Distribution of 137Cs specific activity in river sediments of the Barents Sea basin (Nenets Autonomous Okrug, Russian Arctic).

This article focuses on the study of the distribution of 137Cs in the bottom sediments of Arctic rivers of the Barents Sea basin (using the example of the Nenets Autonomous Okrug, Russian Arctic). This research is relevant due to the poorly studied region and the significant number of radiation-hazardous facilities in the Arctic zone of Russia, both those currently in operation and those that are "nuclear heritage sites". The study of 137Cs specific activity in bottom sediments was carried out in the period from 2020 to 2023 in the rivers Chizha, Nes, Vizhas, Oma, Pechora (river delta), as well as the rivers Kolva and Usa (first and second order tributaries, respectively, of the Pechora River). A total of 199 samples were collected. In addition to 137Cs specific activity, the samples were analysed for sediment particle size distribution, organic matter content, carbonate content and ash content. The 137Cs specific activity mainly ranged from the minimum detectable specific activity to 5.4 ± 0.8 Bq·kg-1. In the Nes River basin (Kaninskaya tundra), the 137Cs content in bottom sediments reached 36.0 ± 3.2 Bq·kg-1 (in the case of lake sediments) and 22.9 ± 3.7 Bq·kg-1 (in the case of river sediments), values that are higher than those of the North-West of Russia. Considering the large area of the study area (Kaninskaya tundra, Pechora river delta, southern part of Bolshezemelskaya tundra) and the similarity of physical and chemical parameters of the studied rivers, it is possible to assume the existence of a zone of increased radionuclide content in the Nes river basin. This may be due to the runoff from the Nes River catchment area, its hydrological features, and the accumulation of 137Cs in the small fractions of bottom sediments. The results confirm the conclusions of previous soil studies in the Nes river basin. The main sources of elevated 137Cs content are global atmospheric deposition and the Chernobyl Nuclear Power Plant accident.

Time regularities of strontium concentration in drinking groundwater distant from the sea coast.

This paper confirms the regularities of the formation of increased concentrations of strontium (Sr) in fresh groundwater used for drinking water supply, depending on the time they are residen in the carbonate deposits of the aquifer. On average, every thousand years, the Sr concentration increases by 2.1-3.5 mg L-1. In addition, high strontium content is positively correlated with altitude and well depth and negatively correlated with redox conditions in the aquifer. Large relief elevations are associated with the development of marginal moraine deposits from the Last Glacial Period composed predominantly of clay, which contributes to a decrease in water exchange. The high Sr content is associated with the dissolution of significant formations of celestite and strontianite, up to their ore occurrences. For this reason, the saturation indices (SIs) for celestite and strontianite correlate with TDS and rise to - 1.42 and 2.05, respectively. Low Sr values do not correlate with the residence time of groundwater in the aquifer or the depth of wells and tend to depressions in the relief, with a virtual absence of overlying sediments and positive Eh values, which indicates an active water exchange. The low level of Sr is associated with the dissolution of gypsum, calcite, and dolomite containing strontium as an impurity. This causes the SIs for gypsum, calcite, and dolomite to correlate with TDS, while for celestite and strontianite, the SI drops to - 5.02 and - 0.92, respectively. The established patterns make it possible to more reasonably choose places for the construction of water wells to obtain drinking water of standard quality.

Trace metals in surface water of the Pechora River and its tributaries: Content, water quality and risks assessment (Arctic Ocean basin).

