Bubble formation at closely spaced orifices in aqueous solutions

A filter cloth with 182 holes per 10−4 m2 has been used to generate air bubbles both in pure water and in aqueous solutions of electrolytes and non-electrolytes at various air flow rates. Potassium bromide and ammonium perchlorate were the electrolytes used, while the non-electrolytes were isopropanol, urea and glycerol. Bubble diameters and their size distribution were measured from photographs. The role of solutes in affecting bubble sizes and their distribution compared to that of pure water is discussed in the light of a hypothesis. This hypothesis assumes that if the final bubble diameter is less than the inter-orifice distance, then bubbles do not coalesce; on the other hand, if it is greater, then coalescence occurs when tf greater-or-equal, slantedti+ts, but does not occur when t

Deviation from 3-D Ising critical behaviour in aqueous electrolyte solutions

The near-critical behaviour in complex fluids, comprising electrolyte solutions, polymer solutions and amphiphilic systems, reveals a marked departure from the 3-D Ising behaviour. This departure manifests itself either in terms of a crossover from Ising to mean-field (or classical) critical behaviour, when moving away from a given critical point (Tc), or by the persistence of only mean-field region in the surprisingly close vicinity of Tc. The ilo,non-Ising features of the osmotic compressibility (chi(T,p)) in solutions of electrolytes, that exhibit orle or many liquid-liquid transitions, will be presented. The underlying cause of the breakdown of the anticipated 3-D Ising behaviour in aqueous electrolyte solutions is traced to the structuring induced by the electrolytes. New evidence constituting, measurements of small-angle X-ray scattering (SAXS) and the excess molar volume, is advanced to support the thesis of the close relationship, between the structuring and the deviation from the 3-D Ising critical behaviour in aqueous electrolyte solutions.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Dimethyl sulfoxide induced structural transformations and non-monotonic concentration dependence of conformational fluctuation around active site of lysozyme

Experimental studies have observed significant changes in both structure and function of lysozyme (and other proteins) on addition of a small amount of dimethyl sulfoxide (DMSO) in aqueous solution. Our atomistic molecular dynamic simulations of lysozyme in water-DMSO reveal the following sequence of changes on increasing DMSO concentration. (i) At the initial stage (around 5% DMSO concentration) protein's conformational flexibility gets markedly suppressed. From study of radial distribution functions, we attribute this to the preferential solvation of exposed protein hydrophobic residues by the methyl groups of DMSO. (ii) In the next stage (10-15% DMSO concentration range), lysozome partially unfolds accompanied by an increase both in fluctuation and in exposed protein surface area. (iii) Between 15-20% concentration ranges, both conformational fluctuation and solvent accessible protein surface area suddenly decrease again indicating the formation of an intermediate collapse state. These results are in good agreement with near-UV circular dichroism (CD) and fluorescence studies. We explain this apparently surprising behavior in terms of a structural transformation which involves clustering among the methyl groups of DMSO. (iv) Beyond 20% concentration of DMSO, the protein starts its final sojourn towards the unfolding state with further increase in conformational fluctuation and loss in native contacts. Most importantly, analysis of contact map and fluctuation near the active site reveal that both partial unfolding and conformational fluctuations are centered mostly on the hydrophobic core of active site of lysozyme. Our results could offer a general explanation and universal picture of the anomalous behavior of protein structure-function observed in the presence of cosolvents (DMSO, ethanol, tertiary butyl alcohol, dioxane) at their low concentrations. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3694268]

Hydration dynamics of protein molecules in aqueous solution: Unity among diversity

