Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

The effect of impaired thyroid function during development on the mechanical properties of avian bone

Thyroid hormones show fluctuating levels during the post-hatching development of birds. In this paper we report the results of the first mechanical tests to quantify the effect of hypothyroidism, during post-natal development, on the skeletal properties of a precocial bird, the barnacle goose, as determined by microhardness testing. The effect of hypothyroidism is tissue-specific; bone from the femora of birds is not significantly affected by induced hypothyroidism, however, there is a strong positive relationship between the levels of circulating thyroid hormones and the mechanical properties of bone from humeri. In the barnacle goose the development of the wing skeleton and musculature depends on an increase in circulating thyroid hormones and our analysis shows that, in its absence, the mechanical competence of the bone mineral itself is reduced in addition to the decreased bone length and muscle development previously reported in the literature. (C) 2004 Wiley-Liss, Inc.

The influence of hydration on the tensile and compressive properties of avian keratinous tissues

Despite recent research exploring the elastic properties of avian keratins, data on failure properties are less common in the literature. In this paper we present data on the failure properties and moduli of both avian feather and claw keratin in tension and the modulus of claw keratin in compression. Increased water content acts to decrease stiffness and strength but to increase strain at failure. The modulus of claw did not differ significantly when tested under tension and compression.

Effect of heat treatment on changes in texture, structure and properties of Thai indigenous chicken muscle

Changes in texture, microstructure, colour and protein solubility of Thai indigenous and broiler chicken Pectoralis muscle stripes cooked at different temperatures were evaluated. The change in shear value of both chicken muscles was a significant increase from 50 to 80 degrees C but no change from 80 to 100 degrees C. A significant decrease in fibre diameter was obtained in samples heated to an internal temperature of 60 degrees C and the greatest shrinkage of sarcomeres was observed with internal temperatures of 70-100 and 80-100 C for broiler and indigenous chicken muscles, respectively (P < 0.05). Cooking losses of indigenous chicken muscles increased markedly in the temperature range 80-100 C and were significantly higher than those of the broiler (P < 0.001). With increasing temperature, from 50 to 70 degrees C, cooked chicken muscle became lighter and yellower. Relationships between changes in sarcomere length, fibre diameter, shear value, cooking loss and solubility of muscle proteins were evaluated. It was found that the solubility of muscle protein was very highly correlated with the texture of cooked broiler muscle while sarcomere length changes and collagen solubility were important factors influencing the cooking loss and texture of cooked indigenous chicken muscle. (c) 2004 Elsevier Ltd. All rights reserved.

Effects of high pressure on functional properties of soy protein

Simultaneous measurement of the effects of low soy protein concentration, pH and high pressure treatment at room temperature on solubility, emulsifying properties and rheological properties (loss modulus, G '') of soy protein isolate (SPI) were evaluated. Central composite rotatable designs (2(3)) were employed over two pH ranges (2.66-4.34 and 5.16-6.84) with SPI concentration (0.32-3.68%) and pressure (198-702 MPa) as the other independent variables. The surface responses were obtained for protein solubility, emulsifying activity index (EAI) and G ''. The samples with the highest effect on protein solubility, EAI and G '' values were evaluated, as well, by electrophoresis and free sulphydryl determination. The pH was the main factor that affected protein solubility, with solubility at a maximum at pH < 3 or pH > 6. Increasing SPI concentration and decreasing/increasing the pH away from the isoelectric point both caused a reduction in EAI. Loss modulus (G '') was found to increase with SPI concentration in both pH ranges. (c) 2006 Elsevier Ltd. All rights reserved.

Effects of fat on the properties of halloumi cheese

Halloumi cheese was produced from 11 bovine milks with fat contents of 1.61-4.04%, giving a range of 32-53% fat in dry matter (FDM) in the cheeses. Starter culture and/or microparticulated whey protein (Simplesse((R)) 100(E)) was also added to selected batches of milk. Hardness decreased with increasing FDM, with increase in moisture and with lower pH. On sensory evaluation, there was an increase in preference score with FDM (R-2 = 0.8). Inclusion of microparticulated whey protein may have had a fat mimetic effect, as preference scores otherwise decreased with increasing protein levels (R-2 = 0.75).

Effects of calcium-chelating agents and pasteurisation on certain properties of calcium-fortified soy milk

Addition of 25 mM calcium chloride to soy milk reduced pH, increased ionic calcium and caused it to coagulate. The effects of different chelating agents were investigated on selected physicochemical properties of soy milk and on preventing coagulation. The soy milks were then pasteurised to examine how heat treatment changed some of these properties as well as to evaluate their effects on heat stability. Sediment formation and susceptibility to coagulation could be reduced by decreasing ionic calcium and increasing pH. To achieve this, the most effective chelating agents were tri-sodium citrate and disodium hydrogen phosphate. These chelating agents also reduce absolute viscosity and particle size. Sodium hexa meta phosphate was also effective, but less so; it reduced ionic calcium but had a less noticeable effect on pH. The disodium salt of ethylenediamine tetraacetic acid was not effective, as it decreased the pH of soy milk. Ionic calcium and pH are useful indicators of heat stability of calcium-fortified soy beverages. (C) 2009 Elsevier Ltd. All rights reserved.

