Risk Factors for Orthostatic Hypertension in Children.

OBJECTIVE: To investigate the risk factors for orthostatic hypertension in children. STUDY DESIGN: Eighty children with orthostatic hypertension were enrolled in the group with orthostatic hypertension, and 51 healthy children served as the control group. Demographic characteristics, clinical history, daily water intake, nightly sleep duration, the results of the standing test, and complete blood count were recorded and compared between the 2 groups. The risk factors for pediatric orthostatic hypertension were determined by logistic regression analysis. RESULTS: Body mass index and red blood cell distribution width were higher in the group with orthostatic hypertension than in healthy children, whereas daily water intake and sleep duration were lower. Logistic regression analyses showed that, if a child suffered from overweight, suffered from obesity, had a daily water intake of less than 800 mL, or had a red blood cell distribution width that was increased by 1%, the risk of orthostatic hypertension would be increased by 6.069 times (95% CI, 1.375-26.783; P < .05), 7.482 times (95% CI, 1.835-30.515; P < .01), 4.027 times (95% CI, 1.443-11.241; P < .01), or 4.008 times (95% CI, 1.698-9.461; P < .01), respectively. However, if the sleep duration was increased by 1 hour, the risk of developing orthostatic hypertension would be decreased by 74.3% (95% CI, 54.6%-85.4%, P < .01). CONCLUSIONS: Increased body mass index, inadequate water intake and sleep duration, and elevated red blood cell distribution width were identified as risk factors for pediatric orthostatic hypertension.

Head-up tilt test provokes dynamic alterations in total peripheral resistance and cardiac output in children with vasovagal syncope.

AIM: This study examined the total peripheral vascular resistance (TPVR) and cardiac output changes due to the head-up tilt test (HUTT) in children with vasovagal syncope (VVS). METHODS: From December 2013 to January 2016, we recruited 77 children diagnosed with VVS group at Peking University First Hospital, China, and 28 children without VVS provided the control group. Heart rate, blood pressure, TPVR, cardiac output and baroreflex sensitivity were monitored during the HUTT. RESULTS: In the supine position, TPVR and baroreflex sensitivity were higher in the patients with VVS than the controls, but cardiac output did not differ between the two groups. There were obvious increases in the VVS patients from TPVR in the supine position to the prepositive response period (p < 0.05), then the positive response period (p < 0.01). However, we noted the opposite trend in cardiac output, from the supine position to the prepositive response period (p < 0.01) then the positive response period (p < 0.01). CONCLUSION: During HUTT, children with VVS demonstrated increases in TPVR but decreases in cardiac output, during the transition from the supine position to the positive response. This response might be involved in the pathogenesis of VVS.

Serum Resistin Negatively Correlates with Clinical Severity of Postural Tachycardia Syndrome in Children.

This study was designed to analyse the serum resistin level in children with postural tachycardia syndrome (POTS) and its clinical significance. Twenty-one children with POTS and 31 healthy children as controls participated in the study. Clinical characteristics, heart rate and blood pressure in the supine and upright positions were monitored and collected during an upright test, and the symptom scoring of POTS patients was recorded. The serum resistin levels of patients in both groups were determined by enzyme-linked immunosorbent assay. The change in serum resistin levels in the POTS group before and after standing, as well as its correlation with symptom scores and change in heart rate after standing, was analysed. Compared with the control group, the serum resistin levels in the POTS group were significantly increased (P < 0.01). The serum resistin levels in the POTS group before and after standing did not differ (P > 0.05). There was a negative correlation between the serum resistin levels and a change in heart rate from the supine to upright position (correlation coefficient = -0.615, P < 0.01). Moreover, serum resistin levels were negatively correlated with symptom scores (correlation coefficient = -0.493, P < 0.05). Serum resistin levels in children with POTS were significantly higher than those in healthy children and negatively correlated with a change in heart rate from the supine to upright position and symptom scores. These results suggest a protective role of increased resistin in the pathogenesis of POTS.

Total peripheral vascular resistance, cardiac output, and plasma C-type natriuretic Peptide level in children with postural tachycardia syndrome.

