Real-life Samples Research Articles

A highly selective multifunctional naphthalene-labeled polymer sensor for Cu2+ and Fe3+ ions in aqueous medium

In this work, the detection of Cu2+ and Fe3+ with naphthalene labeled poly(acrylic acid) (PAA150Np3) was investigated. Other metal ions such as Ag+, Li+, K+, Na+, Ba2+, Mg2+, Ca2+, Zn2+ and Ni2+ were also considered to analyze the sensor performance. The fluorescence quenching of the naphthalene (Np) graft was assessed from the emission spectra and the fluorescence decays of PAA150Np3 in the presence of Cu2+ or Fe3+. The Stern-Volmer and Hill constants, as well as the detection limits of the studied ions were obtained considering the emissions of both the monomer and the excimer of Np. The polymer conformation was investigated by changing the metal ion concentration or the pH. The polymeric sensor showed high selectivity and sensitivity for Cu2+ or Fe3+. A static mechanism of fluorescence quenching was unveiled for the Np graft. A more stable complex formed between PAA150Np3 and Fe3+, as compared to the counterpart system with Cu2+. The sensor’s performance, including detection limit and selectivity of Cu2+ or Fe3+ ions, is higher than of most currently reported sensors. The study shows that the multifunctional fluorescent polymer sensor has the potential to be used in real-life samples, in bio-systems and environmental applications.

Synthesis and fluorescence properties of a two-dimensional Cd-complex for the ratiometric fluorescence detection of Zn2+ ions

The two-dimensional complex [Cd3(L)(2,2'-bpy)2]n (1) was synthesized solvothermally from 4,5-di(3,5-dicarboxylphenoxy)phthalic acid (H6L) and 2,2'-bipyridine (2,2'-bpy) and fully characterized by elemental analysis, infrared spectroscopy, single crystal and powder X-ray diffraction. Complex 1 displays high stability in water and resistance towards acidic and basic media. Fluorescence studies revealed that it may be acted as a ratiometric fluorescence probe to detect Zn2+ ions in water with a superior detection limit of 3.48 nM. The fluorescence recognition mechanism stems from weak interactions between Zn2+ ions and complex 1. Its pronounced stability and recyclability suggest that the new material may be used for high-precision detection of Zn2+ ions in real-life aqueous samples, even under acidic and basic conditions.

Rhinitis Control and Medication Use in a Real-World Sample of Patients With Persistent Rhinitis or Rhinosinusitis: A Community Pharmacy Study

BackgroundLittle is known about rhinitis control in real-life, nor about the contribution of treatment-related and patient-related factors. ObjectiveThis study aimed to examine the level of rhinitis control and rhinitis medication utilization in patients with persistent rhinitis, and to identify predictors of rhinitis control. MethodsA cross-sectional observational study was conducted in patients with persistent rhinitis recruited in community pharmacies. Participants completed the Rhinitis Control Assessment Test (RCAT), and a questionnaire on patient/rhinitis characteristics, and rhinitis medication use. A visual analogue scale (VAS) for nasal symptoms was also completed. Pharmacy dispensing data was used to calculate adherence to intranasal glucocorticoids. Nasal spray technique was evaluated using a standardized checklist. Predictors of rhinitis control were explored using a linear regression model. ResultsA total of 1514 patients, recruited in 215 pharmacies, participated in the study (mean age 48.7 years, 62% female). Almost 60% exhibited suboptimal rhinitis control (RCAT ≤ 21/30). A 50mm cut-off on the VAS yielded 78.1% sensitivity to identify suboptimal rhinitis control. Participants most frequently used intranasal glucocorticoids (55.6%) and intranasal decongestants (47.4%). Only 10.3% of current nasal spray users demonstrated perfect technique. More than half (54.8%) of glucocorticoid users were identified as underadherent. Female sex, self-reported nasal hyperreactivity, active asthma, and use of oral/intranasal decongestants or nasal saline were identified as predictors of worse rhinitis control. ConclusionSuboptimal rhinitis control was common in this real-life sample of persistent rhinitis patients. Improving use of rhinitis medication may be key to increase disease control.