Dielectric dispersion and NMRD experiments have revealed that a significant fraction of water molecules in the hydration shell of various proteins do not exhibit any slowing down of dynamics. This is usually attributed to the presence of the hydrophobic residues (HBR) on the surface, although HBRs alone cannot account for the large amplitude of the fast component. Solvation dynamics experiments and also computer simulation studies, on the other hand, repeatedly observed the presence of a non-negligible slow component. Here we show, by considering three well-known proteins (lysozyme, myoglobin and adelynate kinase), that the fast component arises partly from the response of those water molecules that are hydrogen bonded with the backbone oxygen (BBO) atoms. These are structurally and energetically less stable than those with the side chain oxygen (SCO) atoms. In addition, the electrostatic interaction energy distribution (EIED) of individual water molecules (hydrogen bonded to SCO) with side chain oxygen atoms shows a surprising two peak character with the lower energy peak almost coincident with the energy distribution of water hydrogen bonded to backbone oxygen atoms (BBO). This two peak contribution appears to be quite general as we find it for lysozyme, myoglobin and adenylate kinase (ADK). The sharp peak of EIED at small energy (at less than 2 k(B)T) for the BBO atoms, together with the first peak of EIED of SCO and the HBRs on the protein surface, explain why a large fraction (similar to 80%) of water in the protein hydration layer remains almost as mobile as bulk water Significant slowness arises only from the hydrogen bonds that populate the second peak of EIED at larger energy (at about 4 k(B)T). Thus, if we consider hydrogen bond interaction alone, only 15-20% of water molecules in the protein hydration layer can exhibit slow dynamics, resulting in an average relaxation time of about 5-10 ps. The latter estimate assumes a time constant of 20-100 ps for the slow component. Interestingly, relaxation of water molecules hydrogen bonded to back bone oxygen exhibit an initial component faster than the bulk, suggesting that hydrogen bonding of these water molecules remains frustrated. This explanation of the heterogeneous and non-exponential dynamics of water in the hydration layer is quantitatively consistent with all the available experimental results, and provides unification among diverse features.

Spontaneous formation of branched nanochains from room temperature molten amides: visible and near-IR active, SERS substrates for non-fluorescent and fluorescent analytes

Highly stable, branched gold nanoworms are formed spontaneously in an acetamide-based room temperature molten solvent without any additional external stabilizing or aggregating agent. The nanoworms can be anchored onto solid substrates such as indium tin oxide (ITO) without any change in morphology. The anchored nanoworms are explored as substrates for surface enhanced Raman scattering (SERS) studies using non-fluorescent 4-mercaptobenzoic acid (4-MBA) and fluorescent rhodamine 6G (R6G) as probe molecules. The anchored nanostructured particles respond to near IR (1064 nm) as well as visible (785, 632.8 and 514 nm) excitation lasers and yield good surface enhancement in Raman signals. Enhancement factors of the order 10(6)-10(7) are determined for the analytes using a 1064 nm excitation source. Minimum detection limits based on adsorption from ethanolic solutions of 1028 M 4-MBA and aqueous solutions of 1027 M R6G are achieved. Experimental Raman frequencies and frequencies estimated by DFT calculations are in fairly good agreement. SERS imaging of the nanostructures suggests that the substrates comprising of three dimensional, highly interlinked particles are more suited than particles fused in one dimension. The high SERS activity of the branched nanoworms may be attributed to both electromagnetic and charge transfer effects.

Formulation of nanotized curcumin and demonstration of its antimalarial efficacy

Aim: The present study was conducted to overcome the disadvantages associated with the poor water solubility and low bioavailability of curcumin by synthesizing nanotized curcumin and demonstrating its efficacy in treating malaria. Materials and methods: Nanotized curcumin was prepared by a modified emulsion-diffusion-evaporation method and was characterized by means of transmission electron microscopy, atomic force microscopy, dynamic light scattering, Zetasizer, Fourier transform infrared spectroscopy, and differential thermal analysis. The novelty of the prepared nanoformulation lies in the fact that it was devoid of any polymeric matrices used in conventional carriers. The antimalarial efficacy of the prepared nanotized curcumin was then checked both in vitro and in vivo. Results: The nanopreparation was found to be non-toxic and had a particle size distribution of 20-50 nm along with improved aqueous dispersibility and an entrapment efficiency of 45%. Nanotized curcumin (half maximal inhibitory concentration IC50]: 0.5 mu M) was also found to be ten-fold more effective for growth inhibition of Plasmodium falciparum in vitro as compared to its native counterpart (IC50: 5 mu M). Oral bioavailability of nanotized curcumin was found to be superior to that of its native counterpart. Moreover, when Plasmodium berghei-infected mice were orally treated with nanotized curcumin, it prolonged their survival by more than 2 months with complete clearance of parasites in comparison to the untreated animals, which survived for 8 days only. Conclusion: Nanotized curcumin holds a considerable promise in therapeutics as demonstrated here for treating malaria as a test system.