The article is devoted to the study of trace metals content in the Pechora River and its tributaries, which is the largest river in the Arctic Ocean basin. The study of physico-chemical properties of water showed aerobic conditions of low-mineralised water with pH values suitable for drinking water. Analysis of the content of trace metals has revealed that the main flow of Al, Mn, Co, Cu, Zn, V, As, Mg and Fe into the Pechora River comes from its tributaries. The average content of Cr, Mn, Cu, Zn, Pb, V, As, Mg and Fe in the water of the Pechora River delta was higher than for the main river channel, which indicates the transfer of a large mass of trace metals to the Barents Sea and the Arctic water ecosystem. For the studied river and tributaries, chronic pollution of the Pechora River with Al, Mn, Ba, Fe, Cu, U and Pb metals has adverse effects on waterborne organisms. The degree of contamination of natural waters by metals has been assessed using water quality indices (TMPI, TMEI, TMTI) and public health risks (HI and CR). Low contamination and weak toxicity of the Pechora River water has been determined, but serious contamination, toxicity and high non-carcinogenic risk of some of its tributaries have been observed. A high carcinogenic risk has been established for the consumption of all water sampled. Al, Ni, As, Fe, Mn, Cr, Cd, and Ba were found to be the highest priority contaminating trace metals. At present, contamination of the Pechora River and its tributaries with trace metals is formed under the influence of dissolution processes of rocks of the Ural Mountains, the Taminsky Ridge, underlying mineral deposits, permafrost degradation processes and glacier melting. Anthropogenic factors include oil and gas production and transportation.

Evaluation of current natural and anthropogenic radionuclide activity in coastal area bottom sediments of the Barents Sea (North of the Kola Peninsula).

This article is devoted to the study of the activity of technogenic 137Cs and 90Sr, as well as natural radionuclides 40K, 232Th and 226Ra in bottom sediments of the Kola coast of the Barents Sea, where a significant number of radiation objects are concentrated. In order to characterize and assess the accumulation of radioactivity in the bottom sediments, we studied the particle size distribution and some physicochemical parameters, such as the content of organic matter, carbonates and ash components. The average activities of natural radionuclides 226Ra, 232Th and 40K were 325.0, 25.1 and 466.7 Bq·kg-1, respectively. Levels of natural radionuclides in the coastal zone of the Kola Peninsula are within the range of marine sediments worldwide. Still, they are slightly higher than those observed in the central areas of the Barents Sea, most likely due to the formation of coastal bottom sediments as a result of the destruction of the natural radionuclide-enriched crystalline basement rocks that make up the Kola coast. The average activities of technogenic 90Sr and 137Cs in the bottom sediments of the Kola coast of the Barents Sea are 3.5 and 5.5 Bq·kg-1, respectively. The highest activities of 90Sr and 137Cs were found in the bays of the Kola coast, while they remain below detection limits in the open parts of the Barents Sea. Despite the presence of potential sources of radiation pollution in the coastal zone of the Barents Sea, we did not find any short-lived radionuclides in the bottom sediments, which indicates the absence of a significant influence of local sources on the transformation of the technogenic radiation background. The study of particle size distribution and physicochemical parameters showed that the accumulation of natural radionuclides is largely related to the content of organic matter and carbonates, while the accumulation of technogenic isotopes occurs in the composition of organic matter and the smallest fractions of bottom sediments.

Biosensing with a scanning planar Yagi-Uda antenna.

We investigate a model bioassay in a liquid environment using a z-scanning planar Yagi-Uda antenna, focusing on the fluorescence collection enhancement of ATTO-647N dye conjugated to DNA (deoxyribonucleic acid) molecules. The antenna changes the excitation and the decay rates and, more importantly, the emission pattern of ATTO-647N, resulting in a narrow emission angle (41°) and improved collection efficiency. We efficiently detect immobilized fluorescently-labeled DNA molecules, originating from solutions with DNA concentrations down to 1 nM. In practice, this corresponds to an ensemble of fewer than 10 ATTO-647N labeled DNA molecules in the focal area. Even though we use only one type of biomolecule and one immobilization technique to establish the procedure, our method is versatile and applicable to any immobilized, dye-labeled biomolecule in a transparent solid, air, or liquid environment.

Assessment of physical and chemical properties, health risk of trace metals and quality indices of surface waters of the rivers and lakes of the Kola Peninsula (Murmansk Region, North-West Russia).