Using L. minor and C. elegans to assess the ecotoxicity of real-life contaminated soil samples and their remediation by clay- and carbon-based sorbents

Toxic substances, such as polycyclic aromatic hydrocarbons (PAHs) and heavy metals, can accumulate in soil, posing a risk to human health and the environment. To reduce the risk of exposure, rapid identification and remediation of potentially hazardous soils is necessary. Adsorption of contaminants by activated carbons and clay materials is commonly utilized to decrease the bioavailability of chemicals in soil and environmental toxicity in vitro, and this study aims to determine their efficacy in real-life soil samples. Two ecotoxicological models (Lemna minor and Caenorhabditis elegans) were used to test residential soil samples, known to contain an average of 5.3, 262, and 9.6 ppm of PAHs, lead, and mercury, for potential toxicity. Toxicity testing of these soils indicated that 86% and 58% of soils caused ≤50% inhibition of growth and survival of L. minor and C. elegans, respectively. Importantly, 3 soil samples caused ≥90% inhibition of growth in both models, and the toxicity was positively correlated with levels of heavy metals. These toxic soil samples were prioritized for remediation using activated carbon and SM-Tyrosine sorbents, which have been shown to immobilize PAHs and heavy metals, respectively. The inclusion of low levels of SM-Tyrosine protected the growth and survival of L. minor and C. elegans by 83% and 78%, respectively from the polluted soil samples while activated carbon offered no significant protection. These results also indicated that heavy metals were the driver of toxicity in the samples. Results from this study demonstrate that adsorption technologies are effective strategies for remediating complex, real-life soil samples contaminated with hazardous pollutants and protecting natural soil and groundwater resources and habitats. The results highlight the applicability of these ecotoxicological models as rapid screening tools for monitoring soil quality and verifying the efficacy of remediation practices.

Highly Sensitive and Rapid Screening Technique for the Detection of Organophosphate Pesticides and Copper Compounds Using Bifunctional Recombinant TrxA-PvCarE1.

Enabling the detection of organophosphate pesticide (OP) residues through enzyme inhibition-based technology is crucial for ensuring food safety and human health. However, the use of acetylcholinesterase, the primary target enzyme for OPs, isolated from animals in practical production poses challenges in terms of sensitivity and batch stability. To address this issue, we identified a highly sensitive and reproducible biorecognition element, TrxA-PvCarE1, derived from red kidney beans and successfully overexpressed it in Escherichia coli. The resulting recombinant TrxA-PvCarE1 exhibited remarkable sensitivity toward 10 OPs, surpassing that of commercial acetylcholinesterase. Additionally, this approach demonstrated the capability to simultaneously detect copper compounds with high sensitivity, expanding the range of pesticides detectable using the traditional enzyme inhibition method. Spiking recovery tests conducted on cowpea and carrot samples verified the suitability of the TrxA-PvCarE1-based technique for real-life sample analysis. In summary, this study highlights a promising comprehensive candidate for the rapid detection of pesticide residues.

Self-powered biosensing platform for Highly sensitive detection of soluble CD44 protein

In this study, a self-powered biosensor based on an enzymatic biofuel cell was proposed for the first time for the ultrasensitive detection of soluble CD44 protein. The as-prepared biosensor was composed of the co-exist aptamer and glucose oxidase bioanode and bilirubin oxidase modified biocathode. Initially, the electron transfer from bioanode to biocathode was hindered due to the presence of the aptamer with high insulation, generating a low open-circuit voltage (EOCV). Once the target CD44 protein was present, it was recognized and captured by the aptamer at the bioanode, thus the interaction between the target CD44 protein and the immobilized aptamer caused the structural change at the surface of the electrode, which facilitated the transfer of electrons. The EOCV showed a good linear relationship with the logarithm of the CD44 protein concentrations in the range of 0.5–1000 ng mL−1 and the detection limit was 0.052 ng mL−1 (S/N = 3). The sensing platform showed excellent anti-interference performance and outstanding stability that maintained over 97% of original EOCV after 15 days. In addition, the relative standard deviation (1.40–1.96%) and recovery (100.23–101.31%) obtained from detecting CD44 protein in real-life blood samples without special pre-treatment indicated that the constructed biosensor had great potential for early cancer diagnosis.