OBJECTIVE: To investigate the total peripheral vascular resistance (TPVR), cardiac output (CO), and plasma C-type natriuretic peptide (CNP) levels in children with postural tachycardia syndrome (POTS) during supine, upright, and return to supine. STUDY DESIGN: Twenty-nine children with POTS, aged 12 ± 3 years, were recruited, and 32 healthy children, aged 11 ± 2 years, served as controls. Heart rate (HR), blood pressure, TPVR, and CO were continuously monitored with Finapres Medical System, and plasma CNP levels were detected with Sandwich immunoluminescence assay. RESULTS: In children with POTS, upright TPVR and CO were significantly lower than those in supine position, and they rose again when they returned to supine position. However, in healthy control patients, both TPVR and CO did not change during supine, upright, and supine again positions. Also, in the supine position, there was no significant difference in TPVR and CO between POTS children and control subjects (P > .05). When upright, however, TPVR and CO in children with POTS were significantly lower than those of controls. Plasma CNP levels were significantly greater in children with POTS than that of controls (32.8 ± 9.7 vs 24.2 ± 8.4 [pg/mL], P < .01), and symptom scores and ΔHR positively correlated with plasma CNP levels in children with POTS (symptom scores: r = 0.490, P < .01; ΔHR: r = 0.508, P < .001), but CO negatively correlated with plasma CNP levels (r = -0.446, P < .01). CONCLUSION: Reduced TPVR and CO associated with the elevated plasma CNP might be involved in the pathogenesis of POTS.

[A family-based transmission disequilibrium test of polymorphisms of endothelial nitric oxide synthase gene in children with orthostatic intolerance].

OBJECTIVE: Recent studies have found that the variation of G894T on the region of T786C and 7th exon promoted by endothelial nitric oxide synthase (eNOS) gene is associated with cardiovascular disease. This research explored possible correlations between eNOS gene polymorphisms and orthostatic intolerance (OI) in children through linkage disequilibrium analysis between eNOS genes T786C and G894T and OI. METHODS: PCR, Macrorestriction Map and other molecular biotechnology were used to determine the genotypes of eNOS/T786C and G894T in 60 OI probands and their parents. Correlation analysis and transmission disequilibrium test (TDT) between T786C, G894T and OI were performed. RESULTS: There was linkage disequilibrium of eNOS/T786C and G894T gene polymorphisms in the occurrence of childhood OI (P<0.05). CONCLUSIONS: eNOS genes T786C and G894T may be associated with the pathogenesis of OI.

Plasma human growth cytokines in children with vasovagal syncope.

Purpose: The study was designed to investigate the profile of plasma human growth cytokines in pediatric vasovagal syncope (VVS). Materials and methods: In the discovery set of the study, plasma human growth cytokines were measured using a Quantiboby Human Growth Factor Array in 24 VVS children and 12 healthy controls. Scatter and principal component analysis (PCA) diagrams were used to describe the samples, an unsupervised hierarchical clustering analysis was used to categorize the samples. Subsequently, the cytokines obtained from the screening assays were verified with a suspension cytokine array in the validation set of the study including 53 VVS children and 24 controls. Finally, the factors associated with pediatric VVS and the predictive value for the diagnosis of VVS were determined. Results: In the discovery study, the differential protein screening revealed that the plasma hepatocyte growth factor (HGF), transforming growth factor b1 (TGF-b1), insulin-like growth factor binding protein (IGFBP)-4, and IGFBP-1 in children suffering from VVS were higher than those of the controls (all adjust P- value < 0.05). However, the plasma IGFBP-6, epidermal growth factor (EGF), and IGFBP-3 in pediatric VVS were lower than those of the controls (all adjust P- value < 0.01). Meanwhile, the changes of 7 differential proteins were analyzed by volcano plot. Unsupervised hierarchical cluster analysis demonstrated that patients in the VVS group could be successfully distinguished from controls based on the plasma level of seven differential proteins. Further validation experiments showed that VVS patients had significantly higher plasma concentrations of HGF, IGFBP-1, and IGFBP-6, but lower plasma concentrations of EGF and IGFBP-3 than controls. The logistics regression model showed that increased plasma concentration of HGF and IGFBP-1 and decreased plasma concentration of EGF were correlated with the development of pediatric VVS. ROC curve analysis showed that the abovementioned 3 proteins were useful for assisting the diagnosis of VVS. Conclusion: Plasma human growth cytokine profiling changed in pediatric VVS. Elevated plasma concentrations of HGF and IGFBP-1, and decreased EGF were associated factors in the development of pediatric VVS. The abovementioned three proteins are helpful for the diagnosis of pediatric VVS.