The pollution of waterbodies with trace metals is of concern throughout the world due to their high toxicity. One of the main anthropogenic sources of trace metals entering natural waters is the mining and processing of minerals. Intensive development of the mining industry on the Kola Peninsula (the Murmansk region, Russia), exploration and development of new mineral resources have led to a sharp deterioration in the quality of surface waters of rivers and lakes. As a result of anthropogenic impact, accumulation of a wide range of metals (mainly Cu, Ni, Co, Pb, Cd, Mn, Sr, Al and Fe) is observed, as well as significant changes in the physicochemical parameters and radioactive conditions of surface waters. The most polluted waterbodies of the Kola Peninsula are located in the Monchegorsk, Olenegorsk and Apatit regions. Consumption of water from investigated contaminated sources can cause various high risks of human health. The results of this study will provide an informative basis for future risk assessments of the environment and human health, as well as for the development of integrated measures for managing the quality of surface waters of lakes and rivers of the Kola Peninsula.

Quantitative E. coli Enzyme Detection in Reporter Hydrogel-Coated Paper Using a Smartphone Camera.

There is a growing demand for rapid and sensitive detection approaches for pathogenic bacteria that can be applied by non-specialists in non-laboratory field settings. Here, the detection of the typical E. coli enzyme ß-glucuronidase using a chitosan-based sensing hydrogel-coated paper sensor and the detailed analysis of the reaction kinetics, as detected by a smartphone camera, is reported. The chromogenic reporter unit affords an intense blue color in a two-step reaction, which was analyzed using a modified Michaelis-Menten approach. This generalizable approach can be used to determine the limit of detection and comprises an invaluable tool to characterize the performance of lab-in-a-phone type approaches. For the particular system analyzed, the ratio of reaction rate and equilibrium constants of the enzyme-substrate complex are 0.3 and 0.9 pM-1h-1 for ß-glucuronidase in phosphate buffered saline and lysogeny broth, respectively. The minimal degree of substrate conversion for detection of the indigo pigment formed during the reaction is 0.15, while the minimal time required for detection in this particular system is ~2 h at an enzyme concentration of 100 nM. Therefore, this approach is applicable for quantitative lab-in-a-phone based point of care detection systems that are based on enzymatic substrate conversion via bacterial enzymes.

Atmospheric fallout of radionuclides in peat bogs in the Western Segment of the Russian Arctic.

This article presents the results of studies of the activity of radionuclides in peat-bog profiles of the European subarctic of Russia. Two peat profiles were collected in different areas of the Arkhangelsk region. The peat cores were used to determine 210Pb, 137Cs, 241Am, 239Pu, 240Pu, 238U, and 234U content. To estimate the relationship between radionuclide activity and physicochemical parameters of peat, the content of organic matter, water-soluble salts, carbonates and ash, and the pH of aqueous and salt extracts were studied. Radionuclide activity concentrations in peat samples were measured using inductively coupled plasma mass spectrometry (ICP-MS), low-background semiconductor gamma spectrometry with a high-purity germanium (HPGe) detector, and alpha spectrometry. The 210Pb chronology of peat cores was studied using a constant flow model based on the Monte Carlo simulation method. Comparison of 210Pb dating data showed that the position of the maximum activity peaks of anthropogenic radionuclides shifted along the peat profile. This is probably due to the relative mobility of different radionuclides in the peat massif. Measurement of the atomic ratio 240Pu/239Pu showed that the main sources of pollution in the peatlands of the European subarctic of Russia are global fallout from atmospheric tests from the 1950s through 1980 and fallout from the Chernobyl nuclear accident in 1986. This study shows that a complex of radioactive isotopes in peat deposits can provide valuable information on the environmental pollution loads of subarctic territories.

Assessment of physicochemical parameters and metal distribution in bog peat of the western segment of the North European part of Russia (Arkhangelsk region).