A chromogenic anthraimidazoldione probe for ratiometric analysis of Hg2+ exclusively at mesoscopic interface: Screening of real-life biological samples

In the present work, we have synthesized amphiphilic anthraimidazoldione derivative that can form nanoassembly in the aqueous medium. The π-conjugated backbone with facile intramolecular charge transfer from the substituted aryl residue to anthraquinone unit attributed to the profound orange color. Despite having the metal ion chelating aminoethyl acetamide unit, the compound showed no interaction with metal ions in the aqueous medium. However, a highly selective color-changing response, from orange to yellow (Δλ ∼52 nm), was observed upon addition of Hg2+ ion at micellar interface. Also, a turn-on fluorescence response (∼5.2-fold) was witnessed with Hg2+. It was observed that in addition to hydrophobic microenviroment, the orientation of molecules at water-surfactant interface also responsible for the chromogenic response towards Hg2+ ion. The mechanistic investigation indicated that Hg2+ ion coordinates with the aminoethyl acetamide unit, resulting restriction in the extent of intramolecular charge transfer. Considering such highly ratiometric response, the present system has been employed for analysis of Hg2+ ion in diluted urine and blood serum samples. The high recovery values (95.4 % to 104.3 %) with relatively low standard deviations (< 4.2 %) indicated that the present system is fairly successful in screening of complex real-life samples. Finally, we have designed low-cost, reusable, chemically modified paper strips for on-location, rapid analysis of mercury ions.

Quantification of 2,4-dichlorophenoxyacetic acid in environmental samples using imprinted polyethyleneimine with enhanced selectivity as a selective adsorbent in ambient plasma mass spectrometry

Detection and quantification of various organic chemicals in the environment is critical to track their fate and control their levels. 2,4-Dichlorophenoxyacetic acid (2,4-D) is a widely applied phenoxy herbicide with potential toxicity to fish and other aquatic organisms. In this study, we address the need for improved detection of 2,4-D by introducing a novel analytical method for its quantification. This method relies on the selective extraction of 2,4-D using MIPs and their subsequent direct analysis using ambient plasma mass spectrometry. During the synthesis, MIPs with various degrees of glycidol (GLY) functionalization were obtained. Experimental data showed that MIPs with no GLY functionalization displayed the highest adsorption capacity. Conversely, MIPs with 30% GLY functionalization exhibited the greatest selectivity for 2,4-D, rendering them valuable for extraction of 2,4-D even in the presence of other contaminants. Finally, the obtained MIPs were applied for quantification of 2,4-D in various water samples through direct analysis using a specially designed ambient plasma mass spectrometry setup. This approach improved the detection limits by 200-fold compared to pure solution analysis. The quantification of 2,4-D in river water samples yielded highly satisfactory recoveries, demonstrating the effective utility of the proposed analytical setup for real-life water sample analysis.

Carbon nanotubes in high internal phase emulsion polymer composite for packed-cartridge micro-solid-phase extraction of fluoroquinolones in urine

Aim of this study stands in the evaluation of a carbon nanotubes-based polymerized high internal phase emulsion composite (CNT/polyHIPE) as sorptive phase in biological sample preparation. A micro-solid-phase extraction procedure (µSPE) was developed for trace fluoroquinolone (FQ) antimicrobials, namely Ciprofloxacin, Levofloxacin, Lomefloxacin, Moxifloxacin, Norfloxacin and Sparfloxacin, in human urine samples. PolyHIPEs modified by incorporation of different concentrations of nanotubes (0.2–0.8 wt %) were one-pot synthesized and applied in the packed-cartridge setting. The sorption affinity for the drugs was investigated in tap water and buffered aqueous solutions, demonstrating the key role of the nanotubes embedded in the polymer. The 0.5 wt % CNT composite was selected to develop a straightforward µSPE procedure directly in raw urine (1 mL sample), followed by HPLC-MS/MS. Targets were retained on the sorbent at near neutral pH and, after an aqueous washing (0.1 % v/v formic acid), eluted in a single-step with 4 % v/v ammonia aqueous solution (15 % v/v acetonitrile), thus combining extraction and clean-up. The method allowed accurate quantification of FQs, as evidenced by the recoveries (74–116 %, n = 3) obtained on blank pooled urine samples spiked with 40, 75, 150 µg L−1, accompanied by good inter-day precision (RSD < 14 %, n = 3). To confirm the applicability of the analytical method, some real-life blind samples were processed as a proof of concept.