Risk factors of sitting-induced tachycardia syndrome in children and adolescents.

BACKGROUND: The study was designed to explore the risk factors for sitting-induced tachycardia syndrome (STS) in children and adolescents. METHODS AND RESULTS: In this case-control study, 46 children with STS and 184 healthy children and adolescents were recruited. Demographic characteristics, lifestyle habits, allergy history, and family history were investigated using a questionnaire. The changes in heart rate and blood pressure from supine to sitting were monitored using a sitting test. The possible differences between STS patients and healthy children were analyzed using univariate analysis. Logistic regression analysis was used to explore the independent risk factors for STS. Univariate analysis showed that the daily sleeping time of the STS children were significantly shorter than that of the control group [(8.8 ± 1.2) hours/day vs. (9.3 ± 1.0) hours/day, P = 0.009], and the proportion of positive family history of syncope in the STS patients was higher than the controls (4/42 vs. 3/181, P = 0.044). Multivariate logistic regression studies showed that reduced daily sleeping time was an independent risk factor of STS in children (P = 0.006). Furthermore, when daily sleeping time was prolonged by 1 h, the risk of STS was decreased by 37.3%. CONCLUSION: Reduced daily sleeping was an independent risk factor for STS in children and adolescents.

Baseline left ventricular ejection fraction associated with symptom improvements in both children and adolescents with postural tachycardia syndrome under metoprolol therapy.

BACKGROUND: Postural tachycardia syndrome (POTS) is a common childhood disease that seriously affects the patient's physical and mental health. This study aimed to investigate whether pre-treatment baseline left ventricular ejection fraction (LVEF) and left ventricular fractional shortening (LVFS) values were associated with symptom improvement after metoprolol therapy for children and adolescents with POTS. METHODS: This retrospective study evaluated 51 children and adolescents with POTS who received metoprolol therapy at the Peking University First Hospital between November 2010 and July 2019. All patients had completed a standing test or basic head-up tilt test and cardiac echocardiography before treatment. Treatment response was evaluated 3 months after starting metoprolol therapy. The pre-treatment baseline LVEF and LVFS values were evaluated for correlations with decreases in the symptom score after treatment (ΔSS). Multivariable analysis was performed using factors with a P value of <0.100 in the univariate analyses and the demographic characteristics. RESULTS: A comparison of responders and non-responders revealed no significant differences in demographic, hemodynamic characteristics, and urine specific gravity (all P > 0.050). However, responders had significantly higher baseline LVEF (71.09% ±â€Š4.44% vs. 67.17% ±â€Š4.88%, t = -2.789, P = 0.008) and LVFS values (40.00 [38.00, 42.00]% vs. 36.79% ±â€Š4.11%, Z = -2.542, P = 0.010) than the non-responders. The baseline LVEF and LVFS were positively correlated with ΔSS (r = 0.378, P = 0.006; r = 0.363, P = 0.009), respectively. Logistic regression analysis revealed that LVEF was independently associated with the response to metoprolol therapy in children and adolescents with POTS (odds ratio: 1.201, 95% confidence interval: 1.039-1.387, P = 0.013). CONCLUSIONS: Pre-treatment baseline LVEF was associated with symptom improvement after metoprolol treatment for children and adolescents with POTS.

Sympathetic Overactivation From Supine to Upright Is Associated With Orthostatic Hypertension in Children and Adolescents.

