Microfluidic motion for a direct investigation of solvent interactions with PDMS microchannels

Solid surface/liquid interactions play an important role in microfluidics and particularly in manipulation of films, drops and bubbles, a basic requirement for a number of lab-on-chip applications. The behavior of solvents in coated microchannels is difficult to be predicted considering theories; therefore, experimental methods able to estimate the properties at the interface in real time and during the operational regime are amenable. Here, we propose to use an experimental setup to evaluate the effective dynamics of solvents inside PDMS microchannels. The influence of the solvent properties as well as of the channel wall’s wettability on the fluid movements was evaluated. Modification of the channel properties was achieved by introducing Teflon coatings that allow producing stable hydrophobic microchannel walls. The results were fitted according to Washburn-type power-law and compared with theoretical calculations of the parameter β that expresses the dependence of capillary dynamics on surface tension γ, liquid viscosity η, contact angles θ and the hydraulic radius R _H. A comparison between the calculated and the experimental values reveled that parameters other than the contemplated ones influenced the measurements. The main parameter that affects the flow of solvents such as water, methanol ethanol, dimethylformamide, acetonitrile and acetone was found to be the γ/η ratio. Considering these results, the investigation tool described here is believed to be promising to predict the dynamics of common organic solvents inside integrated functional fluidic devices and to accurately control solvent flow, particularly in capillary-driven pumpless systems, a basic requirement for widening the application range of PDMS lab-on-chip devices.     

Towards mesoscopic thermodynamics: Small systems in higher-order states

A higher-order generalization of the usual thermodynamic formalism is presented for systems with the number of particlesN large in comparison with 1, but sufficiently small that one or many higher-order fluctuations of energy (or other observables) are measurable, directly or indirectly. Then 1 «N «N _A , whereN _A is the Avogadro number, andn2, wheren is the highest order of fluctuations (central statistical moments). The systems are then open, finite and compact, and they have compact boundary surfaces, so that the energy is non-additive and temperatures are non-intensive, in general. Such systems will be called comesoscopic, while a finite or infinite super-system of such systems will be called mesoscopic. Three ideal models of comesoscopic systems are discussed in detail with one or two higher-order temperatures. General conclusions concerning hierarchical composite systems are drawn afterwards.

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Resistant starch formation during baking -effect of baking time and temperature and variations in the recipe

Summary The dietary fibre content in white wheat bread, measured with an enzymatic, gravimetric method, was almost 20% higher than in the corresponding flour. The increment was largely explained by the formation of resistant starch, i.e. starch available to amyloglucosidase only after solubilization with 2m-KOH. The resistant starch was formed in the oven or upon cooling of the finished bread. The water content in the dough seemed to influence the extent of the resistant starch formation, whereas changes in the fat content had no effect. The results indicate that the resistant starch might be hard retrograded starch, possibly amylose.

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Bildung von resistenter Stärke während des Backens in Abhängigkeit von Backzeit, Backtemperatur und Rezeptvariationen

Zusammenfassung Die Menge an Ballaststoffen, die nach einer enzymatisch-gravimetrischen Methode bestimmt wurde, war in weißem Weizenbrot fast 20% höher als in dem entsprechendem Mehl. Die Erhöhung konnte zum großen Teil auf die Bildung von resistenter Stärke zurückgeführt werden, d. h. auf eine Stärkefraktion, die nur nach Auflösung mit 2m-KOH für Amyloglucosidase zugänglich ist. Die resistente Stärke wird während des Backens oder während der Abkühlung des Brotes gebildet, und die Menge scheint vom Wassergehalt des Teiges, aber nicht vom Fettgehalt abhängig zu sein. Die Resultate dieser Untersuchung weisen darauf hin, daß die resistente Stärke retrogradierte Stärke, möglicherweise Amylose, ist.

     

Differential Action of Connexin Hemichannel and Pannexin Channel Therapeutics for Potential Treatment of Retinal Diseases

Dysregulation of retinal function in the early stages of light-induced retinal degeneration involves pannexins and connexins. These two types of proteins may contribute to channels that release ATP, leading to activation of the inflammasome pathway, spread of inflammation and retinal dysfunction. However, the effect of pannexin channel block alone or block of both pannexin channels and connexin hemichannels in parallel on retinal activity in vivo is unknown. In this study, the pannexin channel blocker probenecid and the connexin hemichannel blocker tonabersat were used in the light-damaged rat retina. Retinal function was evaluated using electroretinography (ERG), retinal structure was analyzed using optical coherence tomography (OCT) imaging and the tissue response to light-induced injury was assessed immunohistochemically with antibodies against glial fibrillary acidic protein (GFAP), Ionized calcium binding adaptor molecule 1 (Iba-1) and Connexin43 (Cx43). Probenecid did not further enhance the therapeutic effect of connexin hemichannel block in this model, but on its own improved activity of certain inner retina neurons. The therapeutic benefit of blocking connexin hemichannels was further evaluated by comparing these data against results from our previously published studies that also used the light-damaged rat retina model. The analysis showed that treatment with tonabersat alone was better than probenecid alone at restoring retinal function in the light-damaged retina model. The results assist in the interpretation of the differential action of connexin hemichannel and pannexin channel therapeutics for potential treatment of retinal diseases.     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

Hemi- and Homozygous Loss-of-Function Mutations in DSG2 (Desmoglein-2) Cause Recessive Arrhythmogenic Cardiomyopathy with an Early Onset

