Delta Ip Research Articles

Photoelectron Spectra, Electronic Structures, and Conformational Properties of Substituted 2-Styrylpyrroles

The UV photoelectron spectra of three pairs of cis/trans-isomers of 2-(2-methylstyryl)pyrroles (1-6) have been recorded and analysed, making use of density functional theory (DFT) calculations at the B3LYP level. Compounds 1 and 2 have no further substituents in the pyrrole ring. In the other compounds the pyrrole ring is substituted by a methyl group in the 1-(3,4) or 5-position (5,6). Twisted conformations were calculated for 1-6 in which the toluene ring is generally much more distorted from the plane of the central C=C double bond than the pyrrole ring. In the cis-isomers (2, 4, 6) the torsion angle of the toluene groups amounts to about 50 o, while in the trans-isomers (1, 3, 5) the torsional angle is only about half as large. The energy difference delta IP values of the ionization bands associated with the molecular orbitals (MOs) pi7 and pi3 is related to torsion. Calculated delta IP values are generally 5-10 % larger than the experimental values, indicating that torsional vibrations contribute to the apparent distortion of the molecules. The results clearly indicate that PE spectroscopy - in combination with high-level quantum chemical calculations - is a verasatile method to distinguish E/Z isomers of heterocyclic stilbene-like molecules.

Substituent effects on two-center three-electron bonds and hydrogen bonds involving unsaturated organic functional groups and an ammonia radical cation--the resonance contribution

A theoretical investigation of the substituent effects on the two-center, three-electron (2c-3e) bond involved between unsaturated functional groups and an amine nitrogen is presented. The competitive hydrogen-bonded complexes are also studied. In both cases, the bond energies are found to be in the range of 20-30 kcal mol(-1). The variation of these energies is discussed with respect to the electron-donating effect of the substitutents, as well as with respect to the alpha-bonded atom of the organic functional group (O, S, NH). For the 2c-3e bonds, the results are discussed on the basis of the differences of the ionization potential (delta IP) of the separated fragments and can be rationalized through the valence bond theory. For the hydrogen bonds, the substituent influence is discussed by using the differences of the proton affinities (delta PA) of the substrates. The resonating nature of the hydrogen bond in these cationic systems is investigated and is found to account for most of the binding energy. Marcus theory is compared with the proposed resonating model.

Theoretical calculation of ionization potentials for disubstituted benzenes: additivity vs non-additivity of substituent effects

The ionization potentials of 55 para- and 55 meta-disubstituted benzenes, consisting of all binary combinations of electron-withdrawing groups (-NO2, -CF3, -CHO, -COOH) and electron-donating groups (-Cl, -CH3, -OH, -OCH3, -NH2, and -N(CH3)2) have been calculated using density functional theory with the B3LYP functional and a 6-31G(d) basis set. Relative ionization potentials (delta IP), referred to benzene, are compared with experimental values and shown to be in good agreement. The disubstituted data were correlated with monosubstituted delta IP data and shown to require quadratic terms in order to achieve a good fit; the validity of this conclusion was possible due to the low scatter in the calculated data. A simple MO analysis gives a semiquantitative interpretation of the observed trends in substitutent effects, including a discussion of combinations of substituents for which nonadditivity should be expected.

Effectiveness of calcium lactate added to food in reducing intraoral demineralization of enamel.

Following the demonstration that rinses with solutions of soluble calcium salts reduced sucrose-induced demineralization, a study was undertaken to determine whether a similar effect could be obtained by the supplementation of a solid food with calcium lactate (CL). Subjects wore palatal appliances containing blocks of bovine enamel that were coated with Streptococcus mutans IB 1600 and ate 5-gram portions of cookies made with defined levels of CL. Determinations were made of changes in iodide penetrability (delta Ip) of the enamel, as well as the pH, calcium and inorganic phosphate of the streptococcal plaque. CL at 3.2% (w/w) reduced delta Ip from 12.9 +/- 1.7 to 6.1 +/- 0.9 units, i.e. by 52.7%. Plaque pH was not affected. Demineralization was reduced progressively with increasing concentrations of added CL, and CL was most effective with increasingly sweet cookies. Plaque contained 32.4 +/- 6.0 and 17.1 +/- 4.2 mM calcium after 1 and 5 min, respectively. Calculations showed that the plaque was saturated with respect to enamel during the first 5-10 minutes after food ingestion, in spite of the progressive drop in plaque pH. In conclusion, the present study demonstrated the reduction of the cariogenic potential of solid food by relatively low concentrations of CL. The effect appeared to be related to the ability of the food to maintain high levels of calcium in the streptococcal plaque during the period of active acidogenesis.