Functionalized cyanostilbene-based nano-AIEgens: multipoint binding interactions for improved sensing of gallic acid in real-life food samples.

Cyano-substituted stilbene (CSS) derivatives have been synthesized that can form luminescent nanoscopic assemblies in an aqueous medium. The optical properties of such materials, as governed by the relative ratios of their monomer and aggregated forms, are found to be susceptible to pH and temperature of the medium. The compound with boronic acid attached at the terminal positions shows a turn-on fluorescence response (LOD: 15.4 ppb) with gallic acid (GA). The mechanistic studies indicate that the 1,2-diol unit of GA is involved in ester formation with the boronic acid residue, while the carboxylic end engages in hydrogen bonding interaction with the nitrile unit. Such multi-point binding interaction provides better selectivity over other structurally similar analytes. Moreover, the distinct aggregation properties of such boronate ester derivatives are responsible for the GA-specific optical response. The sensory system has been utilized for the determination of the levels of GA derivatives in tea (green tea and black tea) and various fruit (mango, orange, guava, pomegranate) extracts. In all cases, the estimated values of GAE were found to be in the same range reported by others. Finally, low-cost, chemically-modified paper strips have been designed for rapid, on-location detection of GA.

Exploring the synergistic effect of aggregation and hydrogen bonding: a fluorescent probe for dual sensing of phytic acid and uric acid.

We synthesized an unoxidized bis-indolyl methane (BIM) derivative (probe 1) comprising of tetraphenylethylene (TPE) as the signalling moiety. The amphiphilic probe could form self-assembled nanoscopic aggregates in the aqueous medium. The emission of 1 in non-polar solvents originates from the LE state, while in polar solvents, it is dominated by TICT. Moreover, probe 1 exhibited a 'turn-on' fluorescence response for both uric acid (with a blue shift in emission maxima) and phytic acid (with a red shift in emission maxima). Therefore, the present system provides an exceptional opportunity to distinguish between phytic acid and uric acid by considering two different emission channels. Mechanistic investigations revealed that both H-bonding and electrostatic interactions between the probe and analytes could effectively cause restricted intramolecular rotations, leading to a turn-on response. Additionally, in the case of phytic acid, larger aggregates were observed with prominent CT characteristics. The change in the extent of charge transfer interaction in the formed adducts resulted in distinct fluorescence responses with phytic acid and uric acid. Furthermore, we explored the applicability of the present system in the screening of real-life samples, such as uric acid in urine samples and phytic acid in grains. The LOD for phytic acid and uric acid was found to be ∼5.48 nM and 10.4 nM, respectively. The quantitative nature of the system was confirmed, showing promising results in terms of recovery values (between 95.6% and 104.2%) and detection limits. Additionally, we also employed handy paper strips for the on-site monitoring of phytic acid and uric acid, thereby eliminating the need for complex instrumentation or trained technicians.

Determination of MCPA in environmental samples using an analytical on-line system based on imprinted poly[2-(3-butenyl)-2-oxazoline] and ambient ionization mass spectrometry

Monitoring and quantifying organic chemicals in the environment play a vital role in understanding their behavior and ensuring environmental safety. MCPA (2-methyl-4-chlorophenoxyacetic acid) is a commonly used phenoxy herbicide that poses potential risks to aquatic life. In this study, we present an innovative analytical approach for MCPA quantification, employing molecularly imprinted polymers (MIPs) for selective extraction and ambient plasma mass spectrometry for direct on-line analysis. To synthesize functional MIPs, we employed a post-polymerization strategy based on a thiol-ene click reaction conducted on a short-chain poly[2-(3-butenyl)-2-oxazoline] (poly(ButenOx)) that allowed attachment of 3-mercaptopropionic acid (MPA) to polymer side chains. The incorporation of MPA groups into polymer structure enabled the attainment of elevated maximum adsorption capacities and enhanced selectivity towards MCPA. Utilizing a specially designed ambient plasma mass spectrometry setup, we successfully quantified MCPA in water samples, achieving significantly improved detection limits compared to conventional solution-based analysis, whereas the quantification of MCPA in real-life river water samples demonstrated excellent recoveries. In conclusion, this novel analytical method employing MIPs and ambient plasma mass spectrometry provides an effective and sensitive approach for accurate MCPA detection in environmental water samples. The technique holds promise for facilitating reliable monitoring and management of MCPA levels in aquatic ecosystems.

