Quantum-mechanical approach to predissociation of water dimers in the vibrational adiabatic representation: Importance of channel interactions.

The results of application of the quantum-mechanical adiabatic theory to vibrational predissociation (VPD) of water dimers, (H2O)2 and (D2O)2, are presented. We consider the VPD processes including the totally symmetric OH mode of the dimer and the bending mode of the fragment. The VPD in the adiabatic representation is induced by breakdown of the vibrational adiabatic approximation, and two types of nonadiabatic coupling matrix elements are involved: one provides the VPD induced by the low-frequency dissociation mode and the other provides the VPD through channel interactions induced by the low-frequency modes. The VPD rate constants were calculated using the Fermi golden rule expression. A closed form for the nonadiabatic transition matrix element between the discrete and continuum states was derived in the Morse potential model. All of the parameters used were obtained from the potential surfaces of the water dimers, which were calculated by the density functional theory procedures. The VPD rate constants for the two processes were calculated in the non-Condon scheme beyond the so-called Condon approximation. The channel interactions in and between the initial and final states were taken into account, and those are found to increase the VPD rates by 3(1) orders of magnitude for the VPD processes in (H2O)2 ((D2O)2). The fraction of the bending-excited donor fragments is larger than that of the bending-excited acceptor fragments. The results obtained by quantum-mechanical approach are compared with both experimental and quasi-classical trajectory calculation results.

Coherent π-electron dynamics of (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses: angular momentum and ring current.

The results of a theoretical investigation of coherent π-electron dynamics for nonplanar (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses are presented. Expressions for the time-dependent coherent angular momentum and ring current are derived by using the density matrix method. The time dependence of these coherences is determined by the off-diagonal density matrix element, which can be obtained by solving the coupled equations of motion of the electronic-state density matrix. Dephasing effects on coherent angular momentum and ring current are taken into account within the Markov approximation. The magnitudes of the electronic angular momentum and current are expressed as the sum of expectation values of the corresponding operators in the two phenol rings (L and R rings). Here, L (R) denotes the phenol ring in the left (right)-hand side of (P)-2,2'-biphenol. We define the bond current between the nearest neighbor carbon atoms Ci and Cj as an electric current through a half plane perpendicular to the Ci-Cj bond. The bond current can be expressed in terms of the inter-atomic bond current. The inter-atomic bond current (bond current) depends on the position of the half plane on the bond and has the maximum value at the center. The coherent ring current in each ring is defined by averaging over the bond currents. Since (P)-2,2'-biphenol is nonplanar, the resultant angular momentum is not one-dimensional. Simulations of the time-dependent coherent angular momentum and ring current of (P)-2,2'-biphenol excited by ultrashort linearly polarized UV pulses are carried out using the molecular parameters obtained by the time-dependent density functional theory (TD-DFT) method. Oscillatory behaviors in the time-dependent angular momentum (ring current), which can be called angular momentum (ring current) quantum beats, are classified by the symmetry of the coherent state, symmetric or antisymmetric. The bond current of the bridge bond linking the L and R rings is zero for the symmetric coherent state, while it is nonzero for the antisymmetric coherent state. The magnitudes of ring current and ring current-induced magnetic field are also evaluated, and their possibility as a control parameter in ultrafast switching devices is discussed. The present results give a detailed description of the theoretical treatment reported in our previous paper [H. Mineo, M. Yamaki, Y. Teranish, M. Hayashi, S. H. Lin, and Y. Fujimura, J. Am. Chem. Soc. 134, 14279 (2012)].

Non-Markovian response of ultrafast coherent electronic ring currents in chiral aromatic molecules in a condensed phase.

