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Shuji Kato

Publications and source records attributed to Shuji Kato.

At least 19 recordsLinked to original sources

Thermochemical studies of pyrazolide.

The 351.1 nm photoelectron spectrum of 1-pyrazolide anion has been measured. The 1-pyrazolide ion is produced by hydroxide (HO(-)) deprotonation of pyrazole in a flowing afterglow ion source. The electron affinity (EA) of the 1-pyrazolyl radical has been determined to be 2.938 +/- 0.005 eV. The angular dependence of the photoelectrons indicates near-degeneracy of low-lying states of 1-pyrazolyl. The vibronic feature of the spectrum suggests significant nonadiabatic effects in these electronic states. The gas phase acidity of pyrazole has been determined using a flowing afterglow-selected ion flow tube; Delta(acid)G(298) = 346.4 +/- 0.3 kcal mol(-1) and Delta(acid)H(298) = 353.6 +/- 0.4 kcal mol(-1). The N-H bond dissociation energy (BDE) of pyrazole is derived to be D(0)(pyrazole, N-H) = 106.4 +/- 0.4 kcal mol(-1) from the EA and the acidity using a thermochemical cycle. In addition to 1-pyrazolide, the photoelectron spectrum demonstrates that HO(-) deprotonates pyrazole at the C5 position to generate a minor amount of 5-pyrazolide anion. The photoelectron spectrum of 5-pyrazolide has been successfully reproduced by a Franck-Condon (FC) simulation based on the optimized geometries and the normal modes obtained from B3LYP/6-311++G(d,p) electronic structure calculations. The EA of the 5-pyrazolyl radical is 2.104 +/- 0.005 eV. The spectrum exhibits an extensive vibrational progression for an in-plane CCN bending mode, which indicates a substantial difference in the CCN angle between the electronic ground states of 5-pyrazolide and 5-pyrazolyl. Fundamental vibrational frequencies of 890 +/- 15, 1110 +/- 35, and 1345 +/- 30 cm(-1) have been assigned for the in-plane CCN bending mode and two in-plane bond-stretching modes, respectively, of X (2)A' 5-pyrazolyl. The physical properties of the pyrazole system are compared to the isoelectronic systems, pyrrole and imidazole.

Journal Article↗

Deuterium kinetic isotope effects in gas-phase S(N)2 and E2 reactions: comparison of experiment and theory.

The competition between bimolecular nucleophilc substitution and base-induced elimination is investigated through kinetic isotope effect measurements for gas-phase reactions of RCl + ClO- (R = methyl, ethyl, isopropyl, and tert-butyl) utilizing a FA-SIFT instrument. The overall reaction rate constants and the kinetic isotope effect for the reaction of C2H5Cl + ClO- are compared to computational results. [Hu, W. P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860.] Experimental results show that as the degree of substitution in the neutral reactant increases the E2 channel becomes dominant. The systematic change in the overall kinetic isotope effects indicates that, for the reaction of ClO- with C2H5Cl, both the SN2 and E2 pathways do occur, as predicted by computation; however the experimental reaction rate constants and KIE deviate strongly from the computational result.

Journal Article↗

Recurrence pattern for superficial bladder cancer.

AIM: Patients with superficial bladder tumors sometimes have long recurrence-free intervals. We evaluated whether patients with long recurrence-free periods had subsequent recurrences. We also clarified how these patients should be followed. MATERIALS AND METHODS: We enrolled 244 patients with superficial bladder cancer (62 pTa and 182 pT1) treated by transurethral resection of bladder tumor (TURBT) and adjuvant chemotherapy with pirarubicin. Median follow up was 75.5 months. Patients were stratified by the length of their recurrence-free interval. RESULTS: Recurrences occurred in 124 patients (50.8%). Of 185 patients who did not have a recurrence for the first 3 years, subsequent recurrences occurred in 65 patients; in more than half the first recurrence developed after 5 years or more. Ta tumors had a low recurrence rate (14.5%) with the first recurrence often developing after a long recurrence-free period. Of 40 patients who remained recurrence-free for 3 years or more after at least one recurrence occurred, 16 patients (40%) had subsequent recurrences. Furthermore, most of these patients who remained free of recurrence for more than 5 years eventually had a recurrence. The overall progression rate was 15.6%, and this did not relate to the length of the recurrence-free interval. CONCLUSION: When patients did not have a recurrence for the first 3 years, tumors subsequently often recurred, even in pTa tumors. In patients with at least once recurrence, subsequent recurrences appear to occur irrespective of the length of the recurrence-free period. Thus, we recommend that all patients with superficial bladder tumors be followed for as long as possible.

