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.

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.

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.

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.

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).

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.

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.

Preparing cuprous oxide nanomaterials by electrochemical method for non-enzymatic glucose biosensor.

Cuprous oxide (Cu2O) nanostructure has been synthesized using an electrochemical method with a two-electrode system. Cu foils were used as electrodes and NH2(OH) was utilized as the reducing agent. The effects of pH and applied voltages on the morphology of the product were investigated. The morphology and optical properties of Cu2O particles were characterized using scanning electron microscopy, x-ray diffraction, and diffuse reflectance spectra. The synthesized Cu2O nanostructures that formed in the vicinity of the anode at 2 V and pH = 11 showed high uniform distribution, small size, and good electrochemical sensing. These Cu2O nanoparticles were coated on an Indium tin oxide substrate and applied to detect non-enzyme glucose as excellent biosensors. The non-enzyme glucose biosensors exhibited good performance with high response, good selectivity, wide linear detection range, and a low detection limit at 0.4 µM. Synthesized Cu2O nanostructures are potential materials for a non-enzyme glucose biosensor.

Colorimetric detection of chromium(VI) using graphene oxide nanoparticles acting as a peroxidase mimetic catalyst and 8-hydroxyquinoline as an inhibitor.

A method is described for the colorimetric determination of chromate [chromium(VI)]. It is based on the use of graphene oxide (GO) nanoparticles acting as a peroxidase mimic. A blue color is generated by oxidation of 3,3,5,5-tetramethylbenzidine by H2O2 which is catalyzed by GO. This color-forming reaction is prevented in the presence of 8-hydroxyquinoline (8-HQ). However, in the presence of Cr(VI), the blue color will be formed from TMB owing to the oxidation of the inhibitor 8-HQ by Cr(VI). The color can be measured by a spectrophotometry (at 652 nm) or detected visually. Under optimal experimental conditions, response is linear in the 50 to 430 nM range of chromate concentration, and the limit of detection is 5.8 nM (at S/N = 3). The assay is highly selective and was successfully applied to the determination of Cr(VI) in spiked water samples. Graphical abstract Schematic of the colorimetric assay for Cr(VI). TMB: 3,3,5,5-tetramethylbenzidine.

Fabrication of Two-Dimensional Arrays of Diameter-Tunable PS-b-P2VP Nanowires at the Air/Water Interface.

Composite thin films with well-defined and parallel nanowires were fabricated from the binary blends of a diblock copolymer polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and several homopolystyrenes (h-PSs) at the air/liquid interface through a facile technique, which involves solution self-assembly, interface adsorption, and further self-organization processes. It was confirmed that the nanowires that appeared at the air/water interface came from the cylindrical micelles formed in solution. Interestingly, the diameters of the nanowires are uniform and can be tuned precisely from 45 to 247 nm by incorporating the h-PS molecules into the micellar core. This parallel alignment of the nanowires has potential applications in optical devices and enables the nanowires to be used as templates to prepare functional nanostructures. The extent to which h-PS molecules with different molecular weights are able to influence the diameter control of the nanowires was also systematically investigated.

Influence of gold species (AuCl4(-) and AuCl2(-)) on self-assembly of PS-b-P2VP in solutions and morphology of composite thin films fabricated at the air/liquid interfaces.

Composite thin films doped with Au species were fabricated at an air/liquid interface via a series of steps, including the mass transfer of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) across the liquid/liquid interface between a DMF/CHCl3 solution and an aqueous solution containing either AuCl4(-) or AuCl2(-), self-assembly of PS-b-P2VP in a mixed DMF-water solution, and adsorption and further self-organization of the formed aggregates at the air/liquid interface. This is a new approach for fabricating composite polymer films and can be completed within a very short time. AuCl4(-) and AuCl2(-) ions were found to significantly influence the self-assembly behavior of the block copolymer and the morphologies of the composite films, leading to the formation of nanowire arrays and a foam structure at the air/liquid interface, respectively, which originated from rod-like micelles and microcapsules that had formed in the respective solutions. The effect of the metal complex was analyzed based on the packing parameters of the amphiphilic polymer molecules in different microenvironments and the interactions between the pyridine groups and the metal chloride anions. In addition, these composite thin films exhibited stable and durable performance as heterogeneous catalysts for the hydrogenation of nitroaromatics in aqueous solutions.

Fabrication of composite polymer foam films at the liquid/liquid interface through emulsion-directed assembly and adsorption processes.

