Flow injection analysis of fluoride: optimization of experimental conditions and non-linear calibration using artificial neural networks

This paper deals with the application of artificial neural networks (ANNs) to two common problems in spectroscopy: optimization of experimental conditions and non-linear calibration of the result, with particular reference to the determination of fluoride by flow injection analysis (FIA). The FIA system was based on the formation of a blue ternary complex between zirconium(IV), p-methyldibromoarsenazo and F- with the maximum absorption wavelength at 635 nm. First, optimization in terms of sensitivity and sampling rate was carried out by using jointly a central composite design and ANNs, and a neural network with a 3-7-1 structure was confirmed to be able to provide the maximum performance. Second, the relationship between the concentration of fluoride and its absorbance was modeled by ANNs. In this process, cross-validation and leave-k-out were used. The results showed that good prediction was attained in the 1-4-1 neural net. The trained networks proved to be very powerful in both applications. The proposed method was successfully applied to the determination of free fluoride in tea and toothpaste with recoveries between 96 and 101%.     

Surface mobility and diffusion at interfaces of polystyrene in the vicinity of the glass transition

Symmetric polydisperse (M_w = 23 × 10⁴, M_w/M_n = 2.84) and monodisperse (M_w = 21 × 10⁴, M_w/M_n < 1.05) polystyrene (PS), and asymmetric polydisperse PS/poly(2,6-dimethyl 1,4-phenylene oxide) (PPO) interfaces have been bonded in the vicinity of the glass transition temperature (T_g) of PS. In a lap-shear joint geometry, strength develops in all cases with time to the fourth power, which indicates that it is diffusion controlled. Strength developing at short times at the polydisperse PS/PS interface, at 90°C, is higher than that at the monodisperse interface, at 92°C (at T_g − 13°C in both cases), presumably due to the contribution of the low molecular weight species. The decrease of strength at the PS/PPO interface when the bonding temperature decreases from 113 to 70°C, i.e., from T_g + 10°C to T_g − 33°C of the bulk PS, indicates a high molecular mobility at the surface as compared to that in the bulk, and can be expressed by a classical diffusion equation, which is valid above T_g (of the surface layer). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 567–572, 1998     

Ultrafiltration of BSA in pulsating conditions: an artificial neural networks approach

The aim of the present paper is to analyze membrane systems behavior, operating in pulsating conditions, by means of artificial neural networks (ANNs). Different ANNs have been developed, by means of Matlab^® Neural Network Toolbox, to model the ultrafiltration process of aqueous BSA solutions through poly-ethersulfone membranes. A specific neural network architecture, constituted by one input layer, two hidden layers and one output layer, has been finally identified by a trial-and-error procedure. The network has been trained through a selected set of experimental data obtained for a lab-scale flat sheet membrane module, equipped with a device capable of producing periodic pulses of the applied trans-membrane pressure (TMP) and feed flow rate. It has been found that the developed neural network is capable of offering very accurate predictions of actual system behavior either when it is tested within the range used for training or when the inputs combination has been never exploited during learning phase. The observed reliability of neural networks predictions of membrane performances has suggested to use them for searching an optimal pulsation frequency profile able to maximize permeate flux. The utilization of such a pulse frequency profile allows obtaining, on the basis of theoretical evaluations only, significant improvements of membrane performances with respect to UF experiments performed at fixed and constant pulsation frequencies.     

Anomalous volumetric behavior of water-hexane and water-decane mixtures in the vicinity of the critical region as studied by infrared spectroscopy

Infrared spectra of binary mixtures of water with hexane and decane were measured at temperatures and pressures in the 473-648 K and 70-350 bar ranges, respectively. Volumetric concentrations of water and the hydrocarbons in the mixtures were obtained from absorption intensities of the fundamental OH stretching band of HDO and combination transitions of the hydrocarbons. Using both the concentrations, densities of the aqueous mixtures were estimated and compared with densities before mixing, which were calculated using literature densities of the neat liquids. It is found that anomalously large volume expansion on mixing occurs in the vicinity of the critical region of the mixtures.     

