A new technique to determine organic and inorganic acid contamination

A new acid indicator pad was developed for the detection of acid breakthrough of gloves and chemical protective clothing. The pad carries a reagent which responds to acid contaminant by producing a color change. The pad was used to detect both organic and inorganic acids permeating through glove materials using the modified ASTM F-739 and direct permeability testing procedures. Breakthrough times for each type of glove were determined, and found to range from 4 min to > 4 h for propionic acid, from 3 min to > 4 h for acrylic acid, and from 26 min to > 4 h for HCl. A quantification was performed for propionic and acrylic acids following solvent desorption and gas chromatography. Both acids exhibited > 99% adsorption [the acid and its reactivity (the acid reacted with an indicator to contribute the color change)] on the pads at a spiking level of 1.8 microL for each acid. Acid recovery during quantification was calculated for each acid, ranging from 52-72% (RSD < or = 4.0%) for both acids over the spiking range 0.2-1.8 microL. The quantitative mass of the acids on the pads at the time of breakthrough detection ranged from 260-282 and 270-296 microg cm(-2) for propionic acid and acrylic acid, respectively. The new colorimetric indicator pad should be useful in detecting and collecting acid permeation samples through gloves and chemical protective clothing in both laboratory and field studies, for quantitative analysis.     

Colorimetric Recognition of Aldehydes and Ketones

A colorimetric sensor array has been designed for the identification of and discrimination among aldehydes and ketones in vapor phase. Due to rapid chemical reactions between the solid‐state sensor elements and gaseous analytes, distinct color difference patterns were produced and digitally imaged for chemometric analysis. The sensor array was developed from classical spot tests using aniline and phenylhydrazine dyes that enable molecular recognition of a wide variety of aliphatic or aromatic aldehydes and ketones, as demonstrated by hierarchical cluster, principal component, and support vector machine analyses. The aldehyde/ketone‐specific sensors were further employed for differentiation among and identification of ten liquor samples (whiskies, brandy, vodka) and ethanol controls, showing its potential applications in the beverage industry.     

Colorimetric monitoring of solid-phase aldehydes using 2,4-dinitrophenylhydrazine

A simple and rapid method to achieve colorimetric monitoring of resin-bound aldehydes, based on ambient temperature reaction with 2,4-dinitrophenylhydrazine (DNPH) in the presence of dilute acid, has been developed as an adjunct to solid-phase organic synthesis and combinatorial chemistry. By this test, the presence of aldehydes is indicated by a red to dark-orange appearance, within a minute. Alternatively, resins that are free of aldehydes or in which aldehyde functions have reacted completely retain their original color. The DNPH test was demonstrated for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethyl polystyrene (AMP), cross-linked ethoxylate acrylate resin (CLEAR), and acryloylated O,O'-bis(2-aminopropyl)poly(ethylene glycol) (PEGA) supports and gave results visible to the naked eye at levels as low as 18 micromol of aldehyde per gram of resin.     

An indicator-displacement assay for naked-eye detection and quantification of histidine in human urine

A simple and efficient colorimetric method for the naked-eye detection and quantification of histidine in biological fluids was developed based on an indicator-displacement assay (IDA) and the Ni(2+)-histidine affinity pair. In this IDA approach, a commercially available dye, murexide, was used as the indicator and the selective detection of histidine was achieved based on the competition between indicator and histidine for the binding with Ni(2+). The competition of histidine with murexide for Ni(2+) resulted in an obvious color change of the solution from yellow to purple, and the permitted naked-eye detection of trace histidine. The developed bioassay allows the rapid, sensitive and selective detection of histidine in urine samples, and does not need complicated sample pretreatment. The detection limit was 0.4 μM with a linear range from 2 to 30 μM. The relative standard deviation for 11 replicate detections of 8 μM histidine was 2.0%. The developed sensor was successfully applied to the determination of histidine in human urine samples with recoveries from 97 to 105%.     

Colorimetric detection of oligonucleotides using a polydiacetylene vesicle sensor

A new system for the colorimetric detection of oligonucleotides was developed using polydiacetylene vesicles, which play the dual role of an indicator of color transition and an amplification tag. The results are of significance in understanding the mechanism of color transition of biological recognition in polydiacetylene systems and in designing new biosensors.     