Delayed Effect of Wheat Starch in Foods on the Intraoral Demineralization of Enamel

There is considerable evidence for an association between dental caries and food starches. However, the intraoral utilization of starch may be quite complex, giving rise to conflicting results. Demineralization induced by unsweetened cookies was examined in an intraoral model system that utilized palatal appliances containing blocks of bovine enamel. The enamel surfaces were covered with either a filter paper disc to trap sugars or a layer of Streptococcus mutans to metabolize the sugars and bring about enamel demineralization. Demineralization was determined as an increase in porosity with respect to iodide ions (delta Ip). Measurements revealed a rapid elevation and maintenance of high levels of maltose in the plaque space after ingestion of the unsweetened or sweet cookies. Entrapped food particles appeared to serve as a reservoir of maltose. Unsweetened cookies brought about enamel demineralization, but the pH of the streptococcal plaque fell slowly, and the initiation of demineralization was delayed. Thus, delta Ip and plaque pH were -0.3 +/- 1.3 U and 6.1 +/- 0.3, respectively, after 15 min. The delay was shown to be related to the need to induce the acidogenic streptococci to metabolize maltose. Once induced, delta Ip rose rapidly and reached a maximum at 45 min. Sweet cookies released sucrose and maltose and brought about a rapid onset of demineralization. In summary, the data demonstrated (1) that maltose was released rapidly from unsweetened cookie particles and diffused into the plaque space of the model system and (2) that maltose-dependent demineralization of enamel required time for the induction of the streptococcal cells.(ABSTRACT TRUNCATED AT 250 WORDS)

Reduction of intra-oral demineralization of enamel after single exposures to sodium fluoride.

Studies demonstrated the effects of single rinses with low concentrations of NaF on the intra-oral demineralization of enamel. Blocks of bovine enamel were covered with Streptococcus mutans IB1600, mounted in palatal appliances, and worn in the mouths of volunteers for specified times. Subjects rinsed with solutions of NaF, with or without sucrose. Demineralization was determined as changes in iodide penetrability (delta Ip) of the enamel, while the pH and F of the streptococcal plaque, and enamel F, were determined with ion-specific electrodes. Delta Ip was reduced by about 80% (from 14.5 +/- 2.7 to 2.8 +/- 2.3 units) when 250 micrograms F/mL was added to the sucrose rinse. Corresponding plaque pH's were 4.1 +/- 0.5 and 4.2 +/- 0.3, consistent with a lack of effect on bacterial acidogenesis. Protection against mineral loss was concentration-dependent. Administration of sucrose at different times after NaF revealed that the effect of F persisted for at least 60 min. Analyses of plaque F demonstrated an initial elevation and concentration within the cells, followed by a drop to stable, baseline values. Enamel F increased slowly to almost 500 micrograms/g enamel after 105 min. The protective effect of F appeared to be manifested in two stages, the first related to a high plaque F and the second to F that became incorporated into the enamel. Analysis of the data suggested that F was transferred from plaque to enamel during the experimental period.

Limitations in the intraoral demineralization of bovine enamel.

A model system was used to examine the relation between the duration of plaque pH fall and enamel demineralization following the intake of dietary carbohydrate in humans. Subjects wore palatal appliances containing blocks of bovine enamel covered with Streptococcus mutans IB 1600, and rinsed with 5 or 10% sucrose. Changes in iodide penetrability (delta Ip) of the enamel, and the pH and extracellular calcium and inorganic phosphate (Pi) concentrations of the streptococcal plaque were determined. Following rinses with 5% sucrose, delta Ip increased with time and reached a maximum (11.2 +/- 2.2 units) at 45-60 min although the S. mutans plaque remained acidic (pH = 4.8 +/- 0.6). After 10% sucrose, the maximum (14.7 +/- 3.1 units) was reached while the plaque pH was 4.0 +/- 0.3. Second rinses with sucrose increased delta Ip at most by 30%. Thus, demineralization did not persist throughout the period of low plaque pH, but occurred primarily during the early phase of plaque acidogenesis. Enamel demineralization appeared to be limited by factors other than the pH of the streptococcal plaque. Calcium concentrations in the S. mutans plaque rose to a maximum of 10.9 +/- 2.8 mEq/l at 30 min after the 5% sucrose rinses, then fell; Pi reached a stable level of 12.2 +/- 2.3 mEq/l by 60 min. Calculations showed that conditions approached saturation with respect to enamel and dicalcium phosphate dihydrate as demineralization reached a maximum. Demineralization appeared to be limited at low plaque pH, therefore, by the accumulation of high levels of mineral ions in the streptococcal plaque.(ABSTRACT TRUNCATED AT 250 WORDS)