There are no prior publications or submissions with any overlapping information, including studies and patients. The study data have not been presented as an abstract or poster before the submission. Objectives: The study was conducted to analyze the changes of baroreflex sensitivity and heart rate variability from supine to upright standing in children and adolescents with orthostatic hypertension to explore whether and how the autonomic nerve regulation was involved in the development of pediatric orthostatic hypertension. Methods: This case-control study included twenty-five children with orthostatic hypertension (the patient group) and twenty-six healthy controls (the control group). All subjects underwent a standing test, during which their hemodynamic parameters were continuously monitored by a Finapres Medical System, and baroreflex sensitivity and heart rate variability were calculated. Results: The demographic characteristics, supine baroreflex sensitivity, and supine heart rate variability including time domain and frequency domain indices did not differ between the patients with orthostatic hypertension and healthy subjects (P > 0.05). However, a more obvious drop of baroreflex sensitivity and a greater increase of low frequency/high frequency ratio from supine to upright were observed in subjects with orthostatic hypertension compared with those in the healthy children (P < 0.001 and P < 0.01, respectively). Changes of baroreflex sensitivity were negatively related to mean arterial pressure changes from supine to upright in all subjects (P < 0.01), and the increases in low frequency/high frequency ratio from supine to standing were positively correlated with those in mean arterial pressure in the study subjects (P < 0.001). Conclusion: Upright sympathetic overactivation is associated with pediatric orthostatic hypertension.

Sitting-induced hemodynamic changes and association with sitting intolerance in children and adolescents: a cross-sectional study.

Hemodynamic alteration with postural change from supine to sitting has been unclear in the young. In the cross-sectional study, 686 participants (371 boys and 315 girls, aged 6-18 years) were recruited from 4 schools in Kaifeng city, the central area of China. The active sitting test was performed to obtain heart rate (HR) and blood pressure (BP) changes from supine to sitting in children and adolescents. Hemodynamic change-associated sitting intolerance was analyzed. In the study participants, the 95th percentile (P95) values of changes in HR and BP within 3 min from supine to sitting were 25 beats/min and 18/19 mm Hg, respectively. Sixty-six participants had sitting intolerance symptoms. Compared with participants without sitting intolerance symptoms, those with symptoms more frequently had HR increase ≥ P95 or BP increase ≥ P95 within 3 min from supine to sitting (P < 0.001). Risk factors for sitting intolerance were age (odds ratio 1.218, 95% confidence interval 1.072-1.384, P = 0.002) and changes in HR or BP ≥ P95 within 3 min after sitting (odds ratio 2.902, 95% confidence interval 1.572-5.357, P = 0.001). We firstly showed hemodynamic changing profiles from supine to sitting and their association with sitting intolerance in children and adolescents. Sitting tachycardia is likely suggested with a change in HR ≥ 25 beats/min and sitting hypertension with a change in BP ≥ 20/20 mm Hg when changing from supine to sitting within 3 min. The age and changes in HR or BP were independent risk factors for sitting intolerance.

Increased Endogenous Sulfur Dioxide Involved in the Pathogenesis of Postural Tachycardia Syndrome in Children: A Case-Control Study.

BACKGROUND: The pathogenesis of postural tachycardia syndrome (POTS) remains unclear. This study aimed to explore the changes and significance of sulfur dioxide (SO2) in patients with POTS. METHODS: The study included 31 children with POTS and 27 healthy children from Peking University First Hospital between December 2013 and October 2015. A detailed medical history, physical examination results, and demographic characteristics were collected. Hemodynamics was recorded and the plasma SO2was determined. RESULTS: The plasma SO2was significantly higher in POTS children compared to healthy children (64.0 ± 20.8 µmol/L vs. 27.2 ± 9.6 µmol/L, respectively, P < 0.05). The symptom scores in POTS were positively correlated with plasma SO2levels (r = 0.398, P < 0.05). In all the study participants, the maximum heart rate (HR) was positively correlated with plasma levels of SO2(r = 0.679, P < 0.01). The change in systolic blood pressure from the supine to upright (ΔSBP) in POTS group was smaller than that in the control group (P < 0.05). The ΔSBP was negatively correlated with baseline plasma SO2levels in all participants (r = -0.28, P < 0.05). In the control group, ΔSBP was positively correlated with the plasma levels of SO2(r = 0.487, P < 0.01). The change in HR from the supine to upright in POTS was obvious compared to that of the control group. The area under curve was 0.967 (95% confidence interval: 0.928-1.000), and the cutoff value of plasma SO2 level >38.17 µmol/L yielded a sensitivity of 90.3% and a specificity of 92.6% for predicting the diagnosis of POTS. CONCLUSIONS: Increased endogenous SO2levels might be involved in the pathogenesis of POTS.