Assessment of Humic and Fulvic Acid Sorbing Potential for Heavy Metals in Water

Pollution of water sources with heavy metals is a pressing environmental issue. To this end, various procedures are being used to remediate water, including sorption. The aim of this study was to investigate the effectiveness of humic acids (HAs) and fulvic acids (FAs) for the removal of metals from water. Specifically, HA and FA were examined for their potential to be used as sorbent materials for 26 heavy metals, alkali metals, and alkaline earth metals. HA and FA were isolated from lignite samples from two mines (Mavropigi mine and South Field mine, Kozani, West Macedonia, Greece). Experiments were carried out using natural mineral water without pH adjustment, so as to gain a better overview of the sorption efficiency in real-life samples. The results showed that FAs were able to sorb most of the examined metals compared to HAs. Several metals such as Ba (34.22–37.77%), Ca (99.12–99.58%), and Sr (97.89–98.12%) were efficiently sorbed when 900 ppm of FAs from both sources were used but were not sorbed by HAs from any source (≤0.1%). Due to the functional groups on the surface of FA, it is plausible to conclude that it can remove more metals than HA. Meanwhile, lignite from the South Field mine was found to be more efficient for the sorption efficiency in lower concentrations (300–600 ppm), whereas lignite from the Mavropigi mine was more effective in higher concentrations (900 ppm). For instance, higher removal rates were observed in Mo (62.84%), Pb (56.81%), and U (49.22%) when 300 ppm of HAs of South Field mine were used, whilst the employment of 900 ppm of HAs from Mavropigi mine led to high removal rates of As (49.90%), Se (64.47%), and Tl (85.96%). The above results were also reflected in a principal component analysis, which showed the dispersion of the metal parameters near to or far from the HA and FA parameters depending on their sorption capacity. Overall, both HA and FA could be effectively utilized as sorbent materials for metal removal from water samples. The results of the research indicate a potential application to the remediation of water from metals under dynamic conditions in order to protect public health.

A sensitive signal off photoelectrochemical aptasensor based on CuO nanosheets @Au nanoflowers for the detection of chloramphenicol

A signal off type photoelectrochemical (PEC) aptasensor was constructed for the sensitive detection of chloramphenicol based on CuO nanosheets (CuO NSs) and gold nanoflowers (Au NFs) modified indium tin oxide (ITO) electrode. CuO NSs was p-type photoactive semiconductor materials, which had narrow band gap and high absorption rate of visible light. After combining with Au NFs, the composite CuO NSs@Au NFs produced a strong cathodic photocurrent for the excellent electron conductivity, large specific surface area and Surface Plasmon Resonance effect (SPR) of Au NFs. At the same time, Au NFs provided a binding site for aptamer, which greatly improved the sensitivity of the constructed sensing platform. After the target chloramphenicol (CAP) was specifically captured by the aptamers on the electrode, the formed bioconjugates seriously hindered the transfer of electrons and the absorption of light and caused a reduced photocurrent. For the detection of CAP, this signal off type PEC aptasensor had a linear range of 5 pM-300 nM and a limit of detection of 49.9 fM (S/N = 3) with good stability, selectivity and reproducibility. Meanwhile, the method had satisfactory recovery results in the detection of CAP in real-life samples such as milk, tap water, honey and chloramphenicol eye drops.