Comparison of the Iodide Permeability Test, the Surface Microhardness Test, and Mineral Dissolution of Bovine Enamel following Acid Challenge

The relationship among the iodide permeability (Ip) test, the surface microhardness (SMH) test, and enamel demineralization chemically analyzed as mineral loss was investigated using bovine enamel blocks. Demineralization periods of 0 (control) and 5, 15, 30, and 45 min using 0.05 mol/l lactate (pH 4.75) were chosen to approximate the acid challenge occurring during the intraoral enamel demineralization test. Mineral loss (Ca and PO4) was found to be directly proportional to dissolution time (r = 0.95). Changes (delta) in Ip and SMH each increased linearly over time (r = 0.58 and 0.64, respectively) and were similarly related to mineral loss (r = 0.60 and 0.65, respectively). The correlation between delta Ip and delta SMH was 0.55. When longer demineralization periods (60, 120, and 240 min) were included, the correlation between delta Ip and delta SMH was 0.68. We conclude that both the Ip test and the SMH test can be used as measures of the early stages of enamel dissolution.

Accumulation of Enamel Constituents in Streptococcus mutans Plaque during Intraoral Demineralization

Studies were carried out with an intraoral demineralizing system in order to determine whether calcium and inorganic phosphate (Pi) accumulate in plaque during active demineralization of enamel. Blocks of bovine enamel were coated with Streptococcus mutans and were carried in palatal appliances worn by human volunteers. Demineralization was determined as changes in the iodide penetrability (delta Ip) of the enamel surfaces. Ca and Pi were determined in the extracellular spaces of the synthetic plaque. Delta Ip increased with time after administration of rinses containing 5% (w/v) sucrose, while plaque pH dropped and then returned toward neutrality. Ca increased to 10.9 +/- 2.8 mmol/l at 30 min, while Ca2+ and Pi rose to 3.0 +/- 2.1 and 9.5 +/- 3.1 mmol/l, respectively. The Ca:Pi ratio was 1.15. Rinses with 10% (w/v) sucrose gave similar results. Concentrations of Ca and Pi were considerably higher than those in saliva. Accumulation of the mineral constituents was shown to be dependent on metabolic activity of the S. mutans plaque, and experiments in which enamel blocks were replaced with blocks made of acrylic plastic gave Ca and Pi concentrations of 2.5 +/- 0.6 and 6.6 +/- 2.4 mmol/l, respectively, demonstrating that most of the Ca and about one-third of the Pi were derived from enamel. The data suggested, furthermore, that Ca and Pi were partially bound to complex macromolecules, and that part eventually recrystallized as mineral within the plaque.

Prevention of sucrose-induced demineralization of tooth enamel by chewing sorbitol gum.

Measurements were made of the effect of chewing sorbitol gum on the intra-oral demineralization induced by rinsing with 10% sucrose solutions. Blocks of bovine enamel were covered with a layer of Streptococcus mutans IB1600, and mounted on palatal appliances that were worn by five subjects for defined periods of time. Enamel demineralization was determined by following changes in iodide penetrability (delta Ip) of the enamel surfaces. Delta Ip increased to a maximum of about 15 units between 30 and 45 min, while the pH of the S. mutans plaque dropped to below 4 by 15 min. Plaque pH returned to 4.9 by 60 min. Chewing sorbitol gum after the sucrose rinse minimized further increases in delta Ip and brought about a more rapid return of the S. mutans plaque pH toward neutrality. The effect of chewing gum was greater when chewing was initiated earlier so that, when gum was given at five min after the sucrose rinse, demineralization was only 37% of that obtained without gum. The findings confirm earlier reports on the effect of gum on plaque pH, and directly demonstrate the profound protective effects that chewing sorbitol gum can have on tooth enamel.

Increased Permeability of Enamel to Iodide Ions following the Ingestion of Cookies Varying in Sucrose or Fat Content

Experiments showed that the intraoral iodide permeability (Ip) method can be used in a reproducible and sensitive manner with solid foods. Ingestion of 5-gram portions of cookies made with defined concentrations of sucrose or fat led to an increased Ip (due to demineralization) of Streptococcus mutans-covered bovine enamel blocks in vivo. Demineralization increased with time to a maximum of 45 min, and the pH of the plaque dropped accordingly. Continued exposure in the mouth beyond 45 min led to an elevation of the pH and a decrease in delta Ip consistent with remineralization of the enamel. Control blocks worn without ingestion of cookies exhibited negative delta Ip values. Demineralization increased with increasing sucrose content of the cookies and reached a plateau when cookies containing 1.08 g sucrose per morsel were administered. Cookies prepared without added sucrose gave a high delta Ip. High fat content raised the delta Ip when sucrose was low. These findings are consistent with clinical and other observations, and emphasize the complex relation between foods and enamel demineralization.