Using an indicator displacement assay to monitor glucose oxidase activity in blood serum

[diagram: see text] Using a boronic acid receptor that was previously found to have high affinity for gluconic acid, we created a colorimetric indicator displacement assay (IDA) that can report the concentration of the product of glucose oxidase (GOx) catalyzed glucose oxidation. The color change obtained directly reflects the concentration of glucose. Our sensing ensemble was then successfully applied to determine the glucose concentration in human serum, which offers a facile, colorimetric, sensitive, and accurate glucose test.     

Characterization of Natural Anthocyanin Indicator Based on Cellulose Bio-Composite Film for Monitoring the Freshness of Chicken Tenderloin

Intelligent packaging with indicators that provide information about the quality of food products can inform the consumer regarding food safety and reduce food waste. A solid material for a pH-responsive indicator was developed from hydroxypropyl methylcellulose (HPMC) composited with microcrystalline cellulose (MCC). MCC at 5%, 10%, 20%, and 30% w/w was introduced into the HPMC matrix and the physical, barrier, thermal, and optical properties of the HPMC/MCC bio-composite (HMB) films were analyzed. At 5, 10, and 20% MCC, improved mechanical, transparency, and barrier properties were observed, where HMB with 20% of MCC (H20MB) showed the best performance. Therefore, H20MB was selected as the biodegradable solid material for fabricating Roselle anthocyanins (RA) pH sensing indicators. The performance of the RA-H20MB indicator was evaluated by monitoring its response to ammonia vapor and tracking freshness status of chicken tenderloin. The RA-H20MB showed a clear color change with respect to ammonia exposure and quality change of chicken tenderloin; the color changed from red to magenta, purple and green, respectively. These results indicated that RA-H20MB can be used as a biodegradable pH sensing indicator to determine food quality and freshness.     

Rapid and sensitive colorimetric visualization of phthalates using UTP-modified gold nanoparticles cross-linked by copper(II)

A simple and reliable colorimetric method for determination of phthalates is developed utilizing uridine-5'-triphosphate (UTP)-modified gold nanoparticles as a color indicator and Cu(2+) as a cross-linker. The method demonstrates superior sensitivity with a detection limit of phthalates of ca. 0.5 ppm.     

Method for combinatorial screening of moisture vapor transmission rate

A high-throughput method for screening the moisture vapor transmission rate of barrier films was developed. This moisture high-throughput screening (MHTS) technique is based upon a Nafion-crystal violet (CVN) sensor that changes color from yellow to green upon absorption of water. Using an appropriate set of known standards, the slope of absorbance (at 630 nm) as a function of time can be converted into moisture vapor transmission rate (MVTR) values that agree with those obtained using ASTM F1290. High-throughput screening was demonstrated by depositing 20 emulsion-based poly(vinylidene chloride) films, using a 48-well template, of varying thicknesses onto the CVN sensor film and aging at 40 degrees C and 90% relative humidity for 72 h. MVTR values were accurately determined to a level of 0.9 g/m(2).day, at which point side-diffusion of moisture between the barrier and sensor films prevented observation of lower values. Larger sample size and edge-sealing are two proposed methods for improving the sensitivity of MHTS.     

Colorimetric assay for sulfate using positively-charged gold nanoparticles and its application for real-time monitoring of redox process

A flexible nanoparticle-based sulfate assay is demonstrated in which the positively-charged gold nanoparticles (cysteamine-AuNPs) act as indicator. The aggregation of cysteamine-AuNPs is selectively induced by sulfate, which allows the rapid colorimetric sensing of sulfate without any precipitant, sample preparation and specific instruments. In this work, the cysteamine-AuNPs probe has been successfully applied to the colorimetric detection of sulfate and demonstrates superior sensitivity with a detection limit of sulfate of ~50 ppb. A surprise finding is that the proposed probe can achieve the goal of real-time monitoring and translating a redox process into an appreciable color change via the aggregation of nanoparticles. This is a novel application of a positively-charged AuNPs-based nanoprobe for sulfate detection, kinetic study of the redox process, and opens up new opportunities for design of more novel colorimetric strategies and expansion of AuNPs-based application in different fields.     