Adult↗

Photoelectron spectra and ion chemistry of imidazolide.

The 351.1 nm photoelectron spectrum of imidazolide anion has been measured. The electron affinity (EA) of the imidazolyl radical is determined to be 2.613 +/- 0.006 eV. Vibrational frequencies of 955 +/- 15 and 1365 +/- 20 cm(-1) are observed in the spectrum of the (2)B1 ground state of the imidazolyl radical. The main features in the spectrum are well-reproduced by Franck-Condon simulation based on the optimized geometries and the normal modes obtained at the B3LYP/6-311++G(d,p) level of density functional theory. The two vibrational frequencies are assigned to totally symmetric modes with C-C and N-C stretching motions. Overtone peaks of an in-plane nontotally symmetric mode are observed in the spectrum and attributed to Fermi resonance. Also observed is the photoelectron spectrum of the anion formed by deprotonation of imidazole at the C5 position. The EA of the corresponding radical, 5-imidazolyl, is 1.992 +/- 0.010 eV. The gas phase acidity of imidazole has been determined using a flowing afterglow-selected ion tube; delta(acid)G298 = 342.6 +/- 0.4 and delta(acid)H298 = 349.7 +/- 0.5 kcal mol(-1). From the EA of imidazolyl radical and gas phase acidity of imidazole, the bond dissociation energy for the N-H bond in imidazole is determined to be 95.1 +/- 0.5 kcal mol(-1). These thermodynamic parameters for imidazole and imidazolyl radical are compared with those for pyrrole and pyrrolyl radical, and the effects of the additional N atom in the five-membered ring are discussed.

Journal Article↗

Heat of hydrogenation of 1,5-dehydroquadricyclane. A computational and experimental study of a highly pyramidalized alkene.

The radical anion of the highly pyramidalized alkene 1,5-dehydroquadricyclane (1) was generated in the gas phase from the Squires reaction of 1,5-bis(trimethylsilyl)quadricyclane with F-/F2. The electron binding energy and proton affinity of 1*- were determined by bracketing experiments to be 0.6 +/- 0.1 eV and 386 +/- 5 kcal/mol, respectively. These values are in good agreement with values predicted by density functional theory (B3LYP/6-31+G*) and ab initio (CASPT2/6-31+G*) calculations. The experimental heat of hydrogenation of 1, obtained from a thermochemical cycle, was found to be 91 +/- 9 kcal/mol. This value of deltaH(H2) leads to values of 67 +/- 9 kcal/mol for the olefin strain energy (OSE) of 1, 172 +/- 9 kcal/mol for its heat of formation, and 23 +/- 9 kcal/mol for its pi bond dissociation enthalpy. Since the retro-Diels-Alder reaction of neutral 1 is computed to be highly exothermic, the finding that 1*- apparently does not undergo a retro-Diels-Alder reaction is of particular interest. The B3LYP/6-31+G* optimized geometry of 1 suggests that the bonding in this alkene is partially delocalized, presumably because the highly pyramidalized double bond in 1 interacts with the distal cyclopropane bonds in a manner that eventually leads to a retro-Diels-Alder reaction. The good agreement of the B3LYP and (2/2)CASPT2 values for the heat of hydrogenation and OSE of 1 with the experimentally derived values provides indirect evidence for the correctness of the B3LYP prediction that the equilibrium geometry of 1 lies part way along the reaction coordinate to the transition structure for the retro-Diels-Alder reaction.

Journal Article↗

Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification.