Effects of calcium chloride and sodium hexametaphosphate on certain chemical and physical properties of soymilk

Soymilks with sodium hexametaphosphate (SHMP) (0% to 1.2%) and calcium chloride (12.50, 18.75, and 25.00 mM Ca),were analyzed for total Ca, Ca ion concentration, pH, kinematic viscosity, particle diameter, and sediment after pasteurization. Higher added Ca led to significant (P <= 0.05) increases in Ca ion concentration and significant (P <= 0.05) decreases in pH. At certain levels of SHMP, higher concentrations of added Ca significantly increased (P <= 0.05) kinematic viscosity, particle diameter, and sediment. Increasing SHMP concentration reduced Ca ion concentration, particle diameter, and dry sediment content, but reduced kinematic viscosity of samples (P <= 0.05). Adding SHMP up to 0.7% influenced pH of soymilk in different ways, depending on the level of Ca addition. When the pH of Ca-fortified soymilk was adjusted to a higher level, ionic Ca decreased as pH increased. Ihere was a negative linear relationship between the logarithm of ionic Ca concentration and the adjusted pH of the soymilk. Ionic Ca appeared to be a good indicator of thermally induced sediment formation, with little sediment being produced if ionic Ca was maintained below 0.4 mM.

Effects of lactoperoxidase and hydrogen peroxide on rheological properties of yoghurt

The effects of activation of the lactoperoxidase (LPO) system by H2O2-NaSCN and hydrogen peroxide (H2O2) on the accessibility of sulphydryl groups (SH) in skimmed milk, and on the dynamic rheological properties of the resulting yoghurt were investigated. Four different concentrations of each reagent (20-80 mg H2O2-NaSCN/kg milk and 100-400 mg H2O2/kg milk) were compared. Clear negative correlations were noted between the accessibility of SH groups and both LPO activation rate and H2O2 concentration. Also the native PAGE pattern of the heat-treated samples showed that with increase in the H2O2-NaSCN and H2O2 concentrations, the level of interaction between beta-lactoglobulin (beta-Ig) and kappa-casein (K-CN) decreased. The complex modulus (G*) of skimmed milk yoghurts declined gradually with the decrease in the concentration of accessible SH groups accordingly. Tan delta values of yoghurt samples were found to be different from the control, but close to each other, indicating that protein interaction forces taking place in the formation of gel networks of treated yoghurts were different from the control.

Effects of combined high-pressure and heat treatment on the textural properties of soya gels

sSPI, 7S, and 11S globulin at 12% (w/v) protein concentration, at neutral pH, did not form gels when heat-treated (90 degreesC, 15 min) or when high pressure-treated (300-700 MPa), except for the I IS, which formed a gel when heat-treated. The combination of heat and pressure (that is heating the solutions in a water bath and then pressure-treating at room temperature or the reverse sequence), led to differences: when heat-treatment was before high-pressure treatment, only the I IS fraction formed a self-standing gel; however, when the solutions were pressurised before heat treatment, all the proteins formed self-standing gels. The textural and water-holding properties were measured on the gels formed with the three different soy proteins. (C) 2002 Elsevier Science Ltd. All rights reserved.

Anti-cancer properties of phenolics from apple waste on colon carcinogenesis in vitro

Colorectal cancer is one of the most common cancers in Western countries. The World Health Organisation identifies diet as a critical risk factor in the development and progression of this disease and the protective role of high levels of fruit and vegetable consumption. Several studies have shown that apples contain several phenolic compounds that are potent anti-oxidants in humans. However, little is known about other beneficial properties of apple phenolics in cancer. We have used the HT29, HT115 and CaCo-2 cell lines as in vitro models to examine the effect of apple phenolics (0.01–0.1% apple extract) on key stages of colorectal carcinogenesis, namely; DNA damage (Comet assay), colonic barrier function (TER assay), cell cycle progression (DNA content assay) and invasion (Matrigel assay). Our results indicate that a crude extract of apple phenolics can protect against DNA damage, improve barrier function and inhibit invasion (p < 0.05). The anti-invasive effects of the extract were enhanced with twenty-four hour pretreatment of cells (p < 0.05). We have shown that a crude apple extract from waste, rich in phenolic compounds, beneficially influences key stages of carcinogenesis in colon cells in vitro.

