Water-soluble platinum and palladium porphyrins with peripheral ethyl phosphonic acid substituents: synthesis, aggregation in solution, and photocatalytic properties.

Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.

Simultaneous Imaging of Temperature and Oxygen by Utilizing Thermally Activated Delayed Fluorescence and Phosphorescence of a Single Indicator.

Chemical gradients are essential in biological systems, affecting processes like microbial activity in soils and nutrient cycling. Traditional tools, such as microsensors, offer high-resolution data but are limited to one-dimensional measurements. Planar optodes allow for two-dimensional (2D) and three-dimensional (3D) chemical imaging but are often sensitive to temperature changes.

Multimaterial Digital-Light Processing of Metal-Organic Framework (MOF) Composites: A Versatile Tool for the Rapid Microfabrication of MOF-Based Devices.

Patterning Metal-Organic Frameworks (MOFs) is essential for their use in sensing, electronics, photonics, and encryption technologies. However, current lithography methods are limited in their ability to pattern more than two MOFs, hindering the potential for creating advanced multifunctional surfaces. Additionally, balancing design flexibility, simplicity, and cost often results in compromises.

Lifetime Imaging of the Internal O Dynamics in Corals with near-Infrared-Emitting Sensor Nanoparticles.

Mapping of O with luminescent sensors within intact animals is challenging due to attenuation of excitation and emission light caused by tissue absorption and scattering as well as interfering background fluorescence. Here we show the application of luminescent O sensor nanoparticles (∼50-70 nm) composed of the O indicator platinum(II) tetra(4-fluoro)phenyltetrabenzoporphyrin (PtTPTBPF) immobilized in poly(methyl methacrylate--methacrylic acid) (PMMA-MA). We injected the sensor nanoparticles into the gastrovascular system of intact colony fractions of reef-building tropical corals that harbor photosynthetic microalgae in their tissues.

Live Microscopy of Multicellular Spheroids with the Multimodal Near-Infrared Nanoparticles Reveals Differences in Oxygenation Gradients.

Assessment of hypoxia, nutrients, metabolite gradients, and other hallmarks of the tumor microenvironment within 3D multicellular spheroid and organoid models represents a challenging analytical task. Here, we report red/near-infrared (NIR) emitting cell staining with O-sensitive nanoparticles, which enable measurements of spheroid oxygenation on a conventional fluorescence microscope. Nanosensor probes, termed "MMIR" (multimodal infrared), incorporate an NIR O-sensitive metalloporphyrin (PtTPTBPF) and deep red aza-BODIPY reference dyes within a biocompatible polymer shell, allowing for oxygen gradient quantification via fluorescence ratio and phosphorescence lifetime readouts.

Analysis of per- and polyfluoroalkyl substances (PFAS) in raw materials intended for the production of paper-based food contact materials - evaluating LC-MS/MS versus total fluorine and extractable organic fluorine.

Per- and polyfluoroalkyl substances (PFAS) analysis has become crucial due to their presence in the environment, their persistence and potential health risks. These compounds are commonly used in food contact materials (FCM) as a coating to provide water and grease-repellent properties. One of the pathways for PFAS to enter the human body is either through direct consumption of contaminated food or indirectly through migration from FCM into food.

Influence of Roasting Temperature on the Detectability of Potentially Allergenic Lupin by SDS-PAGE, ELISAs, LC-MS/MS, and Real-Time PCR.

Seeds of "sweet lupins" have been playing an increasing role in the food industry. Lupin proteins may be used for producing a variety of foods, including pasta, bread, cookies, dairy products, and coffee substitutes. In a small percentage of the population, lupin consumption may elicit allergic reactions, either due to primary sensitization to lupin or due to cross-allergy with other legumes.

Tunable Self-Referenced Molecular Thermometers via Manipulation of Dual Emission in Platinum(II) Pyridinedipyrrolide Complexes.