Results of a theoretical study on non-Markov response for femtosecond laser-driven coherent ring currents in chiral aromatic molecules embedded in a condensed phase are presented. Coherent ring currents are generated by coherent excitation of a pair of quasi-degenerated π-electronic excited states. The coherent electronic dynamical behaviors are strongly influenced by interactions between the electronic system and phonon bath in a condensed phase. Here, the bath correlation time is not instantaneous but should be taken to be a finite time in ultrashort time-resolved experiments. In such a case, Markov approximation breaks down. A hierarchical master equation approach for an improved semiclassical Drude dissipation model was adopted to examine the non-Markov effects on ultrafast coherent electronic ring currents of (P)-2,2'-biphenol in a condensed phase. Time evolution of the coherent ring current derived in the hierarchical master equation approach was calculated and compared with those in the Drude model in the Markov approximation and in the static limit. The results show how non-Markovian behaviors in quantum beat signals of ring currents depend on the Drude bath damping constant. Effects of temperatures on ultrafast coherent electronic ring currents are also clarified.

A master equation approach to the dynamics of zero electron kinetic energy (ZEKE) states and ZEKE spectroscopy.

We have theoretically studied important dynamic processes involved in zero electron kinetic energy (ZEKE) spectroscopy using the density matrix method with the inverse Born-Oppenheimer approximation basis sets. In ZEKE spectroscopy, the ZEKE Rydberg states are populated by laser excitation (either a one- or two-photon process), which is followed by autoionizations and l-mixing due to a stray field. The discrimination field is then applied to ionize loosely bound electrons in the ZEKE states. This is followed by using the extraction field to extract electrons from the ZEKE levels which have a strength comparable to that of the extraction field. These extracted electrons are measured for the relative intensities of the ion states under investigation. The spectral positions are determined by the applied laser wavelength and modified by the extraction electric field. In this paper, all of these processes are conducted within the context of the density matrix method. The density matrix method can provide not only the dynamics of system's population and coherence (or phase) but also the rate constants of the processes involved in the ZEKE spectroscopy. Numerical examples are given to demonstrate the theoretical treatments.

Experimental and theoretical investigations of ionization/dissociation of cyclopentanone molecule in a femtosecond laser field.

The ionization/dissociation mechanism of cyclopentanone has been experimentally investigated in molecular beam by irradiating with intense 394 and 788 nm laser fields with pulse duration of 90 fs. The range of laser intensities varied from 3 x 10(13) to 4 x 10(14) W/cm(2). For both wavelengths, the singly charged parent ion is observable while the doubly charged one cannot be found easily, although the fragmentation pattern supports its presence. Meanwhile, the extent of fragmentation at 788 nm is less than that in the 394 nm case. We quantitatively analyze the ionization processes of cyclopentanone in intense femtosecond laser by comparing the calculation results of ionization rate constants obtained from Ammosov-Delone-Krainov, Keldysh, and Keldysh-Faisal-Reiss (KFR) theories based on hydrogenlike atom model. We also compare the experimental and theoretical results; the generalized KFR theory is found to be useful in predicting the ionization yields of singly and doubly charged cyclopentanone ion. To interpret the dissociation patterns of the cyclopentanone ions, we have used the Rice-Ramsperger-Kassel-Marcus theory with the potential surfaces obtained from the ab initio quantum chemical calculations.

Effect of L364718 on interdigestive pancreatic exocrine secretion and gastroduodenal motility in conscious sheep.

The present study examined roles of endogenous cholecystokinin (CCK) and CCK-A receptors in the regulation of pancreatic exocrine secretion and gastroduodenal motility in conscious sheep during interdigestive period. Interdigestive exocrine secretion of ovine pancreas changed cyclically corresponding with cycle of duodenal migrating myoelectric complexes (MMC). During second phase of the duodenal MMC, intravenous injection of L364,718 at 2.45 mumol kg-1 inhibited exogenous CCK-8-induced pancreatic exocrine secretion. Intravenous infusion of the antagonist at 2.45 mumol kg-1/5 min for 5 min also inhibited significantly the pancreatic enzyme secretion without CCK-stimulation to half of that in the control, but not the fluid and bicarbonate secretion. Atropine infusion (i.v.) at 72.0 nmol kg-1/5 min significantly inhibited not only enzyme but also fluid and bicarbonate secretion. Corresponding to the inhibition of the exocrine secretion, L364,718 induced premature phase III in duodenal electromyogram (EMG) in three of the five sheep. Omasal EMG was inhibited slightly but significantly by L364,718, however, neither regular ruminal contractions nor abomasal EMG were altered by L364,718. In contrast, the atropine infusion inhibited only amplitude of ruminal contractions. These results suggest that endogenous CCK contributes to the regulation of interdigestive pancreatic exocrine secretion, omasal contractions and duodenal MMC in the ovine gastrointestinal tract via CCK-A receptors.