NMR characterization of dilauroyl phosphatidylcholine in adsorbed monolayers at fluid interfaces studied by multiscale computations

Structural characteristics of model monolayers of dilauroyl phosphatidylcholine (1,2‐dilauroyl‐sn‐glycerol‐3‐phosphatidylcholine [DLPC]) adsorbed at the water/vapors and water/octane interfaces were studied by means of computational chemistry methods. Coarse‐grained, followed by all‐atom molecular dynamics simulations were used to obtain the monolayers equilibrium structures at room temperature at both fluid interfaces. The analysis of the polar head orientation, polar region thickness, tail lengths, and NMR order parameter revealed that the different interface composition affects only the tail lengths and their orientation with respect to the interface. At the octane/water boundary the DLPC tails are less extended than the tails at the water/vacuum interface and are rather significantly tilted or multiply folded. Very similar structuring of the polar DLPC region at both studied boundaries was established. Dynamic ¹³C NMR chemical shift values, δ(¹³C) computed with density functional theory allowed to identify the interface effect on the DLPC molecular structure and the intramolecular motions in the adsorbed monolayer at the room temperature equilibrium. Detailed analysis of these dynamic δ(¹³C) values compared with available experimental data and static δ(¹³C) estimates of one DLPC low‐energy conformer are presented and discussed.     

Structures and charging of alpha-alumina (0001)/water interfaces studied by sum-frequency vibrational spectroscopy

Sum-frequency vibrational spectroscopy in the OH stretch region was employed to study structures of water/alpha-Al2O3 (0001) interfaces at different pH values. Observed spectra indicate that protonation and deprotonation of the alumina surface dominate at low and high pH, respectively, with the interface positively and negatively charged accordingly. The point of zero charge (pzc) appears at pH approximately = 6.3, which is close to the values obtained from streaming potential and second-harmonic generation studies. It is significantly lower than the pzc of alumina powder. The result can be understood from the pK values of protonation and deprotonation at the water/alpha-Al2O3 (0001) interface. The pzc of amorphous alumina was found to be similar to that of powder alumina.     

Molecular interactions of proteins and peptides at interfaces studied by sum frequency generation vibrational spectroscopy

Interfacial peptides and proteins are critical in many biological processes and thus are of interest to various research fields. To study these processes, surface sensitive techniques are required to completely describe different interfacial interactions intrinsic to many complicated processes. Sum frequency generation (SFG) spectroscopy has been developed into a powerful tool to investigate these interactions and mechanisms of a variety of interfacial peptides and proteins. It has been shown that SFG has intrinsic surface sensitivity and the ability to acquire conformation, orientation, and ordering information about these systems. This paper reviews recent studies on peptide/protein-substrate interactions, peptide/protein-membrane interactions, and protein complexes at interfaces and demonstrates the ability of SFG on unveiling the molecular pictures of complicated interfacial biological processes.     

Structure of polymer networks in liquid crystals studied by 13C NMR

We report on 13C NMR measurements above and below the clearing temperature of the liquid crystal 4-n-hexyloxyphenyl 4-methoxybenzoate constrained to an oriented, low concentration polymer network. The network is obtained by UV-irradiation of the reactive monomer 1,4-di-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene which is in admixture with the liquid crystal. The characterization of orientational order of the mixtures before UV-radiation, and hence before polymerization, reveals the high order of the components at the polymerization temperature. The chosen geometry explains the LC director orientation only by the aligned network. Above the nematic-isotropic transition a strong pretransitional order is detected. Fast molecular translational diffusion averages the order over dimensions smaller than 1 mum. The Landau-de Gennes theory predicts a relation between pretransitional order and the lateral dimension of the LC regions. The experimental data are successfully explained by pore diameters of 35 and 98 nm for concentrations of 20 and 8 mol% of monomer, respectively. The results support the model of nearly cylindrical shaped liquid crystal domains surrounded by thin walls of crosslinked network.     

The study for optimization of chromatographic condition by means of artificial neural networks

In this paper, the optimization of gas chromatographic experimental parameters is investigated using a three layer feed-forward neural network with the back-propagating. The design, development, and testing of the neural network are described in detail. The chosen structure is 4-6-2 system with a learning rate eta of 0.6 and a momentum constant mu of 0.4. The results of several simulations are very satisfactory. Network results are compared with the results obtained by the orthogonal method.     

Hydration of the organized molecular assembly of ionic surfactants as studied by vapor pressure and x-ray diffraction

Equilibrium vapor pressure of water was measured for ionic surfactant-water binary systems as a function of water content over the temperature range 5–11°C. The measurement of x-ray powder diffraction has also been performed to characterize the microscopic structures of these two-component systems. Examined surfactants were the homologs of sodium alkyl sulfate and alkyltrimethylammonium bromide. It was found that dodecyl and decyl sulfate formed solid di-and trihydrate respectively, while octyl sulfate and the cationic surfactants formed lyotropic liquid crystal instead. The x-ray long spacing of the liquid crystals scarcely varied with water content.Enthalpy of vaporization was calculated for both solid hydrates and lyotropic liquid crystals.     

