In this report, we successfully engineered a novel probe based on an acceptor-donor-acceptor (A-D-A) architecture featuring dicyanovinyl-substituted thieno[3,2-b]thiophene, termed DCVTT. The designed probe self-assembles into luminous nanoparticles (DCVTT NPs) upon introducing mixed aqueous solutions. These fluorescent nanostructures served as a ratiometric probe for detecting cyanide (CN-) ions in aqueous-based environments, owing to the robust Intramolecular Charge Transfer (ICT) characteristics of DCVTT. The A-D-A substituents in DCVTT significantly enhanced ICT behavior by promoting more efficient electron transfer between the donor and acceptor groups. This improved electron transfer process leads to heightened sensitivity in detection applications. In the case of cyanide (CN) sensing, this enhanced ICT behavior manifests as a strong colorimetric response, allowing for a visible color change before and after interaction with cyanide. Speculation regarding the interaction mechanism between DCVTT and CN- is proposed based on the findings of various experimental analyses. The detection limit (LOD) for DCVTT in identifying CN- is 0.83 nM, significantly lower than the CN- concentration thresholds deemed safe by the World Health Organization (WHO) and the United States Environmental Protection Agency (EPA). Time-Dependent Density Functional Theory (TD-DFT) has been utilized to theoretically analyze the optical properties of DCVTT both before and after the introduction of the CN- ions. A paper-based test strip was developed to demonstrate its practical application to enable efficient qualitative CN- detection by visual inspection. Furthermore, this sensing platform demonstrates highly accurate quantitative detection of CN- in apple seeds. No prior reports have utilized fluorescence techniques to estimate apple seeds' CN levels.
- MeSH
- fluorescenční barviva * chemie MeSH
- fluorescenční spektrometrie metody MeSH
- kolorimetrie metody MeSH
- kyanidy * analýza chemie MeSH
- limita detekce * MeSH
- Malus * chemie MeSH
- nanočástice * chemie MeSH
- semena rostlinná * chemie MeSH
- thiofeny chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- fluorescenční barviva * MeSH
- kyanidy * MeSH
- thiofeny MeSH
Rapid, simultaneous detection of organic chemical pollutants in water is an important issue to solve for protecting human health. This study investigated the possibility of developing an in situ reusable optical sensor capable of selective measurements utilizing a chalcogenide transducer supplemented by a hydrophobic polymer membrane with detection based on evanescent waves in the mid-infrared spectrum. In order to optimise a polyisobutylene hydrophobic film deposited on a chalcogenide waveguide, a zinc selenide prism was utilized as a testbed for performing attenuated total reflection with Fourier-transform infrared spectroscopy. To comply with the levels mentioned in health guidelines, the target detection range in this study was kept rather low, with the concentration range extended from 50 ppb to 100 ppm to cover accidental pollution problems, while targeted hydrocarbons (benzene, toluene, and xylene) were still detected at a concentration of 100 ppb. Infrared measurements in the selected range showed a linear behaviour, with the exception of two constantly reproducible plateau phases around 25 and 80 ppm, which were observable for two polymer film thicknesses of 5 and 10 μm. The polymer was also found to be reusable by regenerating it with water between individual measurements by increasing the water temperature and flow to facilitate reverse exchange kinetics. Given the good conformability of the hydrophobic polymer when coated on chalcogenide photonic circuits and its demonstrated ability to detect organic pollutants in water and to be regenerated afterwards, a microfluidic channel utilising water flow over an evanescent wave optical transducer based on a chalcogenide waveguide and a polyisobutylene (PIB) hydrophobic layer deposited on its surface was successfully fabricated from polydimethylsiloxane by filling a mold prepared via CAD and 3D printing techniques.
- Publikační typ
- časopisecké články MeSH
The droplet deposition methods in Raman spectroscopy have received considerable attention in the field of analytical sensing focusing on effective pre-concentration of the studied analyte (coffee-ring effect or small spots). This review covers different analytical applications of drop-coating deposition Raman scattering (DCDRS) and droplet deposition surface-enhanced Raman scattering (SERS) spectroscopy. Two main advantages of droplet deposition Raman techniques are considered: the drying-induced segregation of the components from the mixtures (such as body fluids) and the sensitivity of detection of various analytically important molecules. Some recent advanced applications, including clinical cancer diagnosis, are discussed and summarized. Finally, the potential and further perspectives of the droplet deposition Raman methods for analytical studies are introduced.
