Tracing Photoinduced Hydrogen Migration in Alcohol Dications from Time-Resolved Molecular-Frame Photoelectron Angular Distributions.

The recent implementation of attosecond and few-femtosecond X-ray pump/X-ray probe schemes in large-scale free-electron laser facilities has opened the way to visualize fast nuclear dynamics in molecules with unprecedented temporal and spatial resolution. Here, we present the results of theoretical calculations showing how polarization-averaged molecular-frame photoelectron angular distributions (PA-MFPADs) can be used to visualize the dynamics of hydrogen migration in methanol, ethanol, propanol, and isopropyl alcohol dications generated by X-ray irradiation of the corresponding neutral species. We show that changes in the PA-MFPADs with the pump-probe delay as a result of intramolecular photoelectron diffraction carry information on the dynamics of hydrogen migration in real space. Although visualization of this dynamics is more straightforward in the smaller systems, methanol and ethanol, one can still recognize the signature of that motion in propanol and isopropyl alcohol and assign a tentative path to it. A possible pathway for a corresponding experiment requires an angularly resolved detection of photoelectrons in coincidence with molecular fragment ions used to define a molecular frame of reference. Such studies have become, in principle, possible since the first XFELs with sufficiently high repetition rates have emerged. To further support our findings, we provide experimental evidence of H migration in ethanol-OD from ion-ion coincidence measurements performed with synchrotron radiation.

High-energy molecular-frame photoelectron angular distributions: a molecular bond-length ruler.

We present a study on molecular-frame photoelectron angular distributions (MFPADs) of small molecules using circularly polarized synchrotron light. We find that the main forward-scattering peaks of the MFPADs are slightly tilted with respect to the molecular axis. This tilt angle is directly connected to the molecular bond length by a simple, universal formula. We apply the derived formula to several examples of MFPADs of C 1s and O 1s photoelectrons of CO, which have been measured experimentally or obtained by means of ab initio modeling. In addition, we discuss the influence of the back-scattering contribution that is superimposed over the analyzed forward-scattering peak in the case of homo-nuclear diatomic molecules such as N2.

Investigating charge-up and fragmentation dynamics of oxygen molecules after interaction with strong X-ray free-electron laser pulses.

During the last decade, X-ray free-electron lasers (XFELs) have enabled the study of light-matter interaction under extreme conditions. Atoms which are subject to XFEL radiation are charged by a complex interplay of (several subsequent) photoionization events and electronic decay processes within a few femtoseconds. The interaction with molecules is even more intriguing, since intricate nuclear dynamics occur as the molecules start to dissociate during the charge-up process. Here, we demonstrate that by analyzing photoelectron angular emission distributions and kinetic energy release of charge states of ionic molecular fragments, we can obtain a detailed understanding of the charge-up and fragmentation dynamics. Our novel approach allows for gathering such information without the need of complex ab initio modeling. As an example, we provide a detailed view on the processes happening on a femtosecond time scale in oxygen molecules exposed to intense XFEL pulses.

Direct deconvolution of two-state pump-probe X-ray absorption spectra and the structural changes in a 100 ps transient of Ni(II)-tetramesitylporphyrin.

Full multiple scattering (FMS) Minuit XANES (MXAN) has been combined with laser pump-probe K-edge X-ray absorption spectroscopy (XAS) to determine the structure of photoexcited Ni(II)tetramesitylporphyrin, Ni(II)TMP, in dilute toluene solution. It is shown that an excellent simulation of the XANES spectrum is obtained, excluding the lowest-energy bound-state transitions. In ground-state Ni(II)TMP, the first-shell and second-shell distances are, respectively, d(Ni-N) = (1.93 +/- 0.02) A and d(Ni-C) = (2.94 +/- 0.03) A, in agreement with a previous EXAFS result. The time-resolved XANES difference spectrum was obtained (1) from the spectra of Ni(II)TMP in its photoexcited T(1) state and its ground state, S(0). The XANES difference spectrum has been analyzed to obtain both the structure and the fraction of the T(1) state. If the T(1) fraction is kept fixed at the value (0.37 +/- 0.10) determined by optical transient spectroscopy, a 0.07 A elongation of the Ni-N and Ni-C distances [d(Ni-N) and d(Ni-C)] is found, in agreement with the EXAFS result. However, an evaluation of both the distance elongation and the T(1) fraction can also be obtained using XANES data only. According to experimental evidence, and MXAN simulations, the T(1) fraction is (0.60 +/- 0.15) with d(Ni-N) = (1.98 +/- 0.03) A (0.05 A elongation). The overall uncertainty of these results depends on the statistical correlation between the distances and T(1) fraction, and the chemical shift of the ionization energy because of subtle changes of metal charge between the T(1) and S(0) states. The T(1) excited-state structure results, independently obtained without the excited-state fraction from optical transient spectroscopy, are still in agreement with previous EXAFS investigations. Thus, full multiple scattering theory applied through the MXAN formalism can be used to provide structural information, not only on the ground-state molecules but also on very short-lived excited states through differential analysis applied to transient photoexcited species from time-resolved experiments.