Circumventing the problems caused by protein diversity in microarrays: implications for protein interaction networks

Protein microarrays provide a well-controlled, high-throughput way to uncover protein-protein interactions. One problem with this and other standardized assays, however, is that proteins vary considerably with respect to their physical properties. If a simple threshold-based approach is used to define protein-protein interactions, the resulting binary networks can be strongly biased. Here, we investigate the extent to which even closely related protein interaction domains vary when printed as microarrays. We find that, when a collection of well behaved, monomeric Src homology 2 (SH2) domains are printed at the same concentration, they vary by up to 50-fold with respect to the resulting surface density of active protein. When a threshold-based binding assay is performed on these domains using fluorescently labeled phosphopeptides, a misleading picture of the underlying biophysical interactions emerges. This problem can be circumvented, however, by obtaining saturation binding curves for each protein-peptide interaction. Importantly, the equilibrium dissociation constants obtained from these curves are independent of the surface density of active protein. We submit that an increased emphasis should be placed on obtaining quantitative information from protein microarrays and that this should serve as a more general goal in all efforts to define large-scale protein interaction networks.     

States of molecular assembly and physical properties of crystalline long-chain compounds studied by vibrational spectroscopy

Various types of molecular assembly of long-chain compounds in solid states were investigated by means of infrared absorption, Raman and Brillouin spectroscopic methods. As for the polymorphism in even-numbered n-fatty acids, three monoclinic modifications, B, C, and E, all consisting of the orthorhombic polyethylene sublattice, give rise to their characteristic infrared and Raman spectra. A dynamical equilibrium between cis and trans conformations of the hydrogen-bonded carboxyl groups in modification C, which is related to the high-temperature stable character of this phase, is reflected to a dramatic change with temperature in the low-frequency Raman spectra. A new type of reversible solid state phase transition was found between two A-type (triclinic) modifications of myristic, palmitic, and stearic acids. The γ→α phase transition of oleic acid was found to be caused by a conformational disordering of polymethylene chains at the lamellar interfacial region. Two basic polytype structures, Mon and Orth II, of stearic acid B were investigated, and it was found that the low-frequency phonon frequencies (below 50 cm⁻¹) were strongly influenced by the polytype structure. Based on the spectroscopic considerations, Orth II was predicted as the thermodynamically stable phase around room temperature compared with Mon, and the stability is responsible for the vibrational free energy term. Some experimental findings which support this prediction were obtained. The values of the stiffness tensor elements of Mon and Orth II, measured by Brillouin scattering, indicate that the mechanical behavior of bulk crystals is very dependent on the polytype structure. The relationship between the mobility of chain molecules and the width of the spectral bands was investigated in a quantitative manner for the case of n-alkane molecules entrapped in the urea inclusion adducts. The changes in the half-width for the polarization components of various Raman bands on the transition from the orthorhombic to the hexagonal phase are interpreted in terms of the correlation functions of the Raman tensor related to the rotational motion of the alkane molecules around the chain axes.     

Adsorption of monovalent and divalent cations on planar water-silica interfaces studied by optical reflectivity and Monte Carlo simulations

Adsorption on planar silica substrates of various monovalent and divalent cations from aqueous solution is studied by optical reflectivity. The adsorbed amount is extracted by means of a thin slab model. The experimental data are compared with grand canonical Monte Carlo titration simulations at the primitive model level. The surface excess of charge due to adsorbed cations is found to increase with pH and salt concentration as a result of the progressive dissociation of silanol groups. The simulations predict, in agreement with experiments, that the surface excess of charge from divalent ions is much larger than from monovalent ions. Ion-ion correlations explain quantitatively the enhancement of surface ionization by multivalent cations. On the other hand, the combination of experimental and simulation results strongly suggests the existence of a second ionizable site in the acidic region. Variation of the distance of closest approach between the ions and surface sites captures ion specificity of water-silica interfaces in an approximate fashion.     

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of PVA aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug. The drug release followed different release mechanism at pH 4.0 and pH 7.4, respectively.     

Exploiting the multifunctionality of organocations in the assembly of hybrid polyoxometalate clusters and networks

Assembly of an unprecedented [(P(V)Mn(II)W(VI)(11)O(39))2{P(V)O(4)}](13-) and a [P(2)Mn(4)W(18)O(68)](10-) cluster have been observed and structurally characterised and cryospray mass spectroscopic ionization (CSI) has been used to observe one of the very reactive building blocks linking solid state with solution studies.     

