Development of novel methods to determine crystalline glucose content of honey based on DSC, HPLC, and viscosity measurements and their use to examine the setting propensity of honey

Crystallization must occur in honey in order to produce set or creamed honey; however, the process must occur in a controlled manner in order to obtain an acceptable product. As a consequence, reliable methods are needed to measure the crystal content of honey (φ expressed as kg crystal per kg honey), which can also be implemented with relative ease in industrial production facilities. Unfortunately, suitable methods do not currently exist. This article reports on the development of 2 independent offline methods to measure the crystal content in honey based on differential scanning calorimetry and high-performance liquid chromatography. The 2 methods gave highly consistent results on the basis of paired t-test involving 143 experimental points (P > 0.05, r**2 = 0.99). The crystal content also correlated with the relative viscosity, defined as the ratio of the viscosity of crystal containing honey to that of the same honey when all crystals are dissolved, giving the following correlation: μr = 1 + 1398.8∅**2.318. This correlation can be used to estimate the crystal content of honey in industrial production facilities. The crystal growth rate at a temperature of 14 ◦C—the normal crystallization temperature used in practice—was linear, and the growth rate also increased with the total glucose content in the honey.

Experimental viscosity measurements of biodiesels at high pressure

The viscosity of biodiesels of soybean and rapeseed biodiesels blended with mineral diesel fuel were measured at pressures of up to 200 MPa. Using a falling sinker-type viscometer reproducible viscosity data were obtained based on the time taken for a sinker to descend a fixed distance down an enclosed tube under the influence of gravity. Measurements were taken using pressures which correspond to those of interest in automotive common rail diesel engines, and at temperatures of between 25oC and 80oC. In all cases, the viscosity of the biodiesel blends were found to increase exponentially for which the blends were noted as being more viscous than pure mineral fuels. A pressure-freezing effect was not observed for the blends.

Tris(2-ethylhexyl) trimellitate (TOTM) as a potential industrial reference fluid for viscosity at high temperatures and high pressures: New viscosity, density and surface tension measurements

Tris(2-ethylhexyl) trimellitate (TOTM) was recently suggested as a reference fluid for industrial use associated with high viscosity at elevated temperature and pressure. Viscosity and density data have already been published on one sample covering the temperature range (303-373) K and at pressures up to about 65 MPa. The viscosity covered a range from about (9 to 460) mPa s. In the present article we study several other characteristics of TOTM that must be available if it were to be adopted as a standard. First, we present values for the viscosity and density obtained with a different sample of TOTM to examine the important feature of consistency among different samples. Vibrating-wire viscosity measurements were performed at pressures from (5 to 100) MPa, along 6 isotherms between (303 and 373) K. Density measurements were carried out from (293 to 373) K up to 68 MPa, along 4 isotherms, using an Anton Paar DMA HP vibrating U-tube densimeter. Secondly, we report a study of the effect of water contamination on the viscosity of TOTM, performed using an Ubbelhode viscometer under atmospheric pressure. Finally, in order to support the use of TOTM as a reference liquid for the calibration of capillary viscometers, values of its surface tension, obtained by the pendant drop method, are provided. (C) 2016 Elsevier B.V. All rights reserved.

Viscosity measuring cell using ultrasonic wave mode conversion

This work presents a cell to measure dynamic viscosity of liquids using ultrasonic wave mode conversion from longitudinal to shear wave. The strategy used to obtain the viscosity is based on the measurement of the complex reflection coefficient of shear waves at a solid-liquid interface. Viscosity measurements of automotive oils (SAE90 and SAE140) were obtained in the frequency range from 1 to 10 MHz. These results are compared with the Maxwell model with two relaxation times, showing the dependency of viscosity with frequency. Several parameters affecting viscosity measurements, including the solid material properties, liquid viscosity, and operating frequency are discussed.

Viscosity measurement of Newtonian liquids using the complex reflection coefficient

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

P3L-3 Viscosity measurement of Newtonian liquids using the complex reflection coefficient

This work presents the implementation of the ultrasonic shear reflectance method for viscosity measurement of Newtonian liquids using wave mode conversion from longitudinal to shear waves and vice-versa. The method is based on measuring the complex reflection coefficient (magnitude and phase) at a solid-liquid interface. Viscosity measurements were made in the range from 1 to 3.5MHz at 22.5°C for automotive oil (SAE40) and at 15°C for olive oil. Moreover, measurements of the olive oil were also conducted in the range from 15 to 30°C at 3.5MHz. The experimental results agree with those provided by a rotational viscometer. © 2006 IEEE.

Polymer-solvent interaction parameters of SBS rubbers by inverse gas chromatography measurements

The solubility parameters of two SBS commercial rubbers with different structures (lineal and radial), and with slightly different styrene content have been determined by inverse gas chromatography technique. The Flory–Huggins interaction parameters of several polymer–solvent mixtures have also been calculated. The influence of the polymer composition, the solvent molecular weight and the temperature over these parameters have been discussed; besides, these parameters have been compared with previous ones, obtained by intrinsic viscosity measurements. From the Flory–Huggins interaction parameters, the infinite dilution activity coefficients of the solvents have been calculated and fitted to the well-known NRTL model. These NRTL binary interaction parameters have a great importance in modelling the separation steps in the process of obtaining the rubber.