Optical temperature sensors based on self-referenced readout schemes such as the emission ratio and the decay time are crucial for a wide range of applications, with the former often preferred due to simplicity of instrumentation. This work describes a new group of dually emitting dyes, platinum(II) pincer complexes, that can be used directly for ratiometric temperature sensing without an additional reference material. They consist of Pt(II) metal center surrounded by a pyridinedipyrrolide ligand (PDP) and a terminal ligand (benzonitrile, pyridine, 1-butylimidazol or carbon monoxide).

Human Sterols Are Overproduced, Stored and Excreted in Yeasts.

Sterols exert a profound influence on numerous cellular processes, playing a crucial role in both health and disease. However, comprehending the effects of sterol dysfunction on cellular physiology is challenging. Consequently, numerous processes affected by impaired sterol biosynthesis still elude our complete understanding.

DMT1-dependent endosome-mitochondria interactions regulate mitochondrial iron translocation and metastatic outgrowth.

Transient early endosome (EE)-mitochondria interactions can mediate mitochondrial iron translocation, but the associated mechanisms are still elusive. We showed that Divalent Metal Transporter 1 (DMT1) sustains mitochondrial iron translocation via EE-mitochondria interactions in triple-negative MDA-MB-231, but not in luminal A T47D breast cancer cells. DMT1 silencing increases labile iron pool (LIP) levels and activates PINK1/Parkin-dependent mitophagy in MDA-MB-231 cells.

Influence of Fluorinated Substituents on the Near-Infrared Phosphorescence of 5d Metallocorroles.

The influence of fluorinated substituents on the luminescent properties of rhenium-oxo, osmium-nitrido, and gold triarylcorroles was studied via a comparison of four ligands: triphenylcorrole (TPC), tris(-trifluoromethylphenyl)corrole (TCFPC), tris{3,5-bis(trifluoromethyl)phenyl}corrole (T3,5-CFPC), and tris(pentafluorophenyl)corrole (TPFPC). For each metal series examined, fluorinated substituents were found to enhance the luminescent properties, with the phosphorescence quantum yields and triplet decay times increasing in the order TPC < TCFPC < T3,5-CFPC < TPFPC. Among the 11 complexes examined, the highest phosphorescence quantum yield, 2.

Expression of hypoxia-inducible genes is suppressed in altered gravity due to impaired nuclear HIF1α accumulation.

Extravehicular activities, the backbone of manned space exploration programs, set astronauts into mild hypoxia. Unfortunately, microgravity aggravates threatening symptoms of hypoxia such as vision impairment and brain edema. Hypoxia-inducible factors (HIFs) sense cellular hypoxia and, subsequently, change the cells' expression profile instantaneously by rapidly translocating-most likely cytoskeleton-dependently-into the nucleus and subsequently forming transcription complexes with other proteins.

Optical glucose sensor for microfluidic cell culture systems.

Glucose is the primary energy source of human cells. Therefore, monitoring glucose inside microphysiological systems (MPS) provides valuable information on the viability and metabolic state of the cultured cells. However, continuous glucose monitoring inside MPS is challenging due to a lack of suitable miniaturized sensors.

Comparison of gas chromatographic techniques for the analysis of iodinated derivatives of aromatic amines.

Some aromatic amines (AA) have been classified as carcinogens to humans. After entering the body, mainly through tobacco smoke, they can be detected in urine. Thus, their trace analysis as biomarkers in biofluids is of high relevance and can be achieved with gas chromatography (GC-MS), usually after derivatization.

Physicochemical Attributes, Aroma Profile, and Sensory Quality of Organic Crimson Crisp Apples after Storage.

The objective of this study was to determine the effect of various storage conditions (i.e., storage under regular air with temperature control, controlled atmosphere storage and storage after the application of the ethylene blocker (1-MCP)) on the flavor characteristics of Crimson Crisp apples ( Borkh.

Roasting and Cacao Origin Affect the Formation of Volatile Organic Sulfur Compounds in 100% Chocolate.

Chocolate is a highly appreciated food that develops its characteristic flavors in large part during the roasting of cacao beans. Many functional classes have been noted for their importance to chocolate flavor, including volatile organic sulfur compounds (VSCs). Despite this, the effect of roasting on the concentration of VSCs has never been thoroughly assessed.