We have used a newly developed proton-transfer ion-trap mass spectrometry (PIT-MS) instrument for online trace gas analysis of volatile organic compounds (VOCs) during the 2004 New England Air Quality Study-Intercontinental Transport and Chemical Transformation study. The PIT-MS instrument uses proton-transfer reactions with H3O+ ions to ionize VOCs, similarto a PTR-MS (proton-transfer reaction mass spectrometry) instrument but uses an ion trap mass spectrometer to analyze the product ions. The advantages of an ion trap are the improved identification of VOCs and a near 100% duty cycle. During the experiment, the PIT-MS instrument had a detection limit between 0.05 and 0.3 pbbv (S/N = 3 (signal-to-noise ratio)) for 2-min integration time for most tested VOCs. PIT-MS was used for ambient air measurements onboard a research ship and agreed well with a gas chromatography mass spectrometer). The comparison included oxygenated VOCs, aromatic compounds, and others such as isoprene, monoterpenes, acetonitrile, and dimethyl sulfide. Automated collision-induced dissociation measurements were used to determine the contributions of acetone and propanal to the measured signal at 59 amu; both species are detected at this mass and are thus indistinguishable in conventional PTR-MS.

Air Movements↗

100-minute retroperitoneoscopic radical nephrectomy: a new retroperitoneal approach with a hand assisted method.

PURPOSE: A new approach for retroperitoneoscopic radical nephrectomy is introduced. The point of our surgical method is the application of a combination of hand assistance and pure laparoscopic procedures with appropriate surgical steps via the retroperitoneal approach. In our early series we had good surgical results and we completed radical nephrectomy in about 100 minutes using this procedure. MATERIALS AND METHODS: A total of 20 consecutive patients with renal cell carcinoma (cT1-2) who were operated on with this surgical method were analyzed. Surgical procedures occurred in 5 steps. In step 1 the retroperitoneal space was created manually from a pararectal incision at the umbilicus level. In step 2 the lateroconal fascia was incised and the renal hilar area was exposed with hand assistance. In step 3 hilar dissection was performed by pure laparoscopic procedure with another surgical instrument inserted from the hand device. Step 4 involved the application of hand assistance again for the quick mobilization of the kidney and adrenal gland. In step 5 the intact surgical specimen was retrieved from the hand device. RESULTS: Mean operative time and estimated blood loss were 103 +/- 21 minutes (range 70 to 145) and 49 +/- 85 ml (range 5 to 360), respectively. Mean days to oral intake and ambulation were 1.0 and 1.1, respectively. Operative times of the steps of hilar dissection and mobilization of the kidney and adrenal were shorter than in other series performed by standard retroperitoneoscopic radical nephrectomy. Major complications were not experienced. At this point, no metastasis has been experienced. CONCLUSIONS: Our surgical method may have the benefits of the retroperitoneal approach and hand assistance. The retroperitoneoscopic hand assisted method may be another important option in the 3 major approaches for laparoscopic radical nephrectomy, although longer-term followup is clearly required.

Adult↗

Heparin cofactor II is a novel protective factor against carotid atherosclerosis in elderly individuals.

BACKGROUND: Thrombin plays a crucial role in atherothrombotic changes. Because heparin cofactor II (HCII) inhibits thrombin actions after binding to dermatan sulfate at injured arterial walls, HCII may negatively regulate thrombin actions in vascular walls. We hypothesized that plasma HCII activity is a preventive factor against atherosclerotic changes, especially in elderly individuals who already have atherosclerotic vascular injuries. METHODS AND RESULTS: Maximum plaque thickness (MPT) in the carotid artery was measured by ultrasonography in 306 Japanese elderly individuals (154 men and 152 women; age, 40 to 91 years; 68.9+/-11.1 years, mean+/-SD). The relevance of cardiovascular risk factors including plasma HCII activity to the severity of MPT was statistically evaluated. Plasma HCII activity decreased with age. Simple linear regression analysis after adjustments for age and sex showed that lipoprotein(a), glycosylated hemoglobin A1c, and presence of diabetes mellitus significantly contributed to an increase in MPT values (r=0.119, P<0.05; r=0.196, P<0.001; and r=0.227, P<0.0001, respectively). In contrast, high-density lipoprotein (HDL) cholesterol and HCII activity were negatively correlated with MPT values (r=-0.117, P<0.05, and r=-0.202, P<0.0005, respectively). Multiple regression analysis revealed that plasma HCII activity and HDL cholesterol independently contributed to the suppression of MPT values and that the antiatherogenic contribution of HCII activity was stronger than that of HDL cholesterol (P<0.001 and P<0.05, respectively). CONCLUSIONS: These results suggest that HCII can be a novel and independent antiatherogenic factor. Moreover, HCII is a stronger predictive factor than HDL cholesterol against carotid atherosclerosis in elderly individuals.