A bio-attuned ratiometric hydrogen sulfate ion selective receptor in aqueous solvent: structural proof of the H-bonded adduct

A new cell permeable quinazoline based receptor (1) selectively senses HSO4- ions of nanomolar region in 0.1 M HEPES buffer (ethanol-water: 1/5, v/v) at biological pH over other competitive ions through the proton transfer followed by hydrogen bond formation and subsequent anion coordination to yield the LHSO4]-LH+center dot 3H(2)O (2) ensemble, which has been crystallographically characterised to ensure the structure property relationship. This non-cytotoxic HSO4- ion selective biomarker has great potential to recognize the intercellular distribution of HSO4- ions in HeLa cells under fluorescence microscope.

Composition dependent multiple structural transformations of myoglobin in aqueous ethanol solution: A combined experimental and theoretical study

Experimental studies (circular dichroism and ultra-violet (UV) absorption spectra) and large scale atomistic molecular dynamics simulations (accompanied by order parameter analyses) are combined to establish a number of remarkable (and unforeseen) structural transformations of protein myoglobin in aqueous ethanol mixture at various ethanol concentrations. The following results are particularly striking. (1) Two well-defined structural regimes, one at x(EtOH) similar to 0.05 and the other at x(EtOH) similar to 0.25, characterized by formation of distinct partially folded conformations and separated by a unique partially unfolded intermediate state at x(EtOH) similar to 0.15, are identified. (2) Existence of non-monotonic composition dependence of (i) radius of gyration, (ii) long range contact order, (iii) residue specific solvent accessible surface area of tryptophan, and (iv) circular dichroism spectra and UV-absorption peaks are observed. Interestingly at x(EtOH) similar to 0.15, time averaged value of the contact order parameter of the protein reaches a minimum, implying that this conformational state can be identified as a molten globule state. Multiple structural transformations well known in water-ethanol binary mixture appear to have considerably stronger effects on conformation and dynamics of the protein. We compare the present results with studies in water-dimethyl sulfoxide mixture where also distinct structural transformations are observed along with variation of co-solvent composition. (C) 2015 AIP Publishing LLC.

Non-enzymatic electronic detection of glucose using aminophenylboronic acid functionalized reduced graphene oxide

We report the non-enzymatic electronic detection of glucose using field effect transistor (FET) devices made of aminophenylboronic acid (APBA) functionalized reduced graphene oxide (RGO). Detection of glucose molecules was carried out over a wide dynamic range of concentration varying from 100 pM to 100 mM with a detection limit of similar to 2 nM using both covalently and non-covalently functionalized APBA-RGO complex. The normalized change in electrical conductance data shows that the FET devices made of non-covalently functionalized APBA-RGO complex (nc-APBA-RGO) exhibited a linear response to glucose aqueous solution of concentrations varying from 1 nM to 10 mM and showed 4 times enhanced sensitivity over the devices made of covalently functionalized APBA-RGO complex (c-APBA-RGO). Specificity of APBA-RGO complex to glucose is confirmed from the observation of negligible change in electrical conductance after exposure to 0.1 mM of lactose and other interfering factors. (C) 2015 Elsevier B.V. All rights reserved.

Evidence of clustering in an aqueous electrolyte solution: a small-angle X-ray scattering study