About 50% of patients with arrhythmogenic cardiomyopathy (ACM) carry a pathogenic or likely pathogenic mutation in the desmosomal genes. However, there is a significant number of patients without positive familial anamnesis. Therefore, the molecular reasons for ACM in these patients are frequently unknown and a genetic contribution might be underestimated. Here, we used a next-generation sequencing (NGS) approach and in addition single nucleotide polymor-phism (SNP) arrays for the genetic analysis of two independent index patients without familial medical history. Of note, this genetic strategy revealed a homozygous splice site mutation (DSG2–c.378+1G>T) in the first patient and a nonsense mutation (DSG2–p.L772X) in combination with a large deletion in DSG2 in the second one. In conclusion, a recessive inheritance pattern is likely for both cases, which might contribute to the hidden medical history in both families. This is the first report about these novel loss-of-function mutations in DSG2 that have not been previously identi-fied. Therefore, we suggest performing deep genetic analyses using NGS in combination with SNP arrays also for ACM index patients without obvious familial medical history. In the future, this finding might has relevance for the genetic counseling of similar cases.     

Dynamic “Molecular Portraits” of Biomembranes Drawn by Their Lateral Nanoscale Inhomogeneities

To date, it has been reliably shown that the lipid bilayer/water interface can be thoroughly characterized by a sophisticated so-called “dynamic molecular portrait”. The latter reflects a combination of time-dependent surface distributions of various physicochemical properties, inherent in both model lipid bilayers and natural multi-component cell membranes. One of the most important features of biomembranes is their mosaicity, which is expressed in the constant presence of lateral inhomogeneities, the sizes and lifetimes of which vary in a wide range—from 1 to 10³ nm and from 0.1 ns to milliseconds. In addition to the relatively well-studied macroscopic domains (so-called “rafts”), the analysis of micro- and nanoclusters (or domains) that form an instantaneous picture of the distribution of structural, dynamic, hydrophobic, electrical, etc., properties at the membrane-water interface is attracting increasing interest. This is because such nanodomains (NDs) have been proven to be crucial for the proper membrane functioning in cells. Therefore, an understanding with atomistic details the phenomena associated with NDs is required. The present mini-review describes the recent results of experimental and in silico studies of spontaneously formed NDs in lipid membranes. The main attention is paid to the methods of ND detection, characterization of their spatiotemporal parameters, the elucidation of the molecular mechanisms of their formation. Biological role of NDs in cell membranes is briefly discussed. Understanding such effects creates the basis for rational design of new prospective drugs, therapeutic approaches, and artificial membrane materials with specified properties.     

Synthesis of titanium aluminide coatings on aluminum and titanium surfaces by mechanical alloying and subsequent annealing

Intermetallic Ti-Al-based coatings were synthesized by mechanical alloying in a vibratory ball mill and subsequent annealing. A titanium layer was deposited on aluminum specimens and an aluminum layer and aluminum-titanium mixture were deposited on titanium specimens. Under the effect of milling balls, powder particles deposit at the substrates, forming layers that have a very good cohesion with the substrate. During subsequent heating, diffusion layers on the basis of titanium-aluminum phases are synthesized as a result of the chemical interaction between titanium and aluminum. In the case of titanium layer deposited on aluminum, the temperature interval of transformations is 600–650°C; first, a Ti₃Al₅-based phase is formed; then, as diffusion saturation with Al increases, an Al₂Ti-based layer appears; and finally, the Al₃Ti compound is formed. The reaction rates depend on the temperature and the duration of annealing. On titanium with a (Ti + Al) layer deposited on its surface, the Al₃Ti, Al₂Ti, TiAl, and Ti₃Al compounds are formed in a temperature interval of 600–900°C. In the case of deposition a homogeneous aluminum layer on titanium, only Al₃Ti and Ti₃Al phases were observed after annealing.     

Monitoring the tensile deformation in real unidirectional Kevlar-epoxy composites

Two acoustic emission (AE) parameters, event count rate (ER) and the skewness of the peak amplitude distribution (PAD), were found to correlate with mechanical and damage mechanisms in unidirectional Kevlar-epoxy composites loaded in tension. The ER of the AE reached a local maximum at about 0.3σ_cu (σ_cu= composite tensile strength), a minimum at about 0.6–0.7σ_cu, and increasing ER rates were noted as failure stress approached, with a peak at final failure.Along with our proposed approach to evaluate the PAD as a tool for characterizing processes, damage mechanisms and failure modes, the third statistical moment of the PAD, the skewness, was found to be able to distinguish between various mechanisms. From the beginning of loading until completion of the fibre straightening process, 0.6–0.7σ_cu, the value of the skewness steadily decreased, and then gradually increased to final failure. This behaviour is explained by a model based on the non-elastic mechanisms which contribute to the monitored AE. At final failure, the PAD's skewness value was affected by macroscopic failure modes. When this mode comprises fibre fracture with little matrix and interface splitting, the skewness decreased; when fibre failure was accompanied by matrix and interface splitting, its value changed slightly or even increased.     

Synthesis and crosslinking properties of phenolphtalein dimethacrylate

Summary By reacting esterification of phenolphtalein with methacrylate chloride, phenolphtalein dimethacrylate was obtained. Based on the results of elemental analysis, FTIR, ¹H-NMR and ¹³C-NMR spectra, the structure of the product was proposed. The dimethacrylate was used as new crosslinker to crosslink poly(methyl methacrylate) (PMMA). The influence of the amount dimethacrylate on the crosslink density and some properties of the crosslinked polymers networks such as swelling, mechanical properties (tensile strength and elongation at break) and thermal stability were examined.