Diarylprolinol as an Effective Organocatalyst in Asymmetric Cross-Aldol Reactions of Two Different Aldehydes

The aldol reaction is one of the most important carbon-carbon bond-forming reactions in organic chemistry. Asymmetric direct cross-aldol reaction of two different aldehydes has been regarded as a difficult reaction because of the side reactions such as self-aldol reaction and over reaction. We found that trifluoromethyl-substituted diarylprolinol, α,α-bis[3,5-bis(trifluoromethyl)phenyl]-2-pyrrolidinemethanol ( 1 ), is an effective organocatalyst that promotes several cross-aldol reactions of aldehydes with excellent diastereo- and enantioselectivities. Acetaldehyde can be employed as a suitable nucleophilic aldehyde. Successful electrophilic aldehydes are ethyl glyoxylate, chloroacetaldehyde, dichloroacetaldehyde, chloral, α-alkyl-α-oxo aldehyde, trifluoroacetaldehyde, glyoxal, alkenyl aldehyde, alkynyl aldehyde, and formaldehyde. Some of the aldehydes are commercially available as a polymer solution, an aqueous solution, or in the hydrated form. They can be used directly in the asymmetric aldol reaction as a commercially available form, which is a synthetic advantage. Given that the obtained aldol products possess several functional groups along with a formyl moiety, they are synthetically useful chiral building blocks.     

Development of a colorimetric test for quantification of uranium in drinking water

A colorimetric method was developed for the determination of uranium in groundwater. The detection limit for the method is approximately 25 μg/L uranium, which is below the maximum contaminant level for uranium in drinking water, 30 μg/L. The method is rapid and requires little technical training to conduct, allowing it to be used by consumers, in the laboratory, or in the field. The two-step technique involves preconcentrating uranium using a U/TEVA-2 extraction chromatographic resin followed by complexation with a pyridylazo indicator dye, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol. If color change is visible to the eye, the concentration of uranium in groundwater is above the detection limit. Preconcentration using U/TEVA-2 also serves to eliminate metals that may interfere with the quantification of uranium.     

Visual detection of melamine in milk products by label-free gold nanoparticles

A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2 ppm, respectively, within 30 min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15 ppm of melamine in liquid milk and 2.5 ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products.     

Synthesis of tert-butyl peresters from aldehydes by Bu4NI-catalyzed metal-free oxidation and its combination with the Kharasch-Sosnovsky reaction

A new tert-butyl peresters synthesis directly from aldehydes and TBHP was developed via Bu(4)NI-catalyzed aldehyde C-H oxidation. Mechanistic studies suggest that the protocol proceeds via a radical process. Combining the method with the Kharasch-Sosnovsky reaction offers a practical approach for the synthesis of allylic esters from simple aldehydes and alkenes via a two-step one-pot procedure.     

Starch-iodine films respond to water vapor

Starch-iodine indicator films were found to have useful spectroscopic properties for the detection of water vapor. The large colorimetric response of these easily prepared films was easily detected by the absorption of 632.8 nm HeNe laser light, using a planar integrated optical waveguide (IOW) platform. The detection limit of a prototype sensor was found to be below 5% relative humidity (RH), with response times of the order of seconds.     

Rapid and sensitive detection of cholera toxin using gold nanoparticle-based simple colorimetric and dynamic light scattering assay

Herein, a rapid and simple gold nanoparticle based colorimetric and dynamic light scattering (DLS) assay for the sensitive detection of cholera toxin has been developed. The developed assay is based on the distance dependent properties of gold nanoparticles which cause aggregation of antibody-conjugated gold nanoparticles in the presence of cholera toxin resulting discernible color change. This aggregation induced color change caused a red shift in the plasmon band of nanoparticles which was measured by UV–Vis spectroscopy. In addition, we employed DLS assay to monitor the extent of aggregation in the presence of different concentration of cholera toxin. Our assay can visually detect as low as 10 nM of cholera toxin which is lower than the previously reported colorimetric methods. The reported assay is very fast and showed an excellent specificity against other diarrhetic toxins. Moreover, we have demonstrated the feasibility of our method for cholera toxin detection in local lake water.     