[Mitral valve repair in a patient with a porcelain ascending aorta].

A 78-year-old patient with heavily calcified ascending aorta underwent mitral valve repair for mitral valve regurgitation. Chordal replacement with expanded polytetrafluoroethylene (ePTFE) loop technique was done under endo aortic clamp with a balloon catheter. He was discharged from the hospital on the 24th postoperative day without any major complications. Endo aortic clamp is thought to be a useful technique for a case with heavily calcified aorta.

Analysis of poly(ethyl methacrylate)s by on-line hyphenation of liquid chromatography at the critical adsorption point and nuclear magnetic resonance spectroscopy

Liquid chromatography at the critical adsorption point (LC CAP) with on-line NMR detection (on-line LC CAP NMR) was utilized for analysis of tacticity distribution of stereo-regular poly(ethyl methacrylate)s (PEMAs). The separation of a model PEMA sample composed of four constituents with similar molar masses (Mw = (14-16) x 10(3) g mol-1) differing in their tacticity (rr triad content = 0, 33, 68, and 89%) was achieved by LC CAP with a mixed eluent composed of acetone, acetone-d6, and cyclohexane. The tacticity composition within each peak eluted from the LC CAP column was directly determined by a 750-MHz 1H NMR spectrometer that was used as a real-time detector in the continuous-flow mode. Tacticity distribution in a particular PEMA sample with mm/mr/rr = 2/45/53 and narrow molar mass distribution of Mw/Mn = 1.05 has been revealed by the LC CAP NMR technique.

Frequency of pericardial friction rub ("pericarditis") after direct percutaneous transluminal coronary angioplasty in Q-wave acute myocardial infarction.

The clinical significance of infarct-associated pericarditis was examined in 201 consecutive patients with acute Q-wave myocardial infarction with successful direct percutaneous transluminal angioplasty. A pericardial rub was a reliable clinical sign of extensive myocardial damage in patients with direct angioplasty.

Pericardial effusion after primary percutaneous transluminal coronary angioplasty in first Q-wave acute myocardial infarction.

To evaluate the incidence and clinical significance of infarction-associated pericardial effusion in patients with successful primary percutaneous transluminal coronary angioplasty, we studied 214 consecutive patients with a first Q-wave acute myocardial infarction. Based on 9 clinical variables, multivariate analysis was performed to determine the important variables related to the occurrence of pericardial effusion. Pericardial effusion was detected by echocardiography in 45 patients (21%); pericardial rub (p <0.001), number of advanced asynergic segments (p <0.001), ventricular aneurysmal motion (p = 0.03), and pulmonary capillary wedge pressure (p = 0.04) were found to be the important variables related to pericardial effusion. Among 45 patients with pericardial effusion, 29 patients with no pericardial rub had significantly higher pulmonary capillary wedge pressure than those with pericardial rub, whereas 16 patients with pericardial rub had a higher incidence of angiographic no reflow and ventricular aneurysmal motion than those without pericardial rub. Patients with pericardial effusion and a pericardial rub had a higher mortality rate than those without pericardial effusion (19% vs 3%; p = 0.02). Thus, pericardial effusion is still a relatively common clinical finding after primary percutaneous transluminal coronary angioplasty, and those with pericardial effusion and a pericardial rub were associated with more severe transmural myocardial damage and higher in-hospital mortality.

Early identification of impaired myocardial reperfusion with serial assessment of ST segments after percutaneous transluminal coronary angioplasty during acute myocardial infarction.