Demineralization potential of different concentrations of gelatinized wheat starch.

Six subjects wore intraoral devices carrying bovine enamel blocks covered with a layer of Streptococcus mutans. They swished solutions of 5% glucose or maltose, or sols or gels of 3, 5, 10, 15, or 20% gelatinized wheat starch in the mouth for 3 X 1 min. Demineralization was measured after 45 min by determining the change in iodide permeability (delta Ip) of the enamel. Spittings of the administered materials and samples of saliva, taken at intervals during the test, were analyzed for maltose, and the time of clearance was calculated. Demineralization was greatest for glucose followed by maltose, the starch gels, and the sols. The latter gave close to zero scores. The salivary clearance time increased with increase in concentration of the starch. Although the starch was hydrolyzed rapidly in the mouth, its oral retentiveness was greater than that of the maltose rinse. Demineralization was closely correlated with the final pH of the S. mutans cell layer. The data indicate that the starch in baked or cooked foods may have a significant demineralization potential and that it enhances oral retentiveness.

Enamel demineralization and the length of intra-oral exposure to different concentrations of glucose or sucrose.

Six subjects wore intra-oral devices carrying eight bovine enamel blocks which were covered with a layer of S. mutans. They rinsed their mouths for five sec, one min, or multiples of one min with a 5 or 10% glucose (G) solution. Demineralization was measured after 45 min by determining the change in iodide permeability (delta Ip) of the enamel. In addition, saliva samples, taken at intervals during the test, were analyzed for G, and the time of clearance (tc) was calculated. Demineralization scores (delta Ip) were consistently greater from the 10% than from the 5% G solution. Both solutions produced an increase in delta Ip with an increase in the rinsing time (tr). The G remaining in saliva after the rinse did not significantly affect delta Ip. The delta Ip scores showed good correlation with the final pH of the S. mutants cell mass, r = -0.77. For each rinse solution, the scores also showed good correlations with tr (r = 0.87 and 0.79) and much weaker correlations with tr + tc (r = 0.44 and 0.53). Continuous in vitro exposure to 1, 5, or 10% solutions of sucrose (S) in saliva for 30 min or more caused a linear increase in delta Ip with time with no concentration effects. A linear increase was also observed in vivo when a one-minute mouth-rinse with 10% solution of S was administered every 30 min. The findings indicate that significant demineralization may occur while carbohydrate foods are consumed, and that brushing the teeth or rinsing the mouth after meals may not be as effective against caries as is generally believed.

Ionic currents responsible for the generation of pace-maker current in the rabbit sino-atrial node.

The ionic nature of the pace-maker current (delta Ip, If, Ih) was investigated in rabbit sino-atrial node using a single sucrose-gap voltage-clamp technique. The pace-maker current was activated by hyperpolarizing clamp steps negative to -50 mV and the pace-maker potential was activated by an action potential or a depolarizing clamp step. Neither pace-maker current nor pace-maker potential were altered by addition of tetrodotoxin, but a tetrodotoxin-sensitive channel could be activated in sino-atrial nodal strips following hyperpolarizing clamp steps. Ca2+-channel blockers did not affect the voltage dependence of delta Ip or the maximum diastolic potential (m.d.p.) significantly. Removal of Ca2+ did not affect the pace-maker current at clamp potentials near the pace-maker potential range (-60 to -80 mV), but it did reduce the potential dependence of the m.d.p. Removal of Na+ suppressed completely the pace-maker current and hyperpolarized the membrane. Removal of Na+ also increased membrane conductance, most likely through an increase in resting K+ permeability. Low concentration of Cs+ (less than 5 mM), but not Ba2+ or tetraethylammonium, markedly suppressed activation delta Ip and reduced the rate of pacing slightly. Cs+ also decreased the membrane conductance and hyperpolarized the membrane. In 50% of experiments designed to determine contribution of IK to pace-maker current, a double-pulse procedure revealed a time-dependent component of delta Ip which reversed near the K+ equilibrium potential, EK. Release of depolarizing or hyperpolarizing test clamps was followed by pace-maker potentials, the magnitudes of which were dependent on the test-clamp potential. The m.d.p. approached values near EK following depolarizing clamps and near -45 mV following hyperpolarizing clamps. The results suggest that delta Ip is carried primarily by Na+ and is blocked by Cs+. It is likely, however, that Ca2+ alters the rate of pacing not only through its contribution to the Isi system, but also through activation of a K+ conductance.