This article is devoted to the study of physicochemical parameters and the assessment of the accumulation and distribution of metals in peat deposits from the North European part of Russia (Arkhangelsk region). Peat profiles were selected both in the area with a high anthropogenic load and in a bog remote from industrial pollution. The determination of metals was carried out by using the methods X-ray fluorescence analysis and atomic absorption spectroscopy. It was determined that the studied bogs can be attributed to the low ash type, and the recorded pH and mineralisation values make it possible to attribute these deposits to the acid-oxidising facies of oligotrophic peatlands, characteristic of taiga landscapes. Assessment of metal accumulation showed a high content of titanium, chromium, lead, nickel, vanadium, cobalt, aluminium, silicon, and copper in peat, mainly caused by the burning of fossil fuels and industrial production, as well as the burning of urban and industrial waste. The peat profiles are characterised by significant fluctuations in the content of elements in different horizons. Studies have shown the need to monitor the content of metals in peatlands from the Arkhangelsk region to assess atmospheric pollution from industrial emissions, both at the moment and in the past.

Distribution of trace metals and an environmental risk assessment of the river sediments in the area of the Lomonosov diamond deposit (NW Russia).

This article is devoted to the study of trace metals in the bottom sediments of watercourses in the area of the developed Lomonosov diamond deposit, which is the largest industrial diamond deposit in Europe. Samples of river sediments were taken from the Zolotitsa River and all its tributaries in the area of the diamond deposit. In addition, samples of kimberlites and rocks were selected from the quarries. It was established that the average concentration of metals in all types of rocks extracted from the quarries was significantly higher than that in river sediments and naturally decreased in the following order: kimberlites (D3-C2), Vendian enclosing rocks (V2) and overlying Quaternary and Carboniferous deposits (Q and C2). The results suggest that the mining and beneficiation complex plays a significant role in increasing the metal content in the river sediments, which is reliably recorded by the change in the physicochemical parameters of river sediments due to the anthropogenic impacts. The heavy metal pollution in river sediments in the area of Lomonosov diamond deposits is due to three main factors: (1) the discharge of quarry water into the peatbog-filtration fields and then into the river, (2) erosion of the rock dumps and natural factors and (3) the process by which the products from the weathering of kimberlites are transferred to the riverbed, and this transfer process requires further clarification. The results of this research can provide management references for the pollution control of the diamond mining industrial zone and the prevention of basin environmental risks.

Probing of local polarity in poly(methyl methacrylate) with the charge transfer transition in Nile red.

The permittivity of polymers and its spatial distribution play a crucial role in the behavior of thin films, such as those used, e.g., as sensor coatings. In an attempt to develop a conclusive approach to determine these quantities, the polarity of the model polymer poly(methyl methacrylate) (PMMA) in 600 nm thin films on a glass support was probed by the energy of the charge transfer transition in the oxazine dye Nile red (NR) at 25 °C. The absorption and fluorescence spectra of NR were observed to shift to the red with increasing solvent polarity, because of the intramolecular charge transfer character of the optical transition. New types of solvatochromic plots of emission frequency against absorption frequency and vice versa afforded the Onsager radius-free estimation of the ground and excited states dipole moment ratio. With this approach the values of these dipole moments of 11.97 D and 18.30-19.16 D, respectively, were obtained for NR. An effective local dielectric constant of 5.9-8.3 for PMMA thin films was calculated from the solvatochromic plot and the fluorescence maximum of NR observed in the PMMA films. The fluorescence band of NR in the rigid PMMA films shifted to the red by 130 cm-1 with increasing excitation wavelength from 470 to 540 nm, while in a series of liquids the position of the emission maximum of NR remained constant within same range of the excitation wavelength. It is concluded that the fluorescence spectrum of NR in PMMA undergoes inhomogeneous broadening due to different surroundings of NR molecules in the ground state and slow sub-glass transition (T g) relaxations in PMMA.

