Reversible and irreversible pH induced conformational changes in self-assembled weak polyelectrolyte multilayers probed using etched fiber Bragg grating sensors

Polyelectrolytes are charged polymer species which electrostatically adsorb onto surfaces in a layer by layer fashion leading to the sequential assembly of multilayer structures. It is known that the morphology of weak polyelectrolyte structures is strongly influenced by environmental variables such as pH. We created a weak polyelectrolyte multilayer structure (similar to 100 nm thick) of cationic polymer poly-allylamine hydrochloride (PAH) and an anionic polymer poly-acrylic acid (PAA) on an etched clad fiber Bragg grating (EFBG) to study the pH induced conformational transitions in the polymer multilayers brought about by the variation in charge density of weak polyelectrolyte groups as a function of pH. The conformational changes of the polyelectrolyte multilayer structure lead to changes in optical density of the adsorbed film which reflects in the shift of the Bragg wavelength from the EFBG. Using the EFBG system we were able to probe reversible and irreversible pH induced transitions in the PAH/PAA weak polyelectrolyte system. (C) 2014 Elsevier B.V. All rights reserved.

Efficient and practical synthesis of modular chiral beta-organochalcogeno amines, ArYCH2CH(R)NH2, and single crystal structures of (S) - MsOCH2CH(Bz)NH3+ center dot Cl- and (R)-MsOCH2CH(Ph)NH3+ center dot Cl-

Modular chiral I3-organochalcogeno amines, ArYCH2CH(R)NH2 (4a-4g) where R = Me, Bz, Ph; and ArY = PhS, BzSe and 4-MeOC6H4Te respectively have been synthesized and characterized. Compounds 4a-4g were synthesized (Method II) from chiral aminoalkyl 13-methanesulfonate hydrochlorides, MsOCH2CH(R)NH3+ center dot Cl- (2a-2c) through nucleophilic displacement of MsO- with organochalcogenolate (ArY-). In another attempt (Method I) chiral beta-organotelluro amines (4a-4c) were prepared by deprotection of chiral N-boc I3-organotelluro amides, 4-MeOC6H4TeCH2CH(R)NH-Boc (3a-3c), which in turn, 13,-,1 were made from chiral N-boc 13-methanesulfonate amides (la-lc) and ArTeNa. 1H, and FTIR spectra of all the compounds (3a-3c and 4a-4g) were characteristic. The composition of 3a-3c was determined by elemental analysis. The a]TD values of 3b-3c and 4a-4g were determined. The single crystal structures of (S)-2b and (R)-2c were determined by X-Ray diffraction studies. Both (S)-2b and (R)2c were crystallized in orthorhombic system and the Flack parameter x was found 0.08(12) and 0.00(2) respectively. The crystal of (S)-2b contain two asymmetric units with gauche (A) and staggered (B) conformations. There are NH Cl-, NH-O and CH-O intra and intermolecular secondary interactions in (S)-2b and (R)-2c resulting in supramolecular structures. (C) 2015 Elsevier By. All rights reserved.

A fluorescent molecularly-imprinted polymer gate with temperature and pH as inputs for detection of alpha-fetoprotein

In this work, we have reported a new approach on the use of stimuli-responsive molecularly imprinted polymer (MIP) for trace level sensing of alpha-fetoprotein (AFP), which is a well know cancer biomarker. The stimuli-responsive MIP is composed of three components, a thermo-responsive monomer, a pH responsive component (tyrosine derivative) and a highly fluorescent vinyl silane modified carbon dot. The synthesized AFP-imprinted polymer possesses excellent selectivity towards their template molecule and dual-stimuli responsive behavior. Along with this, the imprinted polymer was also explored as `OR' logic gate with two stimuli (pH and temperature) as inputs. However, the non-imprinted polymers did not have such `OR' gate property, which confirms the role of template binding. The imprinted polymer was also used for estimation of AFP in the concentration range of 3.96-80.0 ng mL(-1), with limit of detection (LOD) 0.42 ng mL(-1). The role of proposed sensor was successfully exploited for analysis of AFP in real human blood plasma, serum and urine sample. (C) 2015 Elsevier B.V. All rights reserved.