Adult↗

Gas-phase kinetics and mechanism of the reactions of protonated hydrazine with carbonyl compounds. Gas-phase hydrazone formation: kinetics and mechanism.

The gas-phase reactions of protonated hydrazine (hydrazinium) with organic compounds were studied in a selected ion flow tube-chemical ionization mass spectrometer (SIFT-CIMS) at 0.5 Torr pressure and approximately 300 K and with hybrid density functional calculations. Carbonyl and other polar organic compounds react to form adducts, e.g., N(2)H(5)(+)(CH(3)CH(2)CHO). In the presence of neutral hydrazine, aldehyde adducts react further to form protonated hydrazones, e.g., CH(3)CH(2)CH[double bond]HNNH(2)(+) from propanal. Using deuterated hydrazine (N(2)D(4)) and butanal, we demonstrate that the gas-phase ion chemistry of hydrazinium and carbonyls operates by the same mechanisms postulated for the reactions in solution. Calculations provide insight into specific steps and transition states in the reaction mechanism and aid in understanding the likely reaction process upon chemical or translational activation. For most carbonyls, rate coefficients for adduct formation approach the predicted maximum collisional rate coefficients, k approximately 10(-9) cm(3) molecule(-1) s(-1). Formaldehyde is an exception (k approximately 2 x 10(-11) cm(3) molecule(-1) s(-1)) due to the shorter lifetime of its collision complex. Following adduct formation, the process of hydrazone formation may be rate limiting at thermal energies. The combination of fast reaction rates and unique chemistry shows that protonated hydrazine can serve as a useful chemical-ionization reagent for quantifying atmospheric carbonyl compounds via CIMS. Mechanistic studies provide information that will aid in optimizing reaction conditions for this application.

Journal Article↗

Gas-phase reactions of organic radicals and diradicals with ions.

Reactions of polyatomic organic radicals with gas phase ions have been studied at thermal energy using a flowing afterglow-selected ion flow tube (FA-SIFT) instrument. A supersonic pyrolysis nozzle produces allyl radical (CH2CHCH2) and ortho-benzyne diradical (o-C6H4) for reaction with ions. We have observed: [CH2CHCH2 + H3O+ --> C3H6+ + H2O], [CH2CHCH2 + HO- --> no ion products], [o-C6H4 + H3O+ --> C6H5+ + H2O], and [o-C6H4 + HO- --> C6H3- + H2O]. The proton transfer reactions with H3O+ occur at nearly every collision (kII approximately with 10(-9) cm3 s(-1)). The exothermic proton abstraction for o-C6H4 + HO- is unexpectedly slow (kII approximately with 10(-10) cm3 s(-1)). This has been rationalized by competing associative detachment: o-C6H4 + HO- --> C6H5O + e-. The allyl + HO- reaction proceeds presumably via similar detachment pathways.

Journal Article↗

Characteristics of patients with staghorn calculi in our experience.

PURPOSE: To elucidate the factors contributing to staghorn stone formation in patients. MATERIALS AND METHODS: The records of 82 patients (44 men and 38 women) with complete staghorn calculi were reviewed retrospectively for clinical presentation, metabolic disturbances and anatomical abnormalities. RESULTS: There were 79 unilateral and three bilateral cases. The patient performance of the activities of daily life was assessed with the modified Rankin scale (MRS) and it was found that 69 patients were functionally independent (84.1%, MRS 0-1) and 10 patients had a severe disability (12.2%, MRS 4-5). Seven patients had chronic indwelling catheters (8.5%). A positive urine culture was found in 24.4% of patients. Analysis of stone composition revealed magnesium ammonium phosphate and mixed calcium oxalate-phosphate were the most frequently identified types of stone (32.1% and 22.2%, respectively). Urinary pH was low in patients with uric acid stones (mean 5.4). Hyperuricemia, cystinuria and hypercalciuria were found in 14.6%, 2.4% and 37.8%, respectively. Hypercalciuria was found more frequently in calcium-stone cases. Eleven patients (13.4%) showed structural abnormalities of the kidney. CONCLUSIONS: Our data show that the patients with severe disability, urinary tract infection and hypercalciuria could be recognized more frequently in staghorn calculi compared with common urolithiasis. However, in Western countries, the frequency of both urinary tract infection and struvite stones is much higher than in our data. Other Japanese authors have also reported the low frequency of struvite stones in staghorn calculi, suggesting that various factors other than urinary tract infection possibly contribute to the formation of staghorn calculi in Japan.