PACAP stimulates pancreatic exocrine secretion via the vagal cholinergic nerves in sheep.

The present study evaluates the possible role of the vagus nerves in mediating the stimulatory effect of PACAP-27, PACAP-38 and VIP on the exocrine pancreas, especially on enzyme secretion which is atropine sensitive in sheep. The animals were equipped with two cannulae into the common bile duct, a duodenal cannula, and a ruminal cannula under anesthesia. The bilateral cervical vagus nerves were coiled with a cooling device. In conscious animals, the peptides were infused intravenously for 10 min at 10 pmol kg(-1)min(-1) in phase II of the duodenal migrating motor complexes and the same peptide infusion was repeated in the reversible cooling blockade of the vagus nerves. Increment in fluid secretion was not significantly altered by the vagal blockade in all the peptide infusions, while increment in bicarbonate ion by only PACAP-27 was inhibited by the vagal blockade. Increments in protein and amylase output decreased significantly to 32.0+/-5.0 and 23.2+/-2.6% in PACAP27, and to 26.1+/-7.7 and 20.8+/-6.4% in PACAP-38 in the vagal blockade, but the increments by VIP did not decrease. These results demonstrate that circulating PACAP stimulates pancreatic enzyme secretion via the vagal cholinergic preganglionic neurons in sheep, suggesting the central action of PACAP.

Effects of benzoic acid and its analogues on insulin and glucagon secretion in sheep.

The effects of benzoic acid and its analogues on insulin and glucagon secretion were investigated in conscious sheep. Intravenous injections of benzoic acid increased plasma insulin and glucagon concentrations in a dose-dependent manner between 39-1250 mumol/kg, with ED50s for increasing both hormones of about 625 mumol/kg. Various derivatives of benzoic acid (625 mumol/kg) were administered and structure-activity relationships were examined. A single carboxylic group was essential for stimulating insulin and glucagon secretion, since both hormone responses were abolished with compounds in which the carboxylic group was replaced by sulfonic or phosphoric groups, or in which another carboxylic element was introduced (phthalic acids). Most of the compounds which introduced other elements (amino and hydroxy groups, and halogens) onto the benzene ring had an altered stimulating activity. Thus the pancreatic endocrine system can recognize the chemical structure of benzoic acid and its derivatives in detail and induce insulin and glucagon secretion in sheep.

Short-chain fatty acids enhance diffusional ca transport in the epithelium of the rat cecum and colon.

We examined the effect of short-chain fatty acids (SCFAs) on Ca absorption from the large intestine in rats in vitro. An Ussing-type chamber technique was used to determine the net transport of Ca from the luminal side to the basolateral side of isolated epithelium in cecum and colon preparations. The concentration of Ca in the serosal and mucosal Tris buffer solution was 1.25 mM and 10 mM, respectively. Both solutions were warmed at 37 degrees C and bubbled with 95% O2 and 5% CO2. During and after the incubation period (30 min or 60 min), the Ca concentration in the serosal medium was determined and the net transepithelial Ca transport was evaluated. The addition of 80 mM acetic acid, 40 mM propionic acid and 10 mM butyric acid to the mucosal medium increased net Ca absorption (about 300%) in the cecum and colon. An individual application of acetic, propionic or butyric acid (0.01 to 100 mM) to the mucosal medium also increased net Ca absorption at doses of 10 mM and /or 100 mM in the cecum and colon. An increase in solute concentration in the mucosal medium by addition of glycerol or PGE400, or a decrease in pH (7.0-3.0) by addition of HCl did not affect transepithelial Ca transport. We concluded that SCFAs affect the epithelial tissue and promote Ca absorption from the large intestine in vitro. The enhancement of Ca transport induced by SCFAs might be involved in the paracellular transport mechanism.