Colorimetric and Fluorimetric DNA Detection with a Hydroxystyryl-Quinolizinium Photoacid and Its Application for Cell Imaging.

The combination of styryl dye properties with the acidity and strong photoacidity of the 2,2'-[(1''-hydroxy-4''-methyl-(E)-2'',6''-phenylene)]-bisquinolizinium enables the detection of DNA by distinct absorption and emission color changes and the fluorimetric detection of DNA in cells with epifluorescence and confocal fluorescence microscopy.

Multimodal microscopy-based identification of surface nanobubbles.

HYPOTHESIS: Surface nanobubbles, which were controversially discussed in the literature, promise a number of outstanding applications, and their presence may hamper nanoscale processes at solid-aqueous interfaces. A most crucial and yet unsolved question is the rapid and conclusive identification of gas-filled (surface) nanobubbles. We hypothesize that surface nanobubbles and oil nanodroplets can be conclusively differentiated in co-localization experiments with atomic force microscopy (AFM) and time-resolved fluorescence microscopy by localizing tracer fluorophores and analyzing their fluorescence lifetimes. EXPERIMENTS: Combined AFM and fluorescence lifetime imaging microscopy (FLIM) were conducted to localize the various interfaces labelled by the reporter dye rhodamine 6G (Rh6G). The dependence of the fluorescence lifetime of Rh6G on its local environment was determined for air/water, water/glass and polysiloxane/water interfaces under different conditions. FINDINGS: In in situ co-localization experiments, surface nanobubbles labeled with Rh6G were probed by AFM with high spatial resolution and were differentiated from polysiloxane droplets as well as contamination originating from lubricant-coated syringe needles owing to the characteristic short fluorescence lifetime of Rh6G at the gas/water interface observed in FLIM. In particular, this approach lends itself to conclusively identify and rapidly differentiate these gas-filled entities from adsorbed contamination, such as siloxane-based oil nanodroplets.

Tailored Combinatorial Microcompartments through the Self-Organization of Microobjects: Assembly, Characterization, and Cell Studies.

A new concept enables the generation of cell microenvironments by microobject assembly at an water/air interface. As the orientation of 30 µm sized polymer cubes and their capillary force assembly are controlled by the surface wettability, which in turn can be modulated by coating the initially exposed surfaces with gold and self-assembled monolayers, unique niches in closely packed arrays of cubes with vertex up orientation can be realized. The random assembly of distinctly different cubes, prefunctionalized or surface-structured exclusively on their top surface, facilitates the parallel generation of different microenvironments in a combinatorial manner, which paves the way to future systematic structure-property relationship studies with cells.

Fluorescence of 4-(Diisopropylamino)benzonitrile (DIABN) Single Crystals from 300 K down to 5 K. Intramolecular Charge Transfer Disappears below 60 K.

Single crystals of 4-(diisopropylamino)benzonitrile (DIABN) undergo an intramolecular charge transfer (ICT) reaction in the excited singlet state. At 300 K, the fluorescence consists of emissions from the locally excited (LE) and from the ICT state. Upon cooling to 5 K, the ICT fluorescence intensity gradually decreases relative to that of the LE emission and is absent below 60 K. With crystalline 4-(dimethylamino)benzonitrile (DMABN), in contrast, only LE emission is found over the entire range from 300 to 5 K. The phosphorescence spectra of the DIABN and the DMABN crystals do not present any evidence for an additional ICT emission, showing that ICT does not occur in the triplet state. An activation energy Ea of ∼4 kJ/mol is determined for the LE → ICT reaction of DIABN crystals, from the temperature dependence of the fluorescence decay times τ2 and τ1. Ea is attributed to changes in the molecular conformation of DIABN other than a full rotation of the large diisopropylamino group with respect to the benzonitrile moiety. In a comparison with crystal and solution data, literature results from transient vibrational and absorption spectra are discussed and it is concluded that they cannot be employed to favor the TICT (perpendicular twist) over the PICT (planar) model for DIABN and DMABN.