[Changes of plasma intermedin during head-up tilt test in children with postural tachycardia syndrome and its significance].

OBJECTIVE: To explore possible mechanisms of postural tachycardia syndrome (POTS) by comparing plasma intermedin (IMD) during head-up tilt test (HUTT) in children with POTS. METHOD: The study subjects were divided into two groups: POTS group and control group. The POTS group consisted of twenty-nine children (male 14, female 15) with POTS, the mean age (12.4 ±3.1) years old, admitted into Peking University First Hospital from November 2013 to June 2014. The control group consisted of 32 healthy children (male 17, female 15). Their mean age was (11.6±2.2) years old, who were confirmed as healthy by physical examination and HUTT. Finapres Medical System was used to continuously monitor heart rate and blood pressure during HUTT, and electrocadiogram was performed. Supine systolic and diastolic blood pressure, mean arterial pressure (MAP), ΔMAP (standing mean arterial pressure-supine MAP), supine heart rate and ΔHR (standing HR-supine HR) were compared between POTS group and control group. Sandwich immunoluminescence assay was used to test plasma IMD. The plasma IMD level was compared in supine between POTS and control group. The plasma IMD level in supine was compared with HUTT in POTS group. RESULT: No significant differences were found in age, height, weight, supine systolic and diastolic blood pressure, MAP, ΔMAP and supine heart rate between POTS group and control group (P>0.05). ΔHR in POTS group was significantly higher than that of control group ((48±10) vs. (22±7) beats /min, t=9.797, P<0.05). The plasma IMD level in POTS group was lower than that of control group in supine position ((497±61)×10(-6) vs. (529±58)×10(-6) mg/L, t=2.117, P<0.05). But, it was higher during HUTT than supine IMD in POTS group ((537±57) ×10(-6) vs. (497±61)×10(-6) mg/L, t=-2.464, P<0.05). The plasma delta IMD level (HUTT vs. supine) was positively correlated with delta HR in POTS group (r=0.435, P<0.05). CONCLUSION: The excessively high heart rate during HUTT have a positive correlation with plasma IMD, which may play a role in the pathogenesis of POTS in children.

Plasma C-type natriuretic peptide as a predictor for therapeutic response to metoprolol in children with postural tachycardia syndrome.

POTS is a global public-health disease, but predictor for therapeutic response to metoprolol in children with POTS is lacking. This study was designed to investigate predictive value of plasma C-type natriuretic peptide (CNP) in the therapeutic efficacy of metoprolol on postural tachycardia syndrome (POTS) in children. Totally 34 children with POTS and 27 healthy children were included in the study. The head-up test or head-up tilt test was used to check heart rate and blood pressure from supine to upright in subjects. A double antibody (competitive) sandwich immunoluminometric assay was used to detect plasma CNP. Metoprolol was used to treat children with POTS. The difference in plasma concentrations of CNP between responders and non-responders was compared. An ROC curve was used to analyze plasma CNP to predict efficacy of metoprolol on POTS in children. Plasma CNP in children with POTS was significantly higher than that of healthy children [(51.9 ± 31.4) vs. (25.1 ± 19.1) pg/ml, P <0.001]. Plasma CNP in responders to metoprolol was significantly higher than non-responders [(59.1 ± 33.5) vs. (34.8 ± 16.7) pg/ml, P = 0.037] before treatment. The ROC curve showed that area under the curve was 0.821 (95% CI 0.642-0.999). The cut-off value of plasma CNP > 32.55 pg/ml yielded a sensitivity of 95.8% and specificity of 70% in predicting therapeutic efficacy of metoprolol on POTS children. Plasma CNP might serve as a useful predictor for the therapeutic efficacy of metoprolol on POTS in children.