Activities of Daily Living↗

Gas-phase ion-molecule reactions of small nitroalkanes and their deprotonated anions.

Gas-phase reactions of nitromethane (1), nitroethane (2), 2-nitropropane (3), 2-methyl-2-nitropropane (4) and nitrocyclopropane (5) were studied at 300 K using the flowing afterglow technique. These nitroalkanes react with gas-phase bases HO(-), CH(3)O(-) and HOO(-) very rapidly with rate coefficients of (2.5-4.3) x 10(-9) cm(3) s(-1) and reaction efficiencies of 60-100%, for example, k = 3.2 x 10(-9) cm(3) s(-1) (86%) for 5 reacting with hydroperoxide anion. Proton transfer (PT) is the only reaction observed for 1 while elimination (E2) is the exclusive pathway for 4 yielding isobutene and NO(2)(-). Both PT and E2 reactions are observed for 2, 3 and 5, the former being the major pathway. Deprotonated anions of 1, 2, 3 and 5 were subjected to reactivity studies with CH(3)I, CO(2), CS(2) and SO(2). Nucleophilic substitution (S(N)2) reaction occurs with CH(3)I while characteristic products CS(2)O(-) and SO(3)(-) are formed from CS(2) and SO(2), respectively, along with competing adduct formation. The SN(2) rate is greater, whereas the reactivities with the triatomic reagents are smaller for deprotonated nitrocyclopropane than for the other acyclic anions. These observations strongly suggest that the reactions of nitroalkane [M - H](-) anions occur through initial attack from the terminal oxygen; the nitrocyclopropane carbanion is more strained and, thus, less stabilized by resonance [R(2)C(-) - NO2 <--> R(2)=NO(2)(-)] resulting in the greater basicity/nucleophilicy and the less negative charge on the oxygen site.

Journal Article↗

[Analysis of clinical manifestations and endocrinological aspects of patients having PADAM-like symptoms].

PURPOSE: To analyze clinical manifestations and endocrinological aspects of the patients who visited our hospital to be examined for partial androgen deficiency in the aging male (PADAM). MATERIALS AND METHODS: Two hundred forty-three patients were evaluated. History taking and questionnaires were employed for analysis of their symptoms. Serum total testosterone (T), free-T and other hormones were measured for evaluation of the androgen deficiency. RESULTS: The chief complains of the patients were categorized as psychological symptoms, somatovegatative symptoms, and sexual symptoms, accounting for 51%, 36%, and 13%, respectively. A depressed mood, hot flashes and sweating and erectile dysfunction were dominant in these symptom categories, respectively. The prevalence of the psychological symptoms and somatovegatative symptoms was relatively high in the 30-50-year-old and 60-70-year-old groups, respectively. The free-T, but not total-T, was significantly decreased with aging as measured by the RIA method. Twenty one percent of the patients showed a lower total-T level than the normal range (2.7-10.7 ng/ml). The percentage of those with a total-T level lower than 2.0 ng/dl, which is the criterion for T-replacement recommended by the American Association of Clinical Endocrinologists guidelines, was 9%. Eighty two percent and 30% of the patients had lower free-T levels than the normal range (15.2-43.5 pg/ml) and that of men in their twenties in the Canadian data (9.3-26.5 pg/ml). Depending on the criteria of androgen deficiency, not all patients had low total-T and free-T levels. CONCLUSION: Patients suspected of having PADAM present various clinical symptoms and endocrinological aspects.

Adult↗

Signet-ring cell carcinoma of the prostate effectively treated with maximal androgen blockade.

Primary signet-ring cell carcinoma (SRCC) of the prostate is very rare and has a poor prognosis, even when treated with aggressive therapy. We report herein a case of a 72-year-old man with prostatic SRCC. The patient had a tumor that extended directly to the rectum. Maximal androgen blockade was started and 20 months later, the patient was alive without evidence of recurrence. The present case of prostatic SRCC responded well to medical therapy, however, tumors can recur after a long period of time. Therefore, adjuvant therapy is recommended.

Aged↗

Decreased AP-1 activity and interleukin-11 expression by bone marrow stromal cells may be associated with impaired bone formation in aged mice.