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
Cholesterol plays an important biological role in the body, and its disruption in homeostasis and synthesis has been implicated in several diseases. Mapping the locations of cholesterol is crucial for gaining a better understanding of these conditions. Silver deposition has proven to be an effective method for analyzing cholesterol using mass spectrometry imaging (MSI). We optimized and evaluated thermal evaporation as an alternative deposition technique to sputtering for silver deposition in MSI of cholesterol. A silver layer with a thickness of 6 nm provided an optimal combination of cholesterol signal intensity and mass resolution. The deposition of an ultrathin nanofilm of silver enabled high-resolution MSI with a pixel size of 10 μm. We used this optimized method to visualize the distribution of cholesterol in the senile plaques in the brains of APP/PS1 mice, a model that resembles Alzheimer's disease pathology. We found that cholesterol was evenly distributed across the frontal cortex tissue, with no evidence of plaque-like accumulation. Additionally, we investigated the presence and distribution of cholesterol in myocardial sections of a human heart affected by wild-type ATTR amyloidosis. We identified the presence of cholesterol in areas with amyloid deposition, but complete colocalization was not observed.
- MeSH
- Alzheimerova nemoc metabolismus patologie MeSH
- amyloidní plaky MeSH
- amyloidóza metabolismus patologie MeSH
- cholesterol * analýza chemie MeSH
- lidé MeSH
- mozek metabolismus diagnostické zobrazování MeSH
- myokard metabolismus chemie patologie MeSH
- myši transgenní MeSH
- myši MeSH
- spektrometrie hmotnostní - ionizace laserem za účasti matrice * metody MeSH
- stříbro * chemie MeSH
- teplota MeSH
- volatilizace MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- myši MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- cholesterol * MeSH
- stříbro * MeSH
The popularity and rapid spread of new psychoactive substances is why there is an urgent need for their fast monitoring in saliva in the field with electrodes modified with a selective receptor. Oligomers of electrochemically oxidized 3-aminobenzoic acid that are deposited on the surface of a graphite screen-printed electrode (o-3ABA/G/SPE) is proposed as a selector for the analyte of forensic interest. The oligomeric structure and existence of the zwitterionic form of o-3ABA on the G/SPE surface was confirmed using scanning electron microscopy, Raman spectroscopy and cyclic voltammetry techniques. The equilibrium adsorption constants between o-3ABA and 2-aminoindane (primary amine: Kads(2-AI) = 5.31 × 104) and selected synthetic cathinones (secondary amine: Kads(butylone) = 6.12 × 105, tertiary amines: Kads(MDPV) = 3.41 × 104 and Kads(naphyrone) = 1.01 × 104) were estimated using the electrochemical impedance spectroscopy (EIS) technique. The EIS technique was applied for determining a 1.0 μM concentration of 2-AI (RSD 3.5-4.0%) and butylone (RSD 4.9-6.4%) in the model and oral fluid samples.
- Publikační typ
- časopisecké články MeSH
The default choice of mobile phase acidifier for bottom-up LC-MS proteomic analyses is 0.10% formic acid because of its decent acidity, decent ion pairing ability, and low suppression of electrospray ionization. In recent years, state-of-the-art columns have been designed specifically to provide efficient separation even when using an MS-friendly mobile phase of low ionic strength. Despite this, no attempts have been made to improve the sensitivity of the MS-based analytical methods by reducing the amount of formic acid in the mobile phase. In this study, we evaluated the effect of reduced formic acid concentration in the mobile phase on the chromatographic behavior and MS response of peptides when separated using columns packed with a C18 stationary phase with a positively charged surface. Using 0.01% formic acid in the mobile phase maintained excellent chromatographic performance and increased MS signal response compared to the standard of 0.10%. The enhanced MS response translated to about 50% improved peptide identifications depending on the complexity and amount of sample injected. The increased retention of peptides at a reduced formic acid concentration was directly proportional to the number of acidic residues in the peptide sequence. The study was carried out by covering a spectrum of protein samples with varied complexity using analytical flow, micro-, and nanoflow regimes to expand the applicability in routine practice.