To evaluate the relation between ST-segment analysis and microvascular reperfusion in patients with acute myocardial infarction (AMI), we studied 51 patients with first AMI who were successfully treated by percutaneous transluminal coronary angioplasty (PTCA). The lead showing the greatest ST-segment elevation on the 12-lead electrocardiogram (ECG) was serially investigated until 24 hours after PTCA. Successful reperfusion was determined by technetium-99m tetrofosmin single-photon emission computed tomography. Impaired reperfusion (group 1: < 4 change in the sum of the defect score from before to immediately after PTCA) was observed in 24 patients, and successful reperfusion (group 2) was observed in 27 patients. Although ST-segment elevation was reduced significantly at 30 minutes after PTCA in group 2 (2.2 +/- 1.4 to 1.7 +/- 1.3 mm, p = 0.01), there was no significant change in group 1 (1.9 +/- 1.9 to 2.4 +/- 1.7 mm). Ten of 14 patients (71%) with persistent ST-segment elevation (DeltaST > 0 mm change in ST segment from before to 30 minutes after PTCA > 0) were in group 1, whereas 23 of 37 patients (62%) with ST-segment resolution (DeltaST < or = 0) were in group 2. The sensitivity and specificity of persistent ST-segment elevation for predicting impaired microvascular reperfusion were 42% and 85%, respectively. Thus, persistent ST-segment elevation 30 minutes after primary PTCA was a highly specific electrocardiographic marker of impaired reperfusion in patients with AMI.

The fundamentals of applying electrospray ionization mass spectrometry to low mass poly(methyl methacrylate) polymers.

Electrospray ionization (ESI) is capable of ionizing many soluble polymers. The ESI spectra are complex because of overlap of the multiply charged ions of the oligomer distribution, causing current computer transform programs to fail. However, it is possible to determine the origin of the multiply charged ions, making it feasible to write a program designed to transform ESI polymer spectra. To assess the value of such a program for polymer analysis, isolated monodisperse methyl methacrylate (MMA) oligomers (25 and 50 repeat units) were used to determine molar signal response and propensity for fragmentation.The sum of the peak areas for the multiply charged MMA 50-mer was found to be only about 66% of the summed peak areas for the 25-mer for the same molar concentration. However, conversion of the multiply charged peak areas to the singly charged representations, with peak area compression taken into account, gave equal signal responses for the 25-and 50-mers. Signal response variations due to the tacticity of the MMA oligomers were not observed. Fragmentation of the MMA oligomers also was shown not to occur under normal ESI conditions. Therefore, transformation of the polymer spectra to the singly charged molecular ion distribution should allow accurate calculation of average molecular weights, polydispersity, end group mass, and repeat unit mass.

Clinical significance of coronary flow to the infarct zone before successful primary percutaneous transluminal coronary angioplasty in acute myocardial infarction.

STUDY OBJECTIVE: To assess the effect of coronary flow to the infarct zone before primary coronary angioplasty on hospital complications in patients with acute myocardial infarction (MI). DESIGN: Consecutive case series analysis. SETTING: Coronary-care unit in a university hospital. PATIENTS: Two hundred sixty-four consecutive patients with ST-elevation acute MIs who had successful primary percutaneous transluminal coronary angioplasty. INTERVENTIONS: Coronary angiography on hospital admission and serial echocardiography. MEASUREMENTS AND RESULTS: The status of infarct-related artery flow before primary angioplasty was evaluated on hospital admission. Left ventricular wall motion and pericardial effusions were studied by echocardiography. One hundred ninety patients had total occlusions (Thrombolysis in Myocardial Infarction [TIMI] flow grade, 0 to 1) in the infarct-related artery (group 1), and 74 patients had antegrade flow (TIMI flow grade, 2 to 3) [group 2] before undergoing primary angioplasty procedures. When group 1 was subdivided into two groups (for the presence and absence of collateral flow), the patients with total occlusions and no collateral flow had a higher incidence of left ventricular aneurysmal wall motion (11% vs 1%, respectively; p = 0.03) and pericardial friction rub (15% vs 3%, respectively; p = 0.03) than did those in group 2. Moreover, those patients with total occlusions and no collateral flow had higher incidences of pericardial effusion (34% vs 17%, respectively; p = 0.02; and 34% vs 9%, respectively; p < 0.01) and in-hospital mortality (8% vs 1%, respectively; p = 0.04; and 8% vs 1%, respectively; p = 0.06) than did those patients in the other two groups. CONCLUSIONS: Despite successful primary angioplasty, the absence of antegrade flow in the infarct-related artery and collateral flow to the infarct zone before angioplasty resulted in a higher incidence of in-hospital complications.

