the time and cost of quercetin detection. This approach could be employed for on-site sensing of quercetin in real samples.