AI to Train AI: Using ChatGPT to Improve the Accuracy of a Therapeutic Dialogue System

In this work, we present the use of one artificial intelligence (AI) application (ChatGPT) to train another AI-based application. As the latter one, we show a dialogue system named Terabot, which was used in the therapy of psychiatric patients. Our study was motivated by the fact that for such a domain-specific system, it was difficult to acquire large real-life data samples to increase the training database: this would require recruiting more patients, which is both time-consuming and costly. To address this gap, we have employed a neural large language model: ChatGPT version 3.5, to generate data solely for training our dialogue system. During initial experiments, we identified intents that were most often misrecognized. Next, we fed ChatGPT with a series of prompts, which triggered the language model to generate numerous additional training entries, e.g., alternatives to the phrases that had been collected during initial experiments with healthy users. This way, we have enlarged the training dataset by 112%. In our case study, for testing, we used 2802 speech recordings originating from 32 psychiatric patients. As an evaluation metric, we used the accuracy of intent recognition. The speech samples were converted into text using automatic speech recognition (ASR). The analysis showed that the patients’ speech challenged the ASR module significantly, resulting in deteriorated speech recognition and, consequently, low accuracy of intent recognition. However, thanks to the augmentation of the training data with ChatGPT-generated data, the intent recognition accuracy increased by 13% relatively, reaching 86% in total. We also emulated the case of an error-free ASR and showed the impact of ASR misrecognitions on the intent recognition accuracy. Our study showcased the potential of using generative language models to develop other AI-based tools, such as dialogue systems.

Fast and Accurate Multiplex Identification and Quantification of Seven Genetically Modified Soybean Lines Using Six-Color Digital PCR.

The proliferation of genetically modified organisms (GMOs) presents challenges to GMO testing laboratories and policymakers. Traditional methods, like quantitative real-time PCR (qPCR), face limitations in quantifying the increasing number of GMOs in a single sample. Digital PCR (dPCR), specifically multiplexing, offers a solution by enabling simultaneous quantification of multiple GMO targets. This study explores the use of the Naica six-color Crystal dPCR platform for quantifying five GM soybean lines within a single six-plex assay. Two four-color assays were also developed for added flexibility. These assays demonstrated high specificity, sensitivity (limit of detection or LOD < 25 copies per reaction) and precision (bias to an estimated copy number concentration <15%). Additionally, two approaches for the optimization of data analysis were implemented. By applying a limit-of-blank (LOB) correction, the limit of quantification (LOQ) and LOD could be more precisely determined. Pooling of reactions additionally lowered the LOD, with a two- to eight-fold increase in sensitivity. Real-life samples from routine testing were used to confirm the assays' applicability for quantifying GM soybean lines in complex samples. This study showcases the potential of the six-color Crystal dPCR platform to revolutionize GMO testing, facilitating comprehensive analysis of GMOs in complex samples.

Proposing new clustering-based algorithms for the multi-skilled resource-constrained multi-project scheduling problem with resource leveling adjustments

PurposeThe target of this research is to develop a mathematical model which combines the Resource-Constrained Multi-Project Scheduling Problem (RCMPSP) and the Multi-Skilled Resource-Constrained Project Scheduling Problem (MSRCPSP). Due to the importance of resource management, the proposed formulation comprises resource leveling considerations as well. The model aims to simultaneously optimize: (1) the total time to accomplish all projects and (2) the total deviation of resource consumptions from the uniform utilization levels.Design/methodology/approachThe K-Means (KM) and Fuzzy C-Means (FCM) clustering methods have been separately applied to discover the clusters of activities which have the most similar resource demands. The discovered clusters are given to the scheduling process as priori knowledge. Consequently, the execution times of the activities with the most common resource requests will not overlap. The intricacy of the problem led us to incorporate the KM and FCM techniques into a meta-heuristic called the Bi-objective Symbiosis Organisms Search (BSOS) algorithm so that the real-life samples of this problem could be solved. Therefore, two clustering-based algorithms, namely, the BSOS-KM and BSOS-FCM have been developed.FindingsComparisons between the BSOS-KM, BSOS-FCM and the BSOS method without any clustering approach show that the clustering techniques could enhance the optimization process. Another hybrid clustering-based methodology called the NSGA-II-SPE has been added to the comparisons to evaluate the developed resource leveling framework.Practical implicationsThe practical importance of the model and the clustering-based algorithms have been demonstrated in planning several construction projects, where multiple water supply systems are concurrently constructed.Originality/valueReviewing the literature revealed that there was a need for a hybrid formulation that embraces the characteristics of the RCMPSP and MSRCPSP with resource leveling considerations. Moreover, the application of clustering algorithms as resource leveling techniques was not studied sufficiently in the literature.