Quantification of telomerase activity of regions unstained with iodine solution that surround oral squamous cell carcinoma.

The aim of this study was to analyze the iodine-unstained region expanding around oral squamous cell carcinoma (SCC) by quantification of telomerase activity. The epithelial dysplasia often observed around SCC is considered to cause local recurrence or a second primary cancer. However these areas are hard to distinguish from normal mucosa. To clear the border of the expanding epithelial dysplasia around SCC, we stained with 3% iodine solution, and then decided the surgical margin. We measured quantification of telomerase activity in tumor, in epithelial dysplasia, and also in normal epithelium. Thirty-three primary cases of oral SCC which have iodine-unstained region around lesions were investigated. Fluorescense-based TRAP was applied to obtain quantification of telomerase activity. We obtained the following results: histological examination confirmed that every patient's unstained region consisted of various degrees of epithelial dysplasia. The quantified telomerase activities for squamous cell carcinoma, epithelial dysplasia and normal epithelium were 53.9, 39.6 and 2.7 U/microgP, respectively, and there was a significant difference between carcinoma and normal areas, and between dysplasia and normal epithelium. Therefore, these findings suggest that the areas of epithelial dysplasia unstained by iodine consist of cells that are nearly cancerous and excessively proliferative, and that epithelial dysplasia around SCC should be resected together with the tumor. Vital staining with iodine is useful for identifying epithelial dysplasia around SCC.

Cardiovascular response to combined static-dynamic exercise of patients with myocardial infarction.

BACKGROUND: Graded dynamic exercise-stress testing of patients with acute myocardial infarction prior to discharge from hospital has an important diagnostic and prognostic implication. Although many daily tasks involve combinations of static and dynamic exercise, little is known about cardiovascular responses during combined static-dynamic exercise. OBJECTIVE: To determine the difference between cardiovascular responses during two types of combined static-dynamic exercise (a 10 kg weight in one hand, and a 10 kg weight bearing on the shoulder). METHODS: We studied 27 male patients who had recently suffered myocardial infarction using ear densitography. The patients were divided into two groups: group 1 was comprised of 14 patients with resting left ventricular end-diastolic volumes > or = 140 ml, and group 2 was comprised of 13 patients with left ventricular end-diastolic volumes < 140 ml. RESULTS: For eight patients in group 1 we detected positive electrocardiographic changes during one-hand weight-carrying exercise, but for none of these patients was there an electrocardiographic change during weight-bearing exercise. All the patients in group 2 completed both types of exercise without significant ST-segment change. Although there were no significant differences between values of any of the indices measured for the two groups during weight-bearing exercise, patients in group 1 had significantly shorter diastolic times/min (21.8 +/- 2.1 versus 25.1 +/- 2.4 s/min, P < 0.01) during one-hand weight carrying. CONCLUSIONS: In addition to decrease in subendocardial coronary blood flow associated with increase in left ventricular end-diastolic volume, shortening of diastolic perfusion time during one-hand weight-carrying exercise for patients in group 1 can potentially contribute to subendocardial ischemia, which was favorably altered by bearing a weight on the shoulder.

Clinical characteristics of ST-segment elevation in lead V6 in patients with Q-wave acute inferior wall myocardial infarction.