Absence of Intramolecular Charge Transfer with 4-Fluoro-N,N-dimethylaniline (DMA4F), Contrary to an Experimental Report Supported by Computations.

With 4-fluoro-N,N-dimethylaniline (DMA4F), only a single fluorescence from a locally excited (LE) state is observed, irrespective of solvent polarity, temperature, and excitation wavelength. The relatively small excited state dipole moment µe = 7.3 D confirms the identification as LE. The single exponential fluorescence decays in the nonpolar n-hexane (2.04 ns) and in the strongly polar acetonitrile (5.73 ns) are a further support. Similar results are obtained with 4-chloro-N,N-dimethylaniline (DMA4Cl), having a chlorobenzene subgroup, a somewhat better electron acceptor than the fluorobenzene moiety in DMA4F. The absence of intramolecular charge transfer (ICT) with DMA4F is in accord with its large energy gap ΔE(S1,S2) of 8300 cm-1 in n-hexane between the two lowest singlet excited states, which is even larger than that (6300 cm-1) of N,N-dimethylaniline (DMA), for which an LE → ICT reaction likewise does not occur. The results with DMA4F are in contradiction with a publication by Fujiwara et al. ( Chem. Phys. Lett. 2013 , 586 , 70 ), in which the appearance of dual LE + ICT emission is reported for DMA4F in n-hexane and MeCN at room temperature. The ICT/LE fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) reached a maximum value of ∼2, in n-hexane and surprisingly also in MeCN, as the excitation wavelength approaches the red-edge of the absorption spectrum. These, in our opinion, erroneous observations were supported by time-dependent density functional theory (TDDFT) calculations, which compute a perpendicularly twisted lowest ICT state (TICT) state. This is a further example of the general tendency of computations to find a TICT conformation for the lowest excited singlet state of electron donor/acceptor molecules such as p-substituted anilines.

Thin Poly(Di(Ethylene Glycol)Methyl Ether Methacrylate) Homopolymer Brushes Allow Controlled Adsorption and Desorption of PaTu 8988t Cells.

Poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) brushes, which are known to suppress protein adsorption and prevent cell attachment, are reported here to possess interesting and tunable thermoresponsive behavior, if the brush thickness is reduced or the grafting density is altered. PDEGMA brushes with a dry ellipsometric thickness of 5 ± 1 nm can be switched from cell adherent behavior at 37 °C to cell nonadherent at 25 °C. This behavior coincides with the temperature-dependent irreversible adsorption of fibronectin from phosphate saline buffer and proteins present in the cell culture medium, as unveiled by surface plasmon resonance measurements. Unlike for tissue culture polystyrene reference surfaces, swelling of the PDEGMA chains below the lower critical solution temperature results in the absence of paxillin and actin containing cellular filaments responsible for cell attachment. These tunable properties of very thin homopolymer PDEGMA brushes render this system interesting as an alternative thermoresponsive layer for continuous cell culture or enzyme-free cell culture systems.

Detailed Study of BSA Adsorption on Micro- and Nanocrystalline Diamond/ß-SiC Composite Gradient Films by Time-Resolved Fluorescence Microscopy.