Physicochemical Attributes, Volatile Profile and Sensory Quality of Organic Crimson Crisp Apples during On-Tree Maturation.

When new apple cultivars are planted, knowledge of their maturation and ripening behavior and, as a consequence, the best time for their harvest is of utmost importance for providing fruits of the highest quality to consumers. In this study, we followed the on-tree maturation and ripening behavior of organic Crimson Crisp apples over a period of almost 3 months. With the weekly analyses of basic fruit quality attributes (weight, fruit firmness, total soluble solids, titratable acids, starch degradation) in combination with the fruit volatilome (primary and secondary volatiles) and sensory analysis, we obtained a holistic picture of the maturation and ripening properties of this new variety.

One-dimensional and comprehensive two-dimensional gas chromatographic approaches for the characterization of post-consumer recycled plastic materials.

In September 2022, the European Commission published its new regulation on recycled plastic materials for food contact. It allows newly developed, non-authorized technologies and approaches, or so-called novel technologies, to be deployed in the field to generate the data needed for establishing regulatory and/or fit for purpose processes. The data shall be generated by using suitable methods, but the regulation does not give a more detailed description on those.

Combination of Multidimensional Instrumental Analysis and the Ames Test for the Toxicological Evaluation of Mineral Oil Aromatic Hydrocarbons.

Mineral oil aromatic hydrocarbons (MOAHs) include mutagenic and carcinogenic substances and are considered a potential health risk. Current methods address the total MOAH content but cannot address the actual toxicological hazard of individual components. This work presents a combined methodology closing those gaps: high-performance liquid chromatography (HPLC) coupled to gas chromatography with flame ionization detection was used to determine the MOAH content.

Morphology and Size of Bacterial Colonies Control Anoxic Microenvironment Formation in Porous Media.

Bacterial metabolisms using electron acceptors other than oxygen (e.g., methanogenesis and fermentation) largely contribute to element cycling and natural contaminant attenuation/mobilization, even in well-oxygenated porous environments, such as shallow aquifers.

On-chip analysis of glycolysis and mitochondrial respiration in human induced pluripotent stem cells.

Recent advances in microfluidic engineering allow the creation of microenvironments in which human cells can be cultured under (patho-)physiological conditions with greater reality than standard plastic tissue culture plates. Microfluidic devices, also called Organs-on-Chip (OoC), allow complex engineering of the cellular compartment, yielding designs in which microfluidic flow can be precisely controlled. However, it is important that cellular physiology is not only controlled but can also be monitored in these devices.

Dynamic and Static Assembly of Sulfated Cellulose Nanocrystals with Alkali Metal Counter Cations.

Sulfate groups on cellulose particles such as cellulose nanocrystals (CNCs) provide colloidal stability credit to electrostatic repulsion between the like-charged particles. The introduction of sodium counter cations on the sulfate groups enables drying of the CNC suspensions without irreversible aggregation. Less is known about the effect of other counter cations than sodium on extending the properties of the CNC particles.

Optical Oxygen Sensors Show Reversible Cross-Talk and/or Degradation in the Presence of Nitrogen Dioxide.

A variety of luminescent dyes including the most common indicators for optical oxygen sensors were investigated in regard to their stability and photophysical properties in the presence of nitrogen dioxide. The dyes were immobilized in polystyrene and subjected to NO concentrations from 40 to 5500 ppm. The majority of dyes show fast degradation of optical properties due to the reaction with NO.

Microsensor in Microbioreactors: Full Bioprocess Characterization in a Novel Capillary-Wave Microbioreactor.

Microbioreactors (MBRs) with a volume below 1 mL are promising alternatives to established cultivation platforms such as shake flasks, lab-scale bioreactors and microtiter plates. Their main advantages are simple automatization and parallelization and the saving of expensive media components and test substances. These advantages are particularly pronounced in small-scale MBRs with a volume below 10 µL.