Pituitary adenylate cyclase-activating polypeptide (PACAP) stimulates exocrine pancreas in conscious preruminating calves.

The effects of new hypothalamic peptides, PACAP-27 and PACAP-38, and secretin and VIP on the interdigestive pancreatic secretion and duodenal myoelectric activity during the asecretory phase of the pancreatic interdigestive cycle, compared with the milk ingestion phase, were examined in five calves. Peptides were infused for 5 min into the external jugular vein (0, 3, 10, 30 and 100 pmol/kg body wt during the asecretory phase of the pancreatic interdigestive cycle, and the pancreatic secretory response was compared with that obtained during milk ingestion. Intravenous infusion of PACAP-27 caused dose-related stimulation of pancreatic juice flow and bicarbonate and protein output; this effect was identical to infusion of secretin. The effect of PACAP-38 was less pronounced, and that of VIP was the weakest. Pancreatic juice volume and bicarbonate responses during milk ingestion were similar to responses obtained with the highest doses of hypothalamic peptides and secretin, whereas postprandial protein secretion was much greater than the secretion stimulated with peptides. It was concluded that PACAP from the VIP/secretin family may stimulate pancreatic exocrine secretion in conscious calves and a part of the pancreatic response to food intake can be mediated by PACAP.

Effect of pituitary adenylate cyclase-activating polypeptide on exocrine and endocrine secretion in the ovine pancreas.

The role of pituitary adenylate cyclase-activating polypeptide (PACAP) in the regulation of exocrine and endocrine pancreas was investigated in conscious sheep. Intravenous infusions of PACAP-27 and PACAP-38 (1, 3, and 10 pmol/kg/min) for 10 min during phase II of the duodenal migrating myoelectric complex accelerated pancreatic protein and amylase outputs dose-dependently. The responses in enzyme secretion to both PACAPs at the highest doses were inhibited significantly by atropine infusion (14.4 nmol/kg/min). Vasoactive intestinal polypeptide (VIP) at 3 pmol/kg/min significantly accelerated protein but not amylase outputs, although the response to the highest dose was not significantly influenced by atropine. PACAP-27 and VIP increased pancreatic juice flow and bicarbonate output dose-dependently; however, the responses to the highest dose were not altered significantly by atropine. On the other hand, intravenous injection of PACAP-38 (100 pmol/kg) did not influence basal plasma concentration of insulin, glucagon, and glucose. Moreover, PACAP-38 (1-100 pmol/kg) altered neither pancreatic endocrine response to intravenous infusion of glucose (20 mumol/kg/min) not that to n-butyric acid (33 mumol/kg/min). These results suggest that PACAP contributes to the regulation of exocrine secretion of the ovine pancreas but not to endocrine secretion. PACAP appears to accelerate pancreatic enzyme secretion mostly via the cholinergic nerves.

Effect of feeding on plasma secretin concentrations in sheep.

Changes in plasma secretin concentration during the 24 hours after feeding were observed in five female sheep fed 1500 g of lucerne pellets and 300 g of orchard grass hay once daily. The pre-feeding concentration of plasma secretin was 50 +/- 9 pg ml-1. The plasma secretin concentration began to increase immediately after the beginning of feeding, reached values approximately double the pre-feeding values six hours after feeding, and remained significantly above the pre-feeding value for more than 10 hours after feeding (P less than 0.01 or less than 0.05).

Effects of intravenous infusions of cholecystokinin-8 and pentagastrin on plasma concentrations of insulin and glucagon in sheep.