The adsorption of bovine serum albumin (BSA) on micro- and nanocrystalline diamond/ß-SiC composite films synthesized using the hot filament chemical vapor deposition (HFCVD) technique has been investigated by confocal fluorescence lifetime imaging microscopy. BSA labeled with fluorescein isothiocyanate (FITC) was employed as a probe. The BSAFITC conjugate was found to preferentially adsorb on both O-/OH-terminated microcrystalline and nanocrystalline diamond compared to the OH-terminated ß-SiC, resulting in an increasing amount of BSA adsorbed to the gradient surfaces with an increasing diamond/ß-SiC ratio. The different strength of adsorption (>30 times for diamond with a grain size of 570 nm) coincides with different surface energy parameters and differing conformational changes upon adsorption. Fluorescence data of the adsorbed BSAFITC on the gradient film with different diamond coverage show a four-exponential decay with decay times of 3.71, 2.54, 0.66, and 0.13 ns for a grain size of 570 nm. The different decay times are attributed to the fluorescence of thiourea fluorescein residuals of linked FITC distributed in BSA with different dye-dye and dye-surface distances. The longest decay time was found to correlate linearly with the diamond grain size. The fluorescence of BSAFITC undergoes external dynamic fluorescence quenching on the diamond surface by H- and/or sp2-defects and/or by amorphous carbon or graphite phases. An acceleration of the internal fluorescence concentration quenching in BSAFITC because of structural changes of albumin due to adsorption, is concluded to be a secondary contributor. These results suggest that the micro- and nanocrystalline diamond/ß-SiC composite gradient films can be utilized to spatially control protein adsorption and diamond crystallite size, which facilitates systematic studies at these interesting (bio)interfaces.

Thickness Dependence of Bovine Serum Albumin Adsorption on Thin Thermoresponsive Poly(diethylene glycol) Methyl Ether Methacrylate Brushes by Surface Plasmon Resonance Measurements.

This study reports on the dependence of the temperature-induced changes in the properties of thin thermoresponsive poly(diethylene glycol) methyl ether methacrylate (PDEGMA) layers of end-tethered chains on polymer thickness and grafting density. PDEGMA layers with a dry ellipsometric thickness of 5-40 nm were synthesized by surface-initiated atom transfer radical polymerization on gold. To assess the temperature-induced changes, the adsorption of bovine serum albumin (BSA) was investigated systematically as a function of film thickness, temperature, and grafting density by surface plasmon resonance (SPR), complemented by wettability and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. BSA adsorption on PDEGMA brushes is shown to differ significantly above and below an apparent transition temperature. This surface transition temperature was found to depend linearly on the PDEGMA thickness and changed from 35 °C at 5 nm thickness to 48 °C at 23 nm. Similarly, a change of the grafting density enables the adjustment of this transition temperature presumably via a transition from the mushroom to the brush regime. Finally, BSA that adsorbed irreversibly on polymer brushes at temperatures above the transition temperature can be desorbed by reducing the temperature to 25 °C, underlining the reversibly switchable properties of PDEGMA brushes in response to temperature changes.

Surface Nanobubbles Studied by Time-Resolved Fluorescence Microscopy Methods Combined with AFM: The Impact of Surface Treatment on Nanobubble Nucleation.

The impact of surface treatment and modification on surface nanobubble nucleation in water has been addressed by a new combination of fluorescence lifetime imaging microscopy (FLIM) and atomic force microscopy (AFM). In this study, rhodamine 6G (Rh6G)-labeled surface nanobubbles nucleated by the ethanol-water exchange were studied on differently cleaned borosilicate glass, silanized glass as well as self-assembled monolayers on transparent gold by combined AFM-FLIM. While the AFM data confirmed earlier reports on surface nanobubble nucleation, size, and apparent contact angles in dependence of the underlying substrate, the colocalization of these elevated features with highly fluorescent features observed in confocal intensity images added new information. By analyzing the characteristic contributions to the excited state lifetime of Rh6G in decay curves obtained from time-correlated single photon counting (TCSPC) experiments, the characteristic short-lived (<600 ps) component of could be associated with an emission at the gas-water interface. Its colocalization with nanobubble-like features in the AFM height images provides evidence for the observation of gas-filled surface nanobubbles. While piranha-cleaned glass supported nanobubbles, milder UV-ozone or oxygen plasma treatment afforded glass-water interfaces, where no nanobubbles were observed by combined AFM-FLIM. Finally, the number density of nanobubbles scaled inversely with increasing surface hydrophobicity.