Drop formation and breakup of low viscosity elastic fluids: Effects of molecular weight and concentration

The dynamics of drop formation and pinch-off have been investigated for a series of low viscosity elastic fluids possessing similar shear viscosities, but differing substantially in elastic properties. On initial approach to the pinch region, the viscoelastic fluids all exhibit the same global necking behavior that is observed for a Newtonian fluid of equivalent shear viscosity. For these low viscosity dilute polymer solutions, inertial and capillary forces form the dominant balance in this potential flow regime, with the viscous force being negligible. The approach to the pinch point, which corresponds to the point of rupture for a Newtonian fluid, is extremely rapid in such solutions, with the sudden increase in curvature producing very large extension rates at this location. In this region the polymer molecules are significantly extended, causing a localized increase in the elastic stresses, which grow to balance the capillary pressure. This prevents the necked fluid from breaking off, as would occur in the equivalent Newtonian fluid. Alternatively, a cylindrical filament forms in which elastic stresses and capillary pressure balance, and the radius decreases exponentially with time. A (0+1)-dimensional finitely extensible nonlinear elastic dumbbell theory incorporating inertial, capillary, and elastic stresses is able to capture the basic features of the experimental observations. Before the critical "pinch time" t(p), an inertial-capillary balance leads to the expected 2/3-power scaling of the minimum radius with time: R-min similar to(t(p)-t)(2/3). However, the diverging deformation rate results in large molecular deformations and rapid crossover to an elastocapillary balance for times t>t(p). In this region, the filament radius decreases exponentially with time R-min similar to exp[(t(p)-t)/lambda(1)], where lambda(1) is the characteristic time constant of the polymer molecules. Measurements of the relaxation times of polyethylene oxide solutions of varying concentrations and molecular weights obtained from high speed imaging of the rate of change of filament radius are significantly higher than the relaxation times estimated from Rouse-Zimm theory, even though the solutions are within the dilute concentration region as determined using intrinsic viscosity measurements. The effective relaxation times exhibit the expected scaling with molecular weight but with an additional dependence on the concentration of the polymer in solution. This is consistent with the expectation that the polymer molecules are in fact highly extended during the approach to the pinch region (i.e., prior to the elastocapillary filament thinning regime) and subsequently as the filament is formed they are further extended by filament stretching at a constant rate until full extension of the polymer coil is achieved. In this highly extended state, intermolecular interactions become significant, producing relaxation times far above theoretical predictions for dilute polymer solutions under equilibrium conditions. (C) 2006 American Institute of Physics

Results of the IEA round Robin on viscosity and aging of fast pyrolysis bio-oils:long-term tests and repeatability

An international round robin study of the viscosity measurements and aging of fast pyrolysis bio-oil has been undertaken recently, and this work is an outgrowth from that effort. Two bio-oil samples were distributed to two laboratories for accelerated aging tests and to three laboratories of long-term aging studies. The accelerated aging test was defined as the change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C. The test was repeated 10 times over consecutive days to determine the intra-laboratory repeatability of the method. Other bio-oil samples were placed in storage at three temperatures, 21, 5, and -17 °C, for a period of up to 1 year to evaluate the change in viscosity. The variation in the results of the accelerated aging test was shown to be low within a given laboratory. The long-term aging studies showed that storage of a filtered bio-oil under refrigeration can minimize the amount of change in viscosity. The accelerated aging test gave a measure of change similar to that of 6-12 months of storage at room temperature for a filtered bio-oil. Filtration of solids was identified as a key contributor to improving the stability of the bio-oil as expressed by the viscosity based on results of the accelerated aging tests as well as long-term aging studies. Only the filtered bio-oil consistently gave useful results in the accelerated aging and long-term aging studies. The inconsistency suggests that better protocols need to be developed for sampling bio-oils. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace. © 2012 American Chemical Society.

Microbial susceptibility of condensation products of carboxy-terminated polybutadiene and glycerol

Keeping in view the prospects of biodegradable polymers, a polymer was synthesized by the condensation of carboxy-terminated polybutadiene (CTPB) of Mnsim-5000 with glycerol and tested for its microbial susceptibility. The results of end group estimations and viscosity measurements indicated a quantitative reaction between the two reactants under experimental conditions. The clear-zone method was employed in this investigation to test biodegradability. Two strains of Serratia and three strains of Staphylococcus did show a clear zone surrounding the colony. However, the microbial growth was found to diminish after 4 or 5 days.