Mycobacterium tuberculosis WhiB3 Responds to Vacuolar pH-induced Changes in Mycothiol Redox Potential to Modulate Phagosomal Maturation and Virulence.

The ability of Mycobacterium tuberculosis to resist intraphagosomal stresses, such as oxygen radicals and low pH, is critical for its persistence. Here, we show that a cytoplasmic redox sensor, WhiB3, and the major M. tuberculosis thiol, mycothiol (MSH), are required to resist acidic stress during infection. WhiB3 regulates the expression of genes involved in lipid anabolism, secretion, and redox metabolism, in response to acidic pH. Furthermore, inactivation of the MSH pathway subverted the expression of whiB3 along with other pH-specific genes in M. tuberculosis. Using a genetic biosensor of mycothiol redox potential (E-MSH), we demonstrated that a modest decrease in phagosomal pH is sufficient to generate redox heterogeneity in E-MSH of the M. tuberculosis population in a WhiB3-dependent manner. Data indicate that M. tuberculosis needs low pH as a signal to alter cytoplasmic E-MSH, which activates WhiB3-mediated gene expression and acid resistance. Importantly, WhiB3 regulates intraphagosomal pH by down-regulating the expression of innate immune genes and blocking phagosomal maturation. We show that this block in phagosomal maturation is in part due to WhiB3-dependent production of polyketide lipids. Consistent with these observations, Mtb Delta whiB3 displayed intramacrophage survival defect, which can be rescued by pharmacological inhibition of phagosomal acidification. Last, Mtb Delta whiB3 displayed marked attenuation in the lungs of guinea pigs. Altogether, our study revealed an intimate link between vacuolar acidification, redox physiology, and virulence in M. tuberculosis and discovered WhiB3 as crucial mediator of phagosomal maturation arrest and acid resistance in M. tuberculosis.

Integration of holographic sensors into microfluidics for the real-time pH sensing of L. casei metabolism

We describe developments in the integration of analyte specific holographic sensors into PDMS-based microfluidic devices for the purpose of continuous, low-impact monitoring of extra-cellular change in micro-bioreactors. Holographic sensors respond to analyte concentration via volume change, which makes their reduction in size and integration into spatially confined fluidics difficult. Through design and process modification many of these constraints have been addressed, and a microfluidics-based device capable of real-time monitoring of the pH change caused by Lactobacillus casei fermentation is presented as a general proof-of-concept for a wide array of possible devices.

Calidad bromatológica, organolépticas y ph en ensilaje de pasto cubano (Pennisetum purpureum x Pennisetumtyphoides) CV. CT-115 bajo el efecto de cuatro aditivos utilizados en la conservación de forraje en la finca Santa Rosa, Sabana Grande, Managua

Este estudio se realizó en la finca Santa Rosa propiedad de la Universidad Nacional Agraria en Managua, con el objetivo de evaluar lascaracterísticas organolépticas (olor, color, textura), temperatura, pH y calidadbromatológica (materia seca MS, proteína bruta PB y fibra neutro detergente FND), en ensilaje de pasto Pennisetum purpureum x PennisetumtyphoidesCV. CT- 115, bajo el efecto de cuatro aditivos para conservación: melaza, fermento de malanga, fermento de yuca y fermento de papa. El pasto fue cosechado a 60 días con tamaño de picado de2.5 cm, aplicando 800g de melaza comercial y 150cc de aditivo en cada bolsa de ensilaje, la apertura de las silobolsas se realizó a 20 días, seguidamente fueron evaluados porun jurado de expertos (4 personas). El Diseño utilizado fue un DCA con cuatro tratamientos: T1 ensilaje (CT- 115+melaza), T2 ensilaje (CT-115+melaza+fermento de malanga), el T3 ensilaje (CT- 115+melaza+fermento de yuca) y T4 ensilaje (CT-115+melaza+fermento de papa) y cuatro repeticiones, para 16 unidades experimentales. Los resultados para la variable olor en aproximación al valor ideal fueron del 87.55% para T1; T2: 88.55%, T3: 72.33% y T4: 77.74%; con respecto al color el T1 alcanzó el valor: 77.08%, T2: 100%, T3: 89.58% y T4: 85.41%; en cuanto a la textura los resultados fueron para T1, T2, y T3 del 100%, para T4: 93.77%.La variable temperatura reportó resultadosde 31.75°C para T1, T2 y T3: 32.00°C y T4: 31.50°C.Para la variable pH se encontró que el T2 presentó diferencias significativas (p<0.05) con respecto al T1 y T4, al mismo tiempo presentó diferencias altamente significativas (p<0.01) con el T3. El T1 y T4 no presentaron diferencias significativas, pero presentaron diferencias significativas (p<0.05) con respecto al T3, y obtuvieron medias (por Tukey) para T1 de 4.66, T2: 4.87, T3: 4.22 y T4: 4.45.Los resultados de calidad bromatológica para MS por tratamiento fueron29.94%, 27.84%, 28.20% y 32.59%, respetivamente. La PB alcanzó valores de 5.22%, 4.64%, 4.75% y 4.76%, por tratamiento respectivamente. La FND presentó valores por tratamiento de 55.41%, 64.10%, 63.06% y 57.01%, respectivamente. Con base en estos resultados se estima que el ensilaje del T2 presentó los mejores resultados en cuanto a características organolépticas, aunque bromatológicamente no supero al testigo (T1), el uso de aditivos de fermentos en el ensilaje mejora su calidad organoléptica.