Label-free multimodal analysis of copper ions at below permissible exposure limit in the aqueous medium

An anthraimidazoledione based amphiphilic dye molecule was synthesized that shows formation of tuneable charge-transfer state in solution, susceptible to change in pH, polarity and hydrogen bonding ability of the medium. The compound also showed formation of nanoscopic self-assembled structure in water medium. The probe molecule can achieve multimodal detection (colorimetric, fluorimetric and electrochemical) of copper ions as low as 0.3 ppm in the aqueous medium. Addition of copper leads to dose-dependent ratiometric change in solution color from yellow to purple. The mechanistic investigation indicates that the coordination of copper ions was possible via simultaneous engagement of both imidazole nitrogen ends and neighbouring hydroxyl unit. Not only optical property, the changes in microenvironment also influence the selectivity as well as sensitivity of the probe molecule towards Cu2+ ions. Further, the optical probe is used for detection as well as quantification of copper ions in natural water samples without any sample pretreatment. Low-cost, reusable paper strips are developed for rapid, on-location detection of residual Cu2+ in real-life samples.

Circulating tumor DNA-based copy-number profiles enable monitoring treatment effects during therapy in high-grade serous carcinoma

Circulating tumor DNA (ctDNA) analysis has emerged as a promising tool for detecting and profiling longitudinal genomics changes in cancer. While copy-number alterations (CNAs) play a major role in cancers, treatment effect monitoring using copy-number profiles has received limited attention as compared to mutations. A major reason for this is the insensitivity of CNA analysis for the real-life tumor-fraction ctDNA samples. We performed copy-number analysis on 152 plasma samples obtained from 29 patients with high-grade serous ovarian cancer (HGSC) using a sequencing panel targeting over 500 genes. Twenty-one patients had temporally matched tissue and plasma sample pairs, which enabled assessing concordance with tissues sequenced with the same panel or whole-genome sequencing and to evaluate sensitivity. Our approach could detect concordant CNA profiles in most plasma samples with as low as 5% tumor content and highly amplified regions in samples with ∼1% of tumor content. Longitudinal profiles showed changes in the CNA profiles in seven out of 11 patients with high tumor-content plasma samples at relapse. These changes included focal acquired or lost copy-numbers, even though most of the genome remained stable. Two patients displayed major copy-number profile changes during therapy. Our analysis revealed ctDNA-detectable subclonal selection resulting from both surgical operations and chemotherapy. Overall, longitudinal ctDNA data showed acquired and diminished CNAs at relapse when compared to pre-treatment samples. These results highlight the importance of genomic profiling during treatment as well as underline the usability of ctDNA.

Fluorescent Nanoassembly of Tetrazole-Based Dyes with Amphoteric Surfactants: Investigation of Cyanide Sensing and Antitubercular Activity.

Tetrazole-based easily synthesizable fluorogenic probes have been developed that can form self-assembled nanostructures in the aqueous medium. Though the compounds could achieve detection of cyanide ions in apolar solvents, such as, THF, significant interference was observed from other basic anions, such as F-, AcO-, H2PO4-, etc. On the other hand, a highly specific response was observed for CN- ions in the aqueous medium. However, the sensitivity was so poor that it could hardly be useful for real-life sample analysis. Interestingly, the co-assembly of such probe molecules with hydroxyethyl-anchored amphoteric surfactants could drastically improve the sensitivity toward CN- ions in water without dampening their excellent selectivity. Also, it was observed that the degree of fluorescence response for CN- ions depends on the nature of the polyaromatic scaffolds (naphthyl vs anthracenyl), the nature of the surfactant assembly (micelle vs vesicle), etc. The mechanistic investigation indicates the hydrogen bonding interaction between the tetrazole -NH group and cyanide ions in the aqueous medium, which can effectively change the electronics of the tetrazole unit, resulting in alteration in the extent of charge transfer interaction. Then, the biocompatible composite materials (dye-surfactant assemblies at different ratios) were tested for antituberculosis activity. Fortunately, in a few cases, the compositions were found to be as effective as the commercially available antituberculosis drug, ethambutol.