The effects of cholecystokinin-8 (CCK-8) and pentagastrin on insulin and glucagon secretion were studied in conscious sheep. Intravenous infusions of CCK-8 (3 to 1000 pmol kg-1 min-1 for 30 minutes) induced a dose-dependent increase in plasma insulin, but did not alter plasma glucagon concentration. The threshold dose of CCK-8 for stimulation of insulin secretion was 10 to 30 pmol kg-1 min-1. Pentagastrin was infused intravenously at doses of 10 to 3000 pmol kg-1 min-1. The maximal dose of pentagastrin slightly stimulated insulin, but not glucagon, secretion. The insulin secretory activity of pentagastrin was only 1/300 that of CCK-8 on a molar basis. The threshold dose of CCK-8 for stimulation of insulin secretion was similar to that for exocrine pancreatic secretion obtained in earlier studies. In conclusion, CCK is a potential candidate as a physiological factor regulating insulin secretion in sheep.

Effect of intravenous injection of acetate on the pancreas of sheep.

The effect of an intravenous injection of acetate on plasma insulin and glucagon concentration was examined in conscious sheep. Sodium acetate (312 to 5000 mumol kg-1 bodyweight) injection increased plasma insulin concentrations in a dose-dependent manner. Plasma glucagon concentration was not affected by doses up to 1250 mumol kg-1. Doses of 2500 and 5000 mumol kg-1 produced significant increases (P less than 0.05), but not in a dose related manner. The results of this study indicate that the receptive mechanism of the A cell in the sheep pancreas to acetate might be different from that of the B cell.

Plasma secretin fluctuates in phase with periodic pancreatic secretion and the duodenal migrating myoelectric complex in calves.

Plasma secretin and cholecystokinin (CCK) levels and the periodic secretions of the exocrine pancreas were studied simultaneously with the duodenal migrating myoelectric complexes (MMC) in six milk-fed calves which had been starved overnight. The experiments were performed first when the calves were 10 to 16 days old and subsequently when they were 36 to 45 days old. Plasma secretin and the secretion of pancreatic juice fluctuated periodically in phase with the duodenal MMC: plasma secretin, and the pancreatic secretion of water and protein were significantly higher during the phase of irregular spiking activity than during the phase of no spiking activity in both investigations. Plasma CCK did not change throughout the MMC. The intravenous infusion of secretin at 120 pmol kg-1 bodyweight for one hour markedly stimulated pancreatic secretion and prolonged the duodenal MMC cycle, but it did not abolish pancreatic and duodenal periodic activity.

Responses of glucose absorption and fructose absorption to prostaglandin E2 in intestinal loops of sheep.

This study was designed to clarify whether the anti-absorptive action of prostaglandin E2 (PGE2) on glucose absorption was specific or non-specific to the glucose absorptive process, by investigating its effect on fructose absorption which has a different mechanism from that of glucose absorption. The effect of PGE2 on mucus secretion was also evaluated as one of the non-specific inhibiting factors. PGE2 significantly stimulated the secretion of water and mucus, and the absorptions of glucose and fructose were inhibited 49.3 per cent and 31.1 per cent respectively at the highest dose. However, fructose absorption was not inhibited by lower doses of PGE2, although the secretion of fluid and mucus was stimulated significantly and glucose absorption was inhibited significantly at the lower doses.

Effects of oxytocin, arginine-vasopressin and lysine-vasopressin on insulin and glucagon secretion in sheep.

The effects of the posterior-pituitary peptides oxytocin (OT), arginine-vasopressin (AVP) and lysine-vasopressin (LVP) on insulin and glucagon secretion were examined in adult sheep. Each peptide was injected intravenously at doses from 1 to 3000 pmol kg-1. All three peptides increased plasma insulin and glucagon concentrations, but their dose-response relationships revealed differences between them. The maximal insulin responses induced by OT and AVP were very similar, but the threshold and maximal doses of AVP for increasing plasma insulin were higher than those of OT. OT and AVP had the same activity for stimulating glucagon secretion in respect of the threshold and maximal doses and the maximal hormone response. LVP also increased plasma insulin and glucagon concentrations, but it had the weakest activity for stimulating both hormones. These results suggest that in sheep posterior-pituitary peptide may play a role in regulating nutrient metabolism by influencing pancreatic hormone secretion.