Colorimetric and bare-eye detection of alkaline earth metal ions based on the aggregation of silver nanoparticles functionalized with thioglycolic acid

We describe a simple and rapid method for colorimetric and bare-eye detection of the alkaline earth metal ions Mg(II), Ca(II), Sr(II) and Ba(II) based on the use of silver nanoparticles (AgNPs) functionalized with thioglycolic acid (TGA). The TGA ligand was self-assembled onto the AgNPs to form a probe that undergoes a color change from yellow to orange or red on exposure to the alkaline earth ions. It is presumed that the color change is a result of the aggregation of the AgNPs caused by the interaction of the bivalent ions with the carboxy groups on the AgNPs. The color change can be used for bare-eye and colorimetric determination of the alkaline earth metal ions, for example to rapidly determine water hardness.

Development of a multiresidue method for analyzing herbicide and fungicide residues in bovine milk based on solid-phase extraction and liquid chromatography-tandem mass spectrometry

The adverse effect of reactive chemical residues on the quality of drug products has necessitated the determination of low-molecular-weight aldehydes in pharmaceutical excipients. An analytical methodology for the detection of trace amounts of C1-C8 aliphatic aldehydes and benzaldehyde in excipients is described. The proposed procedure is based on the derivatization of aldehydes in aqueous solution with O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride (PFBHA), followed by static headspace gas chromatographic (SHS-GC) analysis of PFBHA aldehyde oximes with negative chemical ionization (NCI) MS detection. The method developed was demonstrated to be simple, selective, sensitive, and was successfully applied to the screening of aldehydes at sub-microg/g levels in over 30 typical excipients. The most abundant aldehydes found in the samples were formaldehyde and acetaldehyde, for which a rapid and reliable routine quantification method by readily available SHS-GC instrumentation coupled with flame-ionization detection was also developed and validated.     

Unmodified and positively charged gold nanoparticles for sensitive colorimetric detection of folate receptor via terminal protection of small molecule-linked ssDNA

The detection of protein/small molecule interactions plays important roles in drug discovery and protein/metabolite interactions in biology. In this work, by coupling the terminal protection of small molecule-linked ssDNA strategy with the unmodified and positively charged gold nanoparticle ((+)AuNP) nanoprobes, we have developed a sensitive and simple colorimetric sensor for the detection of folate receptor, a highly expressed protein in many kinds of malignant tumors. The target folate receptor binds the folate moieties of the folate-linked ssDNA through high affinity interactions and protects the protein-bound ssDNA from digestion by exonuclease I. The protected ssDNA thus adsorbs the ((+)AuNP) through electrostatic interactions, leading to a red-to-blue color change of the sensing solution for sensitive colorimetric detection of folate receptor at the sub-nanomolar level. Besides, this colorimetric sensor shows high selectivity toward folate receptor against other control proteins. The developed sensor avoids the modification/conjugation of the AuNP nanoprobes and the involvement of any expensive instruments for signal transduction in protein detection. Featured with these obvious advantages, the colorimetric sensor strategy demonstrated herein can be easily expanded for sensitive and convenient detection of various protein/small molecule interactions.     

Colorimetric determination of Cu2+ in simulated wastewater using naphthalimide-based Schiff base

A new Cu²⁺-selective colorimetric sensor was developed by combining the chromophore 3-hydroxynaphthalimide with diaminomaleonitrile. The sensor showed Cu²⁺-selective colorimetric signaling behavior in dimethylsulfoxide, indicated by a solution color change from yellow to pink, which was readily discernible without any external devices. Practical application of the sensor to the detection of Cu²⁺ in an aqueous solution containing other environmentally relevant metal ions by selective two-phase liquid-liquid extraction with ethyl acetate was possible. Particularly, extractive signaling of Cu²⁺ in simulated semiconductor wastewater with a readily-usable smartphone as a colorimetric data capture and analysis tool was successfully conducted.