A cross-sectional study on upright heart rate and BP changing characteristics: basic data for establishing diagnosis of postural orthostatic tachycardia syndrome and orthostatic hypertension.

OBJECTIVE: We aimed to determine upright heart rate and blood pressure (BP) changes to suggest diagnostic criteria for postural orthostatic tachycardia syndrome (POTS) and orthostatic hypertension (OHT) in Chinese children. METHODS: In this cross-sectional study, 1449 children and adolescents aged 6-18 years were randomly recruited from two cities in China, Kaifeng in Henan province and Anguo in Hebei province. They were divided into two groups: 844 children aged 6-12 years (group I) and 605 adolescents aged 13-18 years (group II). Heart rate and BP were recorded during an active standing test. RESULTS: 95th percentile (P(95)) of δ heart rate from supine to upright was 38 bpm, with a maximum upright heart rate of 130 and 124 bpm in group I and group II, respectively. P(95) of δ systolic blood pressure (SBP) increase was 18 mm Hg and P(95) of upright SBP was 132 mm Hg in group I and 138 mm Hg in group II. P(95) of δ diastolic blood pressure (DBP) increase was 24 mm Hg in group I and 21 mm Hg in group II, and P(95) of upright DBP was 89 mm Hg in group I and 91 mm Hg in group II. CONCLUSIONS: POTS is suggested when δ heart rate is ≥ 38 bpm (for easy memory, ≥ 40 bpm) from supine to upright, or maximum heart rate ≥ 130 bpm (children aged 6-12 years) and ≥ 125 pm (adolescents aged 13-18 years), associated with orthostatic symptoms. OHT is suggested when δ SBP (increase) is ≥ 20 mm Hg, and/or δ DBP (increase) ≥ 25 mm Hg (in children aged 6-12 years) or ≥ 20 mm Hg (in adolescents aged 13-18 years) from supine to upright; or upright BP ≥ 130/90 mm Hg (in children aged 6-12 years) or ≥ 140/90 mm Hg (in adolescents aged 13-18 years).

Risk factors for postural tachycardia syndrome in children and adolescents.

BACKGROUND: Postural tachycardia syndrome (POTS) is prevalent in children and adolescents and has a great impact on health. But its risk factors have not been fully understood. This study aimed to explore possible risk factors for children and adolescents with POTS. METHODS AND FINDINGS: 600 children and adolescents (test group) aged 7-18 (11.9 ± 3.0) years old, 259 males and 341 females, were recruited for identifying its risk factors. Another 197 subjects aged from 7 to 18 (11.3 ± 2.3) years old were enrolled in the validation group. Heart rate (HR) and blood pressure (BP) were monitored during upright test. Risk factors were analyzed and sensitivity and specificity for predicting POTS were tested via receiver operating characteristic curve. Among 600 subjects, 41 were confirmed with POTS patients (6.8%) based on clinical manifestation and upright test. The results showed a significant difference in daily water intake, the daily sleeping hours, supine HR, HR increment and maximum HR during upright test between POTS and the unaffected children (P<0.05). Likelihood of POTS would increase by 1.583 times if supine HR was increased by 10 beats/min (95%CI 1.184 to 2.116, P<0.01), by 3.877 times if a child's water intake was less than 800 ml/day (95%CI 1.937 to 7.760, P<0.001), or by 5.905 times (95%CI 2.972 to 11.733, P<0.001) if sleeping hours were less than 8 hours/day. Supine HR, daily water intake and sleeping hours showed the capability of predicting POTS in children and adolescents with an AUC of 83.9% (95% CI: 78.6%-89.1%), sensitivity of 80.5% and specificity of 75%. Furthermore, in validation group, predictive sensitivity and specificity were 73.3% and 72.5%. CONCLUSION: Faster supine HR, less water intake and shorter sleeping hours were identified as risk factors for POTS.