Adsorption behaviour and surfactant elution of cationic salivary proteins at solid/liquid interfaces,studied by in situ ellipsometry

Adsorption of the cationic salivary proteins lactoferrin, lactoperoxidase, lysozyme and histatin 5 to pure (hydrophilic) and methylated (hydrophobized) silica surfaces was investigated by in situ ellipsometry. Effects of concentration (≤10 μg ml⁻¹, for lysozyme ≤200 μg ml⁻¹) and dependence of surface wettability, as well as adsorption kinetics and elutability of adsorbed films by buffer and sodium dodecyl sulphate (SDS) solutions were investigated. Results showed that the amounts adsorbed decreased in the order lactoferrin ≥ lactoperoxidase > lysozyme ≥ histatin 5. On hydrophilic silica, the adsorption was most likely driven by electrostatic interactions, which resulted in adsorbed amounts of lactoferrin that indicated the formation of a monolayer with both side-on and end-on adsorbed molecules. For lactoperoxidase the adsorbed amounts were somewhat higher than an end-on monolayer, lysozyme adsorption showed amounts corresponding to a side-on monolayer, and histatin 5 displayed adsorbed amounts in the range of a side-on monolayer. On hydrophobized substrata, the adsorption was also mediated by hydrophobic interactions, which resulted in lower adsorbed amounts of lactoferrin and lactoperoxidase; closer to side-on monolayer coverage. For both lysozyme and histatin 5 the adsorbed amounts were the same as on the hydrophilic silica. The investigated proteins exhibited fast adsorption kinetics, and the initial kinetics indicated mass transport controlled behaviour at low concentrations on both types of substrates. Buffer rinsing and SDS elution indicated that the proteins in general were more tightly bound to the hydrophobized surface compared to hydrophilic silica. Overall, the surface activity of the investigated proteins implicates their importance in the salivary film formation.     

The secondary structure of a membrane-modifying peptide in a supramolecular assembly studied by PELDOR and CW-ESR spectroscopies.

The new technique of pulsed electron-electron double resonance in electron spin-echo (PELDOR) in combination with the CW-ESR method has been used to investigate the secondary structure of a double spin-labeled peptide (the [TOAC-1,8]-analogue of the peptaibol antibiotic trichogin GA IV) that is hidden into a tetrameric supramolecular assembly of unlabeled peptide molecules. The magnetic dipole-dipole relaxation of spin labels has been experimentally studied in glassy solutions of the double-labeled peptide frozen to 77 K in a mixture of chloroform-toluene with an excess of unlabeled peptide. The PELDOR signal oscillations have been observed at high degrees of dilution with unlabeled peptide. The intramolecular distance between the spin labels of the peptide molecule in the aggregate has been determined from the oscillation frequency to be 15.7 A which is close to the value of (approximately equal to) 14 A calculated for a 3(10)-helical structure. Estimation of the fraction of this ordered secondary structure shows that about 19% of the peptide molecules in aggregates are folded in the 3(10)-helical conformation. The present experimental results are consistent with our molecular model presented in J. Am. Chem. Soc. 2000, 122, 3843-3848, wherein four amphiphilic 3(10)-helical peptide molecules form a vesicular system with the polar amino acid side chains pointing to the interior, and the apolar side chains, to the exterior of the cluster. The experimental data were compared with the results obtained with other techniques.     

Unusual oxidation of organics at interfaces from the bottom up and atmospheric implications

Photolysis of a mixture of NaNO2 with NaCl with an adsorbed coating of 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (OPPC) is shown to lead to oxidation of the OPPC. This oxidation "from the bottom up" is due to the generation of the OH free radical from nitrite ion photochemistry in the presence of water and its addition to the OPPC double bond. Such chemistry may be important in the lower atmosphere.     

Optimization of a high-performance liquid chromatography system by artificial neural networks for separation and determination of antioxidants

A high-performance liquid chromatography (HPLC) system was used to determine the antioxidants tert-butyl-hydroquinone (TBHQ), tert-butylhydroxyanisole (BHA), and 3,5-di-tert-butylhydroxytoluene (BHT) simultaneously in oils. The paper presents a new methodology for the optimized separation of antioxidants in oils based on the coupling of experimental design and artificial neural networks. The orthogonal design and the artificial neural networks with extended delta-bar-delta (EDBD) learning algorithm were employed to design the experiments and optimize the variables. The response function (Rf) used was a weighted linear combination of two variables related to separation efficiency and retention time, according to which the optimized conditions were obtained. The above-mentioned antioxidants in rapeseed oils were separated and determined simultaneously under optimized conditions by HPLC with UV detection at 280 nm. Linearity was obtained over the range of 10-200 microg/mL with recoveries of 98.3% (TBHQ), 98.1% (BHT), and 96.2% (BHA).