Effects of C-terminal fragments of cholecystokinin on plasma insulin and glucagon concentrations in sheep.

The effects of three C-terminal fragments of cholecystokinin (CCK) (CCK-8-sulphated form [SF], CCK-8-non-sulphated form [NSF] and CCK-4) on insulin and glucagon secretion were examined in sheep in vivo. Each CCK fragment was injected intravenously at a wide range of doses (1 pmol to 3 x 10(5) pmol kg-1). CCK-8(SF) had the lowest threshold dose (10 pmol kg-1) and a maximal response dose of 10(3) pmol kg-1 for increasing plasma insulin concentration; the respective threshold doses of CCK-8(NSF) and CCK-8 for increasing plasma insulin were 30 and 100 times greater than that of CCK-8(SF). A maximal insulin response was not obtained at the highest doses of CCK-8(NSF) or CCK-4 tested (3 x 10(3) and 3 x 10(5) pmol kg-1, respectively). These results indicate that CCK-A type receptors rather than CCK-B receptors may be involved in CCK-induced insulin secretion in sheep. None of the CCK fragments affected plasma glucagon concentration. The lack of a glucagon response to exogenous CCK-fragments may be one of the characteristics of the endocrine pancreatic responses of ruminant species.

Effects of perfusion rate and glucose concentration on glucose absorption in intestinal thiry-vella loop in sheep.

The effects of the perfusion rate and glucose concentration in perfusate on glucose absorption in the intestinal Thiry-Vella loop of conscious sheep were studied. When 10 mM glucose was perfused at the rates of 0.5, 1, 2 and 4 ml/min, the absorption rates were 77.1 +/- 2.2, 54.9 +/- 2.3, 31.6 +/- 2.1 and 12.9 +/- 0.3%, respectively. When 5, 10, 20 and 40 mM glucose solutions were perfused at 1 ml/min, the absorption rates were 75.5 +/- 1.7, 52.2 +/- 2.2, 29.4 +/- 1.9 and 19.5 +/- 0.1%, respectively. We conclude that the perfusion of 10 mM glucose solution at 1 ml/min, in which about a 50% absorption rate was obtained, are the optimal conditions for the study of glucose absorption in the intestinal loop of sheep.

Effect of vasoactive intestinal polypeptide (VIP) on the net movement of electrolytes and water and glucose absorption in the jejunal loop of sheep.

The effect of vasoactive intestinal polypeptide (VIP) on glucose absorption and the net movement of electrolytes and water in the jejunum of sheep was investigated using a Thiry-Vella loop. Intraluminal perfusion of glucose solution (10 mM) containing NaCl (149 mM) and PEG (1 mg/ml) was done at 1 ml/min and the outflow solution was collected every ten minutes. After a 30 min control period. VIP was infused into the jugular vein for 30 min at rates of 10, 30, 100, 300 and 1,000 pmol/kg/hr. In the control period, water, sodium, chloride and glucose were absorbed, while bicarbonate and potassium were secreted. VIP decreased water absorption at 10 and 30 pmol/kg/hr and converted to secretion at over 100 pmol/kg/hr in a dose-dependent manner. Sodium flux changed to secretion only at 1,000 pmol/kg/hr, but chloride flux remained absorptive even at the highest dose. Bicarbonate secretion was stimulated dose-dependently by VIP. Potassium secretion was also increased at all doses, though this response was not dose-dependent. The net glucose absorption was not altered by VIP at any dose. Our findings indicate that VIP stimulates the jejunal secretion of water, sodium, potassium and bicarbonate and that VIP does not inhibit glucose absorption when the secretion of luminal fluid is accelerated by VIP in the jejunal loop of sheep.