The study demonstrates that a combination of plasmonic nanostructures and artificial receptors can be applied for sensing small molecular species. Gold nanoshells containing magnetic cores are used as the SERS-active substrates, which opens the way for the development of multimodal contrast agents with applicability extended to sensing or for the separation of analytes by magnetic solid-phase extraction. Disubstituted ureas forming hydrogen-bonded complexes with certain anions can be employed as molecular sensors. In this case study, gold nanoshells with silica-coated Mn-Zn ferrite cores were prepared by a multistep procedure. The nanoshells were co-functionalized with an N-(4-mercaptophenyl)-N'-(4-nitrophenyl)urea sensor synthesized directly on the gold surface, and with 4-nitrothiophenol, which is adopted as an internal standard. SERS measurements were carried out with acetonitrile solutions of tetrabutylammonium fluoride (Bu4NF) over a concentration range of 10-10-10-1 mol L-1. The spectral response of the sensor is dependent on the fluoride concentration in the range of 10-5-10-1 mol L-1. To investigate further the SERS mechanism, a model sensor, N-(4-bromophenyl)-N'-(4-nitrophenyl)urea, was synthesized and used in Raman spectroscopy with solutions of Bu4NF, up to a molar ratio of 1 : 20. The spectra and the interactions between the sensors and fluoride anions were also studied by extensive DFT computations.
- Publikační typ
- časopisecké články MeSH
More than one fifth of the world's population suffers from liver cirrhosis or other chronic liver diseases. Unfortunately, some of them will inevitably develop hepatocellular carcinoma (HCC), due to the vast majority of HCC cases arising against the background of liver cirrhosis. Despite this clearly identified high-risk group, the lack of early diagnostic options causes HCC mortality to approach its incidence. As opposed to many types of cancer, the incidence of HCC is expected to grow in the coming decades, which makes the search for an effective early diagnostic option a pressing necessity. This study presents evidence that blood plasma analysis employing a combination of chiroptical and vibrational spectroscopic methods might be the key to the improvement of the current status. One hundred samples of patients with HCC and controls with cirrhosis were classified using principal component analysis together with a random forest algorithm. Differentiation of the specific spectral patterns of the studied groups was successful in more than 80%, indicating the prospect of including spectroscopy in the screening of high-risk groups, such as patients with cirrhosis.
- MeSH
- hepatocelulární karcinom * diagnóza MeSH
- incidence MeSH
- jaterní cirhóza diagnóza MeSH
- lidé MeSH
- nádory jater * diagnóza patologie MeSH
- rizikové faktory MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
Early detection and accurate diagnosis of colorectal carcinoma are crucial for successful treatment, yet current methods can be invasive and even inaccurate in some cases. In this work, we present a novel approach for in vivo tissue diagnostics of colorectal carcinoma using Raman spectroscopy. This almost non-invasive technique allows for fast and accurate detection of colorectal carcinoma and its precursors, adenomatous polyps, enabling timely intervention and improved patient outcomes. Using several methods of supervised machine learning, we were able to achieve over 91% accuracy in distinguishing colorectal lesions from healthy epithelial tissue and more than 90% classification accuracy for premalignant adenomatous polyps. Moreover, our models enabled the discrimination of cancerous and precancerous lesions with a mean accuracy of almost 92%. Such results demonstrate the potential of in vivo Raman spectroscopy to become a valuable tool in the fight against colon cancer.
- MeSH
- adenomové polypy * diagnóza patologie MeSH
- kolorektální nádory * MeSH
- lidé MeSH
- nádory tračníku * diagnóza MeSH
- prekancerózy * MeSH
- Ramanova spektroskopie metody MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
Single-benzene fluorophores are bright and the smallest fluorochromes known so far. In single-benzene fluorophores, the fluorescence is mediated by the push/pull effect of substituting groups. Despite a plethora of advantageous properties, this group of molecules has not been extensively studied for design of high-performance fluorescent sensors of catalytic or enzymatic activities. Thus, herein, new fluorescent probes based on the Tsuji-Trost reaction were developed for the selective detection of palladium and other transition metals (platinum and gold) in an aqueous/organic mixed solvent with the sensitivity down to 2.5 nM (for palladium). The relative flexibility in the synthesis of these probes allows for facile color tuning of the emitted fluorescence. In this study, we have successfully utilized a yellow emission variant for sensitive detection of palladium under cell-free conditions and in living cells, validating its possible applicability for high-throughput optical sensing of catalysts for bioorthogonal chemistry under physiological conditions.
- MeSH
- benzen MeSH
- fluorescenční barviva chemie MeSH
- palladium * chemie MeSH
- přechodné kovy * MeSH
- rozpouštědla MeSH
- viabilita buněk MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- benzen MeSH
- fluorescenční barviva MeSH
- palladium * MeSH
- přechodné kovy * MeSH
- rozpouštědla MeSH