BACKGROUND: Precordial ST-segment depression in acute inferior infarction is well recognized, but few studies have evaluated ST-segment elevation in lateral precordial leads. The present study examined the clinical significance of ST-segment elevation in lead V6 in patients with acute Q-wave inferior myocardial infarction. METHODS: We studied the initial electrocardiography of 125 consecutive patients with acute Q-wave inferior myocardial infarction admitted to hospital within 12 h of the onset of chest pain. They were classified into two groups: group 1 = 34 patients with ST-segment elevation in lead V6; group 2 = 91 patients with no ST-segment elevation in lead V6. RESULTS: Among the seven clinical variables examined, the number of left ventricular asynergic segments (P < 0.001) and pulmonary capillary wedge pressure (P = 0.001) were related to ST-segment elevation in lead V6. The incidences of major arrhythmias (50% compared with 31%, P = 0.04), pericardial effusion (32% compared with 9%, P = 0.003), and pericardial rub (15% compared with 2%, P = 0.02) during the patients' stay in hospital were greater in group 1 than in group 2. Among the patients in group 1, the right coronary artery was the culprit artery in 22 of 24 patients (92%) with ST segment depression in lead I, whereas the circumflex artery was the culprit artery in nine of 10 patients (90%) with isoelectric or ST-segment elevation in lead I. CONCLUSION: The presence of ST-segment elevation in lead V6 in patients with acute Q-wave inferior myocardial infarction was associated with larger infarct size, and greater incidences of major arrhythmias and pericardial involvement during the patient's stay in hospital.

Correlates of bundle-branch block in patients undergoing primary angioplasty for acute myocardial infarction.

BACKGROUND: Early reperfusion therapy has reduced the infarct size and mortality rate in patients with acute myocardial infarction (AMI). The occurrence of bundle-branch block in AMI is related to the amount of myocardial damage and the insult to the conduction system. HYPOTHESIS: To evaluate the clinical and angiographic factors related to the occurrence of bundle-branch block (BBB) in patients with primary percutaneous transluminal coronary angioplasty (PTCA), we investigated consecutive series of patients with their first Q-wave AMI and successful PTCA. METHODS: Coronary angiogram at the time of admission, electrocardiogram, and echocardiogram were evaluated in 279 patients with their first Q-wave AMI and successful PTCA. RESULTS: Bundle-branch block was detected in 26 patients (9%); 16 patients had transient and 10 patients had persistent block, while 16 patients had bifascicular block and 10 patients had right BBB. The patients with BBB had a significantly larger number of left ventricular asynergic segments, higher incidence of total occlusion of infarct-related artery, angiographic no reflow, and pericardial rub than those without BBB. When the multivariate analysis was performed using five clinical markers of infarct severity, angiographic no reflow (F = 20.2, p < 0.001) and total occlusion of infarct-re-lated artery (F = 4.2, p = 0.04) were found to be the significant variables related to BBB. CONCLUSIONS: Despite successful primary PTCA, absence of antegrade flow in the infarct-related artery at the onset of AMI and/or angiographic no reflow resulted in more severe transmural myocardial damage and, hence, the occurrence of BBB.

A prospective study on mortality among Japanese coal miners.

We conducted a prospective study to clarify mortality patterns among Japanese coal miners in a former coal mining area. Subjects included 1,796 coal miners and 4,022 non-coal-miners, who were identified by a mail survey between 1987 and 1989, and then followed up from the date of the survey to April 30th, 1994. We applied Cox's proportional hazards model to compare the mortalities between coal miners and non-coal-miners. Among the coal miners, significantly high risk ratios were observed in all causes of death (risk ratio = 1.4, p < 0.05) and all malignant neoplasms (risk ratio = 1.5, p < 0.05). Risk ratios for all causes of death and all malignant neoplasms also rose with the length of experience in coal mining. Analysis of the results for sites of cancer showed that coal miners had high risk ratios for stomach cancer (risk ratio = 1.6), liver cancer (risk ratio = 1.4) and lung cancer (risk ratio = 1.6), though these ratios were not statistically significant. When the risk ratio for lung cancer was analyzed according to the length of experience in coal mining, coal miners with at least 15 years' experience had a significantly high risk ratio (risk ratio = 2.4, p < 0.05), though coal miners with less than 15 years' experience had almost the same risk as non-coal-miners.

Energy expenditure of paraplegic marathon runners measured during a wheelchair marathon.

Wheelchair bound paraplegics tend to spend a sedentary life. They seem to be vulnerable to prolonged strenuous exertion because of their many physical handicaps such as metabolic depression, cardiovascular instability, urinary incontinence, pressure sores and so on. In commemoration of The International Year of the Disabled, The First Oita International Wheelchair Marathon was held in Autumn of 1981. This paper is to review the results of an experiment made at this half marathon. The course length was 21.1 km. Ten competitors were selected at random as the subjects for measuring energy expenditure during the race. As a preliminary examination, a work load test was performed by using a wheelchair treadmill to obtain a regression equation of the individual relationship between oxygen uptake and heart rates. The oxygen uptake of individuals during the race was estimated from the heart rates which were recorded by the small memory box fixed beneath the wheelchair. Six subjects were successfully examined. The results revealed that paraplegics safely tolerated the prolonged strenuous exercise. Their average oxygen uptake, mean heart rate and the lap time during the race were 34.17 +/- 8.11 ml/kg/min (mean +/- SD), 167.6 +/- 15.8 beats/min and 87.1 +/- 9.1 min respectively. Heart rate of the subjects was always very high during the race, although oxygen consumption was fairly low in comparison to able-bodied elite marathon runners.

