Quantum Dots in Peroxidase-like Chemistry and Formamide-Based Hot Spring Synthesis of Nucleobases.

Quantum dots (QDs) are usually seen as artificial semiconductor particles exhibiting optical and electronic properties interesting for nanotechnological applications. However, they may also play a role in prebiotic chemistry. Starting from zinc acetate, cadmium acetate, and mercaptosuccinic acid, we demonstrate the formation of ZnCd QDs upon UV irradiation in prebiotic liquid formamide. We show that ZnCd QDs are able to increase the yield of RNA nucleobase synthesis from formamide up to 300 times, suggesting they might have served as universal catalysts in a primordial milieu. Based on the experimentally observed peroxidase-like activity of ZnCd QDs upon irradiation with visible light, we propose that QDs could be relevant to a broad variety of processes relating to the emergence of terrestrial life.

Detection of pesticides in food products using paper-based devices by UV-induced fluorescence spectroscopy combined with molecularly imprinted polymers.

In this proof-of-concept study, we explore the detection of pesticides in food using a combined power of sensitive UV-induced fingerprint spectroscopy with selective capture by molecularly imprinted polymers (MIPs) and portable cost-effective paper-based analytical devices (PADs). The specific pesticides used herein as model compounds (both pure substances and their application products for spraying), were: strobilurins (i.e. trifloxystrobin), urea pesticides (rimsulfuron), pyrethroids (cypermethrine) and aryloxyphenoxyproponic acid herbicides (Haloxyfop-methyl). Commercially available spraying formulations containing the selected pesticides were positively identified by MIP-PADs swabs of sprayed apple and tomato. The key properties of MIP layer - imprinting factor (IF) and selectivity factor (α) were characterized using trifloxystrobin (IF-3.5, α-4.4) was demonstrated as a potential option for in-field application. The presented method may provide effective help with in-field testing of food and reveal problems such as false product labelling.

Mapping of MeLiM melanoma combining ICP-MS and MALDI-MSI methods.

Here we developed a powerful tool for comprehensive data collection and mapping of molecular and elemental signatures in the Melanoma-bearing Libechov Minipig (MeLiM) model. The combination of different mass spectrometric methods allowed for detail investigation of specific melanoma markers and elements and their spatial distribution in tissue sections. MALDI-MSI combined with HPLC-MS/MS analyses resulted in identification of seven specific proteins, S100A12, CD163, MMP-2, galectin-1, tenascin, resistin and PCNA that were presented in the melanoma signatures. Furthermore, the ICP-MS method allowed for spatial detection of zinc, calcium, copper, and iron elements linked with the allocation of the specific binding proteins.

Targeted volatolomics of human monocytes: Comparison of 2D-GC/TOF-MS and 1D-GC/Orbitrap-MS methods.

Blood is a complex biological matrix providing valuable information on nutritional, metabolic, and immune status. The detection of blood biomarkers requires sensitive analytical methods because analytes are at very low concentrations. Peripheral blood monocytes play a crucial role in inflammatory processes, and the metabolites released by monocytes during these processes might serve as important signalling molecules and biomarkers of particular physiological states. Headspace solid-phase microextraction (HS-SPME) combined with two different mass spectrometric platforms, two-dimensional (2D) gas chromatography coupled to time-of-flight mass spectrometry (2D-GC/TOF-MS) and one-dimensional gas chromatography coupled to Orbitrap mass spectrometry (GC/Orbitrap-MS), were applied for the investigation of volatile organic compounds (VOCs) produced by human peripheral blood monocytes. An optimized method was subsequently applied for the characterization of changes in VOCs induced by lipopolysaccharides (LPS) and zymosan (ZYM) stimulation. Overall, the 2D-GC/TOF-MS and the 1D-GC/Orbitrap-MS analyses each yielded about 4000 and 400 peaks per sample, respectively. In total, 91 VOCs belonging to eight different chemical classes were identified. The samples were collected in two fractions, conditioned media for monitoring extracellularly secreted molecules and cell pellet samples to determine the intracellular composition of VOCs. Alcohols, ketones, and hydrocarbons were the main chemical classes of the metabolic profile identified in cell fractions. Aldehydes, acids and cyclic compounds were characteristic of the conditioned media fraction. Here we demonstrate that HS-SPME-2D-GC/TOF-MS is more suitable for the identification of specific VOC profiles produced by human monocytes than 1D-GC/Orbitrap-MS. We define the signature of VOCs occurring early after monocyte activation and characterise the signalling compounds released by immune cells into media.