Influence of some processing and storage conditions on the mechanical properties of oat flakes

Flake breakage and texture are important quality, criteria in oat flakes. These properties are determined by the mechanical properties of the flakes, which may be influenced by process variables such as kilning and flake thickness. A pin deformation method was used to measure the rupture force of individual oat flakes at different water activities. The monolayer value of ground oat flakes ranged from 5.83 to 684 g/100 g dry matter Thick flakes were strongest, requiring 3.4 N to rupture the flake compared to 2.2 N for the thin flakes. Water softened the flakes, causing a decrease in rupture force from 3.6 N to 2.4 N as water activity; increased from 0.115 to 0.848. Kilning had a significant effect on flake thickness but not on the mechanical properties. This study suggests that oat flakes should be stored at water activity 0.4 or less as there is a sharp loss of flake strength above this point.

Effect of chymosin reduction and salt substitution on the properties of white salted cheese

A whey salts mixture was used as a partial substitute for sodium chloride to provide a modified Na:K ratio (1:3.4) in the manufacture of white salted cheese using ultrafiltration. Reduction of chymosin addition from 20 to 8 mu L kg(-1) of cheese was also investigated. Variation of salt and chymosin levels did not result in any significant differences in composition and physicochemical properties. The rates of proteolysis in terms of water-soluble nitrogen (WSN) and nitrogen soluble in 12% trichloroacetic acid (TCA-SN) were affected by chymosin levels but not by salt treatment. Urea-PAGE electrophoretic analysis of caseins from the cheeses manufactured using three levels of chymosin and two salt types showed that the hydrolysis of alpha(s1)-casein was higher than for beta-caseins but the differences between the cheeses were not significant (P > 0.05). The chymosin level did not have a significant effect (P > 0.05) on hardness and fracturability, suggesting that any variation in hardness due to the initial hydrolysis was being confounded by other variables. Cheeses including the whey salts product were harder and more fracturable (P < 0.01) than the cheese treated with NaCl only. Both hardness and fracturability values decreased (P < 0.05) over the maturation period. The scores for bitterness were low; neither the effects of salt nor chymosin levels were significant (P > 0.05). (c) 2005 Elsevier Ltd. All rights reserved.

The effects of paeonol on the electrophysiological properties of cardiac ventricular myocytes

Previous studies have shown that "Mudanpi", a Chinese herbal medicine, has a significant cardioprotective effect against myocardial ischaemia. Based on these findings we hypothesised that paeonol, the main component of Mudanpi, might have an effect on the cellular electrophysiology of cardiac ventricular myocytes. The effects of paeonol on the action potential and ion channels of cardiac ventricular myocytes were studied using the standard whole-cell configuration of the patch-clamp technique. Ventricular myocytes were isolated from the hearts of adult guinea-pig by enzymic dispersion. The myocytes were continuously perfused with various experimental solutions at room temperature and paeonol applied in the perfusate. Action potentials and membrane currents were recorded using both current and voltage clamp modes of the patch-clamp technique. Paeonol, at concentrations 160 mu M and 640 mu M, decreased the action potential upstroke phase, an action associated with the blockade of the voltage-gated, fast sodium channel. The effects of paeonol on both action potential and Na+ current were concentration dependent. Paeonol had a high affinity for inactivated sodium channels. Paeonol also shortened the action potential duration, in a manner not associated with the blockade of the calcium current, or the enhancement of potassium currents. These findings suggest that paeonol, and therefore Mudanpi, may possess antiarrhythmic activity, which may confer its cardioprotective effects. (c) 2006 Elsevier B.V All rights reserved.

Design of mucoadhesive polymeric films based on blends of poly(acrylic acid) and (hydroxypropyl)cellulose

Mixing of aqueous solutions of poly(acrylic acid) and (hydroxypropyl) cellulose results in formation of hydrogen-bonded interpolymer complexes, which precipitate and do not allow preparation of homogeneous polymeric films by casting. In the present work the effect of pH on the complexation between poly(acrylic acid) and (hydroxypropyl)cellulose in solutions and miscibility of these polymers in solid state has been studied. The pH-induced complexation-miscibility-immiscibility transitions in the polymer mixtures have been observed. The optimal conditions for preparation of homogeneous polymeric films based on blends of these polymers have been found, and the possibility of radiation cross-linking of these materials has been demonstrated. Although the gamma-radiation treatment of solid polymeric blends was found to be inefficient, successful cross-linking was achieved by addition of N, N'- methylenebis(acrylamide). The mucoadhesive potential of both soluble and cross-linked films toward porcine buccal mucosa is evaluated. Soluble films adhered to mucosal tissues undergo dissolution within 30-110 min depending on the polymer ratio in the blend. Cross-linked films are retained on the mucosal surface for 10-40 min and then detach.