Determinación de la concentración de pH en hojas de cultivares clonales Spondias purpurea L, en el arboretum Alain Meyrat de la Universidad Nacional Agraria, Managua, Nicaragua

La presente investigación tiene como objetivo determinar la concentración de pH en las hojas de 17 cultivares clónales de Spondias purpurea L, ubicado en el Arboretum Alain Meyrat de la Universidad Nacional Agraria, la metodología utilizada consistió en la recolección del material vegetativo de las cuales se seleccionaron 20 hojas de cada cultivar clonal en buen estado (sanas, verdes y completas). Se procedió medir con ayuda de una balanza el peso verde de las hojas separando los foliolos y el raquis la cuales se rotularon con el nombre de cada cultivar clonal. Para determinar la concentración pH de cada cultivar se recortó los foliolos y el raquis utilizando 3 g de cada muestra, se macera con un mortero hasta obtener materia molida. Una vez macerado los 3 g de cada muestra se determina la solubilidad de las hojas, haciendo uso de solventes como el agua (H₂0), benceno (C₆H₆), etanol (CH₃-CH₂-0H), y tetracloruro de carbono (CCL₄), para ello se utilizó 3 ml de cada solvente. Se empleó el uso de un pHmetro para determinar la concentración de pH de las muestras combinadas con los solventes y pH de la muestra sin solvente. Se obtuvo que el pH del cultivar San franciscano posee mayor contenido de acidez empleando los solventes químicos y el raquis seco para elaborar infusiones, por el contrario las infusiones con los foliolos secos del cultivar Cocer se obtuvo la mayor concentración de acidez

Effects of pH on Growth of Salvinia molesta Mitchell

Growth of giant salvinia ( Salvinia molesta Mitchell) under different pH regimes was examined at the Lewisville Aquatic Ecosystem Research Facility (LAERF) in Lewisville, Texas.(PDF has 5 pages.)

The Influence of Formulation, Buffering, pH and Divalent Cations on the Activity of Endothall on Hydrilla.

Endothall has been used as an aquatic herbicide for more than 40 years and provides very effective weed control of many weeds. Early research regarding the mechanism-of-action of endothall contradicts the symptomology normally associated with the product. Recent studies suggest endothall is a respiratory toxin but the mechanism-of-action remains unknown. To further elucidate the activity of endothall, several endothall formulations were evaluated for their effects on ion leakage, oxygen consumption and photosynthetic oxygen evolution from hydrilla shoot tips. The influence of pH, buffering and divalent cations was also evaluated. (PDF contains 6 pages.)