UV-induced Zn:Cd/S quantum dots in-situ formed in the presence of thiols for sensitive and selective fluorescence detection of thiols.

In this work, we explored a new approach to a simple and sensitive fluorescence detection of thiols. The approach takes advantage of an in-situ formation of UV light-induced fluorescent nanoparticles (ZnCd/S quantum dots), while utilizing the thiol group of the analyte as a capping agent. The selectivity is ensured by the selective isolation of the thiol analyte by a polydopamine molecularly imprinted polymeric (MIP) layer. Based on this approach, a method for determination of thiols was designed. Key experimental parameters were optimized, including those of molecular imprinting and of effective model thiol molecule (L-cysteine) isolation. The relationship between the fluorescence intensity of ZnCd/S quantum dots and the concentration of L-cysteine in the range of 12-150 µg/mL was linear with a detection limit of 3.6 µg/mL. The molecularly imprinted polymer showed high absorption mass capacity (1.73 mg/g) and an excellent selectivity factor for L-cysteine compared to N-acetyl-L-cysteine and L-homocysteine of 63.56 and 87.48, respectively. The proposed method was applied for L-cysteine determination in human urine with satisfactory results. Due to a high variability of molecular imprinting technology and versatility of in-situ probe formation, methods based on this approach can be easily adopted for analysis of any thiol of interest.

Prebiotic Route to Thymine from Formamide-A Combined Experimental-Theoretical Study.

Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.

UV-Induced Nanoparticles-Formation, Properties and Their Potential Role in Origin of Life.

Inorganic nanoparticles might have played a vital role in the transition from inorganic chemistry to self-sustaining living systems. Such transition may have been triggered or controlled by processes requiring not only versatile catalysts but also suitable reaction surfaces. Here, experimental results showing that multicolor quantum dots might have been able to participate as catalysts in several specific and nonspecific reactions, relevant to the prebiotic chemistry are demonstrated. A very fast and easy UV-induced formation of ZnCd quantum dots (QDs) with a quantum yield of up to 47% was shown to occur 5 min after UV exposure of the solution containing Zn(II) and Cd(II) in the presence of a thiol capping agent. In addition to QDs formation, xanthine activity was observed in the solution. The role of solar radiation to induce ZnCd QDs formation was replicated during a stratospheric balloon flight.

Molecularly imprinted polymers and capillary electrophoresis for sensing phytoestrogens in milk.

Dairy cow feed contains, among other ingredients, soybeans, legumes, and clover, plants that are rich in phytoestrogens. Several publications have reported a positive influence of phytoestrogens on human health; however, several unfavorable effects have also been reported. In this work, a simple, selective, and eco-friendly method of phytoestrogen isolation based on the technique of noncovalent molecular imprinting was developed. Genistein was used as a template, and dopamine was chosen as a functional monomer. A layer of molecularly imprinted polymers was created in a microtitration well plate. The binding capability and selective properties of obtained molecularly imprinted polymers were investigated. The imprinted polymers exhibited higher binding affinity toward chosen phytoestrogen than did the nonimprinted polymers. A selectivity factor of 6.94 was calculated, confirming satisfactory selectivity of the polymeric layer. The applicability of the proposed sensing method was tested by isolation of genistein from a real sample of bovine milk and combined with micellar electrokinetic capillary chromatography with UV-visible detection.

Magnetic molecularly imprinted polymers used for selective isolation and detection of Staphylococcus aureus.

In this work, a novel method was developed, for isolation of S. aureus from complex (food) samples using molecular imprinting.  Dopamine was used as a functional monomer and fluorescence microscopy was used for detection. Conditions for preparation of molecularly imprinted polymers (MIPs), adsorption performance, adsorption kinetic, and selectivity of the polymeric layers were investigated. The various procedures were combined in a single extraction process, with the imprinted layer on the surface of the magnetic particles (magnetic MIPs). Subsequently, MIPs were used for extraction of S. aureus from milk and rice. Moreover, raw milk from cows with mastitis was tested successfully. Using this novel MIP-based method, it was possible to detect bacteria in milk at 1 × 103CFU·ml-1, which corresponds to the limit set in European Union legislation for microbial control of food.