Reaction mechanisms of riboflavin triplet state with nucleic acid bases.

ESR and laser flash photolysis studies have determined a reasonable order of reactivity of nucleotides with triplet riboflavin (3Rb*) for the first time. ESR detection of triplet state reactivity of Rb with nucleoside, polynucleotide and DNA has been obtained simultaneously. In addition, ESR spin elimination measurement of the reactivity of 3Rb* with nucleotides in good accord with laser flash photolysis determination of the corresponding rate constants offers a simple and reliable method to detect the reactivities of nucleic acids and its components with photoexcited flavins. Kinetic, ESR and thermodynamic studies have demonstrated that Rb should be a strong endogenous photosensitizer capable of oxidizing all nucleic acid bases, and preferentially two purine nucleotides with high rate constants.

Time-dependent radiolytic yields of the solvated electrons in 1,2-ethanediol, 1,2-propanediol, and 1,3-propanediol from picosecond to microsecond.

The absorption spectra of the solvated electron in 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD) have been determined by nanosecond pulse radiolysis techniques. The maximum of the absorption band located at 570, 565, and 575 nm for these three solvents, respectively. With 4,4'-bipyridine (44Bpy) as a scavenger, the molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol-1 m2 for 12ED, 12PD, and 13PD, respectively. These values are two-thirds or three-fourths of the value usually reported in the literature. With these extinction coefficients, picosecond pulse radiolysis studies have allowed us to depict the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of water solution.

Pulse radiolysis of 4,4'-bipyridyl aqueous solutions at elevated temperatures: spectral changes and reaction kinetics up to 400 degrees C.

The spectral changes as well as the reaction kinetics of the transient species of 4,4'-bipyridyl (4,4'-bpy) have been experimentally investigated by pulse radiolysis techniques up to 400 degrees C. The results show that the transient species such as OH adduct 4,4'-bpyOH*, monoprotonated electron adduct 4,4'-bpyH*, and doubly protonated electron adduct 4,4'-bpyH2+* have 15-20 nm blue shifts from room temperature to 400 degrees C. For a deaerated neutral solution of 4,4'-bpy in the presence of tert-butyl alcohol, ethanol, or NaCOOH, the doubly protonated electron adduct is the main transient species at room temperature. But at temperatures > 350 degrees C, a monoprotonated form, the N-hydro radical 4,4'-bpyH*, becomes predominant. Interestingly, at room temperature, CO2-* could not efficiently react with 4,4'-bpy, but the reaction was accelerated with increasing temperature; at 350 degrees C, this reaction completed within 2 mus. Using an alkaline solution (pH = 11.5) of 4,4'-bpy in the presence of tert-butyl alcohol, we studied the N-hydro radical 4,4'-bpyH* from room temperature to 400 degrees C at 25 MPa. An estimation of the temperature-dependent G(e(aq)-) at 25 MPa agrees with our previous result with methyl viologen as a scavenger.

The formation and properties of the melatonin radical: a photolysis study of melatonin with 248 nm laser light.

The photolysis of melatonin in aqueous solution has been studied spectrometrically with a 248 nm laser. The formation of hydrated electrons in a monophotonic process has been confirmed in neutral solution with a quantum yield of 0.22. Two main absorption bands at 340 and 460 nm plus an absorption shoulder resulted from the counterpart of the ejected electron, a melatonin radical, in solution. The big difference for the relative intensity of the absorption peaks under various pH conditions reveals that the melatonin radical exists in the solution through an acid-base equilibrium. In support from the pH dependence of the spectrum of the intermediate, the pKa1 for the doubly-protonated melatonin radical against the mono-protonated melatonin cation radical was estimated to be -0.95 and the pKa2 for the mono-protonated melatonin cation and melatonin neutral radical was 4.5 +/- 0.5. This work will benefit the basic understanding about melatonin as a UV-light protector, as a light receptor and the antioxidation functions of melatonin.