In situ measurement of dissolved inorganic carbon speciation in natural waters, pH, pC02, TA, & TC02, Honolulu, Hawaii, February 16-18, 2005: workshop proceedings

The Alliance for Coastal Technology (ACT) convened a workshop on the in situ measurement of dissolved inorganic carbon species in natural waters in Honolulu, Hawaii, on February 16, 17, and 18, 2005. The workshop was designed to summarize existing technologies for measuring the abundance and speciation of dissolved inorganic carbon and to make strategic recommendations for future development and application of these technologies to coastal research and management. The workshop was not focused on any specific technology, however, most of the attention of the workshop was on in situ pC02 sensors given their recent development and use on moorings for the measurement of global carbon fluxes. In addition, the problems and limitations arising from the long-term deployment of systems designed for the measurement of pH, total dissolved inorganic carbon (DIC), and total alkalinity (TA) were discussed. Participants included researchers involved in carbon biogeochemistry, industry representatives, and coastal resource managers. The primary questions asked during the workshop were: I. What are the major impediments to transform presently used shipboard pC02 measurement systems for use on cost-eficient moorings? 2. What are the major technical hurdles for the in situ measurement of TA and DIC? 3. What specific information do we need to coordinate efforts for proof of concept' testing of existing and new technologies, inter-calibration of those technologies, better software development, and more precise knowledge quantzjjing the geochemistry of dissolved inoeanic carbon species in order to develop an observing system for dissolved inorganic carbon? Based on the discussion resulting from these three questions, the following statements were made: Statement No. 1 Cost-effective, self-contained technologies for making long-term, accurate measurements of the partial pressure of C02 gas in water already exist and at present are ready for deployment on moorings in coastal observing systems. Statement No. 2 Cost-effective, self-contained systems for the measurement of pH, TA, and DIC are still needed to both fully define the carbonate chemistry of coastal waters and the fluxes of carbon between major biogeochemical compartments (e.g., air-sea, shelf-slope, water column-sediment, etc.). (pdf contains 23 pages)

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

WEFTA-Laborvergleichsuntersuchungen zur pH-Bestimmung in Fischerei-Erzeugnissen - Eine gemeinsame Aktion der Western European Fish Technologists' Association

12 samples (6 original samples and 6 diluted samples) were analysed by 14 WEFTA laboratories for their pH values in an inter-laboratory comparison exercise. As a result it can be stated that the majority of participating laboratories could determine the pH values very exactly. The pH values obtained are ranging only little around the calculated mean (less than 0.1 pH unit). It could also be demonstrated that the participating institutes could analyse both, pH values in fishery products and aqueous salt solutions. However, also in this exercise a number of outliers and deviating values have been detected. Therefore it is of utmost importance to calibrate the pH electrodes in regular intervals and to maintain them carefully. Intra-laboratory comparison measurements are recommended to detect weak points.

Adsorption of Pb(II) and Cu(II) on α-quartz from aqueous solutions: influence of pH, ionic strength, and complexing ligands

Adsorption of aqueous Pb(II) and Cu(II) on α-quartz was studied as a function of time, system surface area, and chemical speciation. Experimental systems contained sodium as a major cation, hydroxide, carbonate, and chloride as major anions, and covered the pH range 4 to 8. In some cases citrate and EDTA were added as representative organic complexing agents. The adsorption equilibria were reached quickly, regardless of the system surface area. The positions of the adsorption equilibria were found to be strongly dependent on pH, ionic strength and concentration of citrate and EDTA. The addition of these non-adsorbing ligands resulted in a competition between chelation and adsorption. The experimental work also included the examination of the adsorption behavior of the doubly charged major cations Ca(II) and Mg(II) as a function of pH.

The theoretical description of the experimental systems was obtained by means of chemical equilibrium-plus-adsorption computations using two adsorption models: one mainly electrostatic (the James-Healy Model), and the other mainly chemical (the Ion Exchange-Surface Complex Formation Model). Comparisons were made between these two models.

The main difficulty in the theoretical predictions of the adsorption behavior of Cu(II) was the lack of the reliable data for the second hydrolysis constant(*β_2) The choice of the constant was made on the basis of potentiometric titratlons of Cu^(2+)

The experimental data obtained and the resulting theoretical observations were applied in models of the chemical behavior of trace metals in fresh oxic waters, with emphasis on Pb(II) and Cu(II).