The foam films of polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-b-PAA-b-PS) doped with Cd(II) or Pb(II) species were fabricated at the planar liquid/liquid interfaces between a DMF/chloroform (v/v: 1/1) solution of the polymer and aqueous solutions containing cadmium acetate or lead acetate at ambient temperature. Optical microscopic observation shows the thin film is uniform on a larger length scale. Transmission electron microscopic (TEM) investigations reveal that the foam films are made up of microcapsules with the size of several hundreds of nanometers to micrometers. The walls of the microcapsules have a layered structure decorating with nanofibers and hollow nanospheres, where numerous inorganic fine nanoparticles are dispersed homogeneously. The film formation is a result of emulsion droplet-templated assembly and adsorption of the formed microcapsules at the planar liquid/liquid interface. Because of the miscibility of DMF with chloroform and water, DMF migrates to the aqueous phase while water migrates to the organic phase across the interface, resulting in the formation of a W/O emulsion, as revealed by optical microscopic observation, freeze fracture transmission electron microscopic (FF-TEM) observation, and dynamic laser scattering (DLS) investigation. The triblock copolymer molecules and the inorganic species adsorb and self-assemble around the emulsion drops, leading to the formation of the composite microcapsules. X-ray photoelectron spectroscopic (XPS) and FTIR spectroscopic results indicate that two kinds of Cd(II) or Pb(II) species, metal oxide or hydroxide, resulting from the hydrolysis of the metal ions and the coordinated metal ions to the carboxyl groups coexist in the formed thin films, which transform to metal sulfide completely after treating with hydrogen sulfide to get metal sulfide nanoparticle-doped polymer thin films.

Liquid/Liquid interfacial fabrication of thermosensitive and catalytically active Ag nanoparticle-doped block copolymer composite foam films.

An aqueous solution of AgNO3 (upper phase) and a DMF/CHCl3 solution of polystyrene-b-poly(acryl acid)-b-polystyrene (PS-b-PAA-b-PS) or PS-b-PAA-b-PS/1,6-diaminohexane (DAH) (lower phase) constituted a planar liquid/liquid interface. The lower phase gradually transformed to a water-in-oil (W/O) emulsion via spontaneous emulsification due to the "ouzo effect". Polymer molecules, DAH molecules, and Ag(+) ions assembled into microcapsules around emulsion droplets that adsorbed at the planar liquid/liquid interface, resulting in formation of a foam film. DAH acted as a cross-linker during this process. Transmission electron microscopic observations indicated that Ag nanoclusters that were generated through reduction of Ag(+) ions by DMF were homogeneously dispersed in the walls of the foam structure. X-ray photoelectron spectroscopic investigations revealed that Ag(I) and Ag(0) coexisted in the film, and Ag(I) transformed to Ag(0) after further treatment. The film formed without DAH was not stable, while the film formed with DAH was very stable due to intermolecular attraction between PAA and DAH and formation of amides, as revealed by FTIR spectra. The film formed with DAH exhibited high and durable catalytic activity for hydrogenation of nitro compounds and, very interestingly, exhibited thermoresponsive catalytic behavior.

Controllable synthesis of thiol-capped CdTe nanoparticles for optical sensing of triethylenetetramine dihydrochloride.

Highly luminescent CdTe quantum dots (QDs) were synthesized through a co-precipitation route in aqueous salt solutions using different thiols as stabilizers. The synthetic procedure was simple, efficient, and stable. It could also allow controlling the emission wavelength by varying the experimental conditions such as reaction time and pH values. The strong luminescence of the QDs was observed under UV-excitation and emission colors could be adjusted. The interaction between CdTe QDs and triethylenetetramine dihydrochloride (TETA) which is a candidate treatment for diabetic cardiovascular complication was investigated by fluorescence spectroscopy. Based on the quenching effect on CdTe photoluminescence intensity by TETA, a simple assay system for analyzing the content of TETA in aqueous samples was developed. The linearity was maintained in the range of 0.2 µM to 1.2 µM (R2 = 0.994) with a limit of detection (LOD; S/N = 3) at 28 nM. The results showed that CdTe QDs capped with diverse thiols has a potential for the quantitative analysis of TETA in urine samples.

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.

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.

LED-induced in-column molecular imprinting for solid phase extraction/capillary electrophoresis.

A novel light-emitting diode-induced polymerization technology was demonstrated, which could be applied for the on-line construction of an in-column molecularly imprinted solid phase extraction concentrator for capillary electrophoresis. Such a strategy exhibited the advantages of simplicity, zero dead volume, and ease of renewing the concentrator.

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.