The work reported hen was motivated by a desire to verify the existence of structure - specifically MP-rich clusters induced by sodium bromide (NaBr) in the ternary liquid mixture 3-methylpyridine (Mf) + water(W) + NaBr. We present small-angle X-ray scattering (SAXS) measurements in this mixture. These measurements were obtained at room temperature (similar to 298 K) in the one-phase region (below the relevant lower consolute points, T(L)s) at different values of X (i.e., X = 0.02 - 0.17), where X is the weight fraction of NaBr in the mixture. Cluster-size distribution, estimated on the assumption that the clusters are spherical, shows systematic behaviour in that the peak of the distribution shifts rewards larger values of cluster radius as X increases. The largest spatial extent of the clusters (similar to 4.5 nm) is seen at X = 0.17. Data analysis assuming arbitrary shapes and sizes of clusters gives a limiting value of cluster size (- 4.5 nm) that is not very sensitive to X. It is suggested that the cluster size determined may not be the same as the usual critical-point fluctuations far removed from the critical point (T-L). The influence of the additional length scale due to clustering is discussed from the standpoint of crossover from Ising to mean-field critical behaviour, when moving away from the T-L.

Transition from disc to rod-like shape of 16-3-16 dimeric micelles in aqueous solutions

Small-angle neutron scattering (SANS) measurements from bis-cationic C16H33N+(CH3)(2)-(CH2)(3)-N+ (CH3)(2)C16H33 2Br(-) dimeric surfactant, referred to as 16-3-16, at different concentrations and temperatures, are reported. It is seen that micelles are disc-like for concentrations C = 2.5 and 10 mM at temperature T = 30 degrees C. At low concentration C = 0.5 mM micelles are rod-like. Similarly, there is a disc to rod-like transition of micelles on increasing the temperature. For C = 2.5 mM, micelles are rod-like at T = 45 and 70 degrees C.

Mixed convection in non-Newtonian fluids along a vertical plate in a porous medium

The problem of mixed convection from vertical surfaces in a porous medium saturated with a power-law type non-Newtonian fluid is investigated. The transformed conservation laws are solved numerically for the case of variable wall temperature conditions. Results for the details of the velocity and temperature fields as well as the Nusselt number have been presented. The viscosity index ranged from 0.5-2.0.

Crossover from Ising to mean-field critical behavior in an aqueous electrolyte solution

The near-critical behavior of the susceptibility deduced from light-scattering measurements in a ternary liquid mixture of 3-methylpyridine, water, and sodium bromide has been determined. The measurements have been performed in the one-phase region near the lower consolute points of samples with different concentrations of sodium bromide. A crossover from Ising asymptotic behavior to mean-field behavior has been observed. As the concentration of sodium bromide increases, the crossover becomes more pronounced, and the crossover temperature shifts closer to the critical temperature. The data are well described by a model that contains two independent crossover parameters. The crossover of the susceptibility critical exponent γ from its Ising value γ=1.24 to the mean-field value γ=1 is sharp and nonmonotonic. We conclude that there exists an additional length scale in the system due to the presence of the electrolyte which competes with the correlation length of the concentration fluctuations. An analogy with crossover phenomena in polymer solutions and a possible connection with multicritical phenomena is discussed.

Non-linear regression model for spatial variation in precipitation chemistry for South India

Chemical composition of rainwater changes from sea to inland under the influence of several major factors - topographic location of area, its distance from sea, annual rainfall. A model is developed here to quantify the variation in precipitation chemistry under the influence of inland distance and rainfall amount. Various sites in India categorized as 'urban', 'suburban' and 'rural' have been considered for model development. pH, HCO3, NO3 and Mg do not change much from coast to inland while, SO4 and Ca change is subjected to local emissions. Cl and Na originate solely from sea salinity and are the chemistry parameters in the model. Non-linear multiple regressions performed for the various categories revealed that both rainfall amount and precipitation chemistry obeyed a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km, and later stabilize. Regression parameters estimated for different cases were found to be consistent (R-2 similar to 0.8). Variation in one of the parameters accounted for urbanization. Model was validated using data points from the southern peninsular region of the country. Estimates are found to be within 99.9% confidence interval. Finally, this relationship between the three parameters - rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted in a small experimental watershed in the south-west India. Chemistry estimated using the model was in good correlation with observed values with a relative error of similar to 5%. Monthly variation in the chemistry is predicted from a downscaling model and then compared with the observed data. Hence, the model developed for rain chemistry is useful in estimating the concentrations at different spatio-temporal scales and is especially applicable for south-west region of India. (C) 2008 Elsevier Ltd. All rights reserved.