[Readmission among discharged psychiatric patients and it's correlates].

OBJECTIVE: This study investigated the incidence of readmission among discharged psychiatric patients and examined factors predicting early readmission. METHODS: A cohort of 343 patients, who had been hospitalized involuntarily to mental hospitals for medical care and custody, and who were discharged between April 1991 and September 1993, in two areas served by Fukuoka Prefectural Yamato Health Center (n = 163) and Tagawa Health Center (n = 180) were followed up until November 1994. RESULTS: The readmission rates within 6 months of discharge in Yamato Health Center and Tagawa Health Center were 17% and 22%, and within 1 year were 30% and 31% respectively. From Cox's proportional hazards model, alcohol/drug abuse, many of previous admission, long length of recent hospitalization, payment of medical care cost from public assistance, complication of physical disorders, living without a person responsible for custody after discharge, no request of health center's service by the hospital and discharge from a large-scale mental hospital were significantly related to increased risk of readmission. Not a few patients could not be followed up completely because of early drop-out of treatment. The drop-out rates within 1 month of discharge in Yamato Health Center and Tagawa Health Center were 10% and 26%, and within 1 year were 15% and 27% respectively. CONCLUSIONS: The rates of readmission and drop-out of treatment among discharged psychiatric patients were considerably high. This study clarified that rapid establishment of a mental health system supporting the mentally disabled in a community is an urgent need in Japan.

The carcinostatic effects of 1-(2-tetrahydrofuryl)-5-fluorouracil and uracil (UFT) on tongue carcinoma induced by 4-nitroquinoline 1-oxide (4NQO) in rats.

UFT is a carcinostatic agent used in adjuvant chemotherapy for head and neck cancer. In the present study. UFT was given orally to treat tongue carcinoma in rats induced by 4-nitroquinoline 1-oxide. The antitumor effects of UFT were studied macroscopically and histologically. In addition, the antitumor effects of UFT were evaluated in relationship to lesions of the clinical and, invasive types, and to there vascular structure. In clinical lesions, the antitumor effect of UFT was higher in extrovert tumor-mass lesions and lower in ulcerous lesions. With regard to vascular structure, the effect was higher in cases demonstrating irregular net-like patterns and branch-like patterns and lower in cases in which the pattern had been destroyed. There was a correlation between antitumor effect and invasive type. As invasive tendency the 3H-thymidine labeling index, and mitotic index increased, antitumor effect and degree of tumor cell degeneration decreased.

Clinicostatistical study of ameloblastoma treatment.

The purpose of this study was to investigate the treatment of 190 cases of ameloblastoma in our department from 1966 to 1994. The statistical results with regard to age, sex and region agreed with those of other investigators. Thirty-five of 43 (81.4%) cases underwent enucleation in 1960s, but the sixteen of 27 (59.3%) cases underwent partial resection of mandible in 1990s. The defect of mandible was reconstructed with iliac bone grafting since 1968, grafts with a mixture of iliac blocked bone and PCBM (particulate cancellous bone and marrow) have been used since 1975. Grafting of the inferior alveolar nerve with the great auricular nerve to the defect has been performed in our department since 1977. Recently, technique involving pull-through of the inferior alveolar nerve bundle has been used in our department. When the reconstruction method for the mandible and nerve has been established, it becomes possible to operate radically and positively. Recurrence occurred in 17 cases after the primary enucleation. It is thought that the primary treatment of ameloblastoma must be as radical as possible. It appears to be necessary to observe progress and perform follow-up in cases of ameloblastoma for more than ten years, because there was one recurrence at 9 years and 4 months after the first operation. In fact, three quarters of our cases were lost to follow-up. Such losses can problems in confirming recurrence and responding rapidly.