Cytotoxicity of half sandwich ruthenium(II) complexes with strong hydrogen bond acceptor ligands and their mechanism of action

Neutral and cationic organometallic ruthenium(II) piano stool complexes of the type [(eta(6)-cymene)R-uCl(X)(Y)] (complexes R1-R8) has been synthesized and characterized. In cationic complexes, X, Y is either a eta(2) phosphorus ligand such as 1,1-bis(diphenylphosphino)methane (DPPM) and 1,2-bis(diphenylphosphino)ethane (DPPE) or partially oxidized ligands such as 1,2-bis(diphenylphosphino)methane monooxide (DPPMO) and 1,2-bis(diphenylphosphino)ethane monooxide (DPPEO) which are strong hydrogen bond acceptors. In neutral complexes. X is chloride and Y is a monodentate phosphorous donor. Complexes with DPPM and DPPMO ligands ([(eta(6)-cymene)Ru(eta(2)-DPPM)Cl]PF6 (R2), [(eta(6)-cymene)Ru(eta(2)-DPPMO)Cl]PF6 (R3), [(eta(6)-cymene)Ru(eta(1)-DPPM)Cl-2] (R5) and [(eta(6)-cymene)Ru(eta(1)-DPPMO)Cl-2] (R6) show good cytotoxicity. Growth inhibition study of several human cancer cell lines by these complexes has been carried out. Mechanistic studies for R5 and R6 show that inhibition of cancer cell growth involves both cell cycle arrest and apoptosis induction. Using an apoptosis PCR array, we identified the sets of antiapoptotic genes that were down regulated and pro-apoptotic genes that were up regulated. These complexes were also found to be potent metastasis inhibitors as they prevented cell invasion through matrigel. The complexes were shown to bind DNA in a non intercalative fashion and cause unwinding of plasmid DNA in cell-free medium by competitive ethidium bromide binding, viscosity measurements, thermal denaturation and gel mobility shift assays.

Folding a Polymer via Two-Point Interaction with an External Folding Agent: Use of H-Bonding and Charge-Transfer Interactions

A polymer containing electron-rich aromatic donors (1,5-dialkoxynaphthalene (DAN)) was coerced into a folded state by an external folding agent that contained an electron-deficient aromatic acceptor (pyromellitic diimide (PM)) unit. The donor-containing polymer was designed to carry a tertiary amine moiety in the linking segment, which served as an H-bonding site for reinforcing the interaction with the acceptor containing folding agent that also bore a carboxylic acid group. The H-bonding interaction of the carboxylic acid and the tertiary amine brings the PDI unit between two adjacent DAN units along the polymer backbone to induce charge-transfer (C-T) interactions, and this in turn causes the polymer chain to form a pleated structure. Evidence for the formation of such a pleated structure was obtained from NMR titration studies and also by monitoring the C-T band in their UV-visible spectra. By varying the length of the segment that links the PDI acceptor to the carboxylic acid group, we showed that the most effective folding agent was the one that had a single carbon spacer, as evident from the highest value of the association constant. Control experiments with propionic acid clearly demonstrated the importance of the additional C-T interactions for venerating the folded structures. Further, solution viscosity measurements in the presence of varying amounts of the folding agent revealed a gradual stiffening of the chain in the case of the PDI carrying carboxylic acid, whereas no such affect was seen in the case of simple propionic acid. These observations were supported by D FT calculations of the interactions of a dimeric model of the polymer with the various folding agents; here too the stability of the complex was seen to be highest in the case of the single carbon spacer.

Synthesis and characterization of thiocarbonohydrazone-based epoxy resins

Novel epoxy resins of various thiocarbonohydrazones have been synthesized by reacting the aldehyde or ketone derivatives of thiocarbohydrazide with excess of epichlorohydrin. The resins have been characterized by elemental analyses, epoxy equivalents, 1H-NMR and IR spectra, thermal analyses, and viscosity measurements. Curing of the resins has been carried out by mixing with thiocarbohydrazide or ethylenediamine and heating at 80°C for 48 h. A comparison of the thermal stability of the cured resin samples has been made.

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Cobalt(II), Nickel(II) and Copper(II) complexes of a tetradentate Schiff base as photosensitizers: Quantum yield of O-1(2) generation and its promising role in anti-tumor activity

In the present investigation, a Schiff base N'(1),N'(3)-bis(E)-(5-bromo-2-hydroxyphenyl)methylidene]benzene-1,3-d icarbohydrazide and its metal complexes have been synthesized and characterized. The DNA-binding studies were performed using absorption spectroscopy, emission spectra, viscosity measurements and thermal denatuaration studies. The experimental evidence indicated that, the Co(II), Ni(II) and Cu(II) complexes interact with calf thymus DNA through intercalation with an intrinsic binding constant K-b of 2.6 x 10(4) M-1, 5.7 x 10(4) M-1 and 4.5 x 10(4) M-1, respectively and they exhibited potent photo-damage abilities on pUC19 DNA, through singlet oxygen generation with quantum yields of 0.32, 0.27 and 0.30 respectively. The cytotoxic activity of the complexes resulted that they act as a potent photosensitizers for photochemical reactions. (C) 2012 Elsevier B.V. All rights reserved.