UNLABELLED: Expression of an osteogenic cytokine, IL-11, is decreased in SAMP6. We show here that IL-11 transcription largely depends on AP-1 transcription factors, activities of which are decreased in SAMP6 as well as aged ICR mice. Therefore, diminished AP-1 activity and the resultant decline in IL-11 expression may play a role in impaired bone formation in the aged. INTRODUCTION: Evidence suggests that impaired osteoblastogenesis contributes to aging-associated osteopenia. The P6 strain of senescence-accelerated mice (SAM) is an animal model of senile osteoporosis, which exhibits low bone mass caused by impaired bone formation. Bone marrow stromal cells from SAMP6 show decreased osteoblastogenesis and increased adipogenesis. We previously demonstrated that these abnormalities of SAMP6 stromal cells may be attributed to decreased expression of interleukin (IL)-11. METHODS: In this study, we attempted to determine the molecular mechanism of decreased IL-11 expression by SAMP6 stromal cells by cloning and analyzing the mouse IL-11 gene promoter. RESULTS AND CONCLUSIONS: We found that two tandem activating protein-1 (AP-1) sites that reside immediately upstream of TATA box play critical roles in IL-11 gene transcription. Gel shift analysis showed that binding activity to the IL-11 AP-1 sites was reduced in SAMP6 stromal cell nuclear extracts. Among multiple components of AP-1 transcription factors, Jun D binding was particularly decreased. Furthermore, decreased Jun D binding and IL-11 expression by stromal cells was also observed in aged mice of the ICR strain. Therefore, decreased AP-1 activity and a resultant decline in IL-11 expression by bone marrow stromal cells may play a role in impaired bone formation in the aged.

5' Untranslated Regions↗

[Marked 99mTc-PYP myocardial accumulation immediately after reperfusion in a patient with acute myocardial infarction].

We reported a case of a 72-year-old man with chest pain. An electrocardiogram showed ST segment elevation in I, II, III, aVL, aVF and V1-6 leads. 99mTc-tetrofosmin myocardial SPECT showed defect in the anterior, septal, apical and inferior walls. Coronary angiography showed 99% stenosis of the proximal right coronary artery and total occlusion of the midsegment of the left anterior descending coronary artery. Therefore, direct PTCA was performed for each lesion to achieve reperfusion. We didnt's see reperfusion injury during PTCA of the left coronary artery. On the other side, we saw severe reperfusion injury, such as slow-flow, arrhythmia and falling blood pressure during PTCA of the right coronary artery. After four hours, 99mTc-PYP myocardial SPECT showed marked uptake in the apical and inferior walls, and mild uptake in the anterior and posterior walls. After three days, severely-reduced uptake of 99mTc-PYP in the apex was noted, and mild uptake in the mid-portion of the anterior wall and the mid-portion of the inferior wall. Though reperfusion injury was seen, three was mild myocardial uptake of 99mTc-PYP in the area of the right coronary artery. On the other side, despite no reperfusion injury, there showed marked uptake during the acute phase and defect during the subacute phase in the area of the left coronary artery. Wall motion of the left ventricle was normal in the area of the right coronary artery and akinesis was seen on the left. These findings suggest that 99mTc-tetrofosmin and 99mTc-PYP myocardial SPECT are useful for visualization of reperfusion injury during the acute phase and for estimation of function during the chronic phase, better even than electrocardiogram or coronary angiography.

Acute-Phase Reaction↗

[Assessment of microcirculation disturbance with nuclear cardiology in a patient with coronary ectasia: a case report].

A 69-year-old woman presented with dyspnea on exertion. Echocardiography showed dilatation and diffuse hypokinesis of the left ventricle. 99mTc-tetrofosmin myocardial SPECT showed moderately reduced uptake in the anteroseptal wall and the inferior wall on the rest images, but was improved on the ATP loading images. 123I-BMIPP myocardial SPECT showed severely reduced uptake in the anterior wall and the inferior wall. These SPECT findings suggested ischemic heart disease rather than dilated cardiomyopathy. Coronary angiography showed no organic stenosis, but diffuse coronary ectasia was noted in three vessels. Intravascular ultrasound revealed remarkable coronary ectasia, with a maximal diameter of 8.2 mm. Coronary flow velocity as measured by Doppler blood flow guide wire was remarkably reduced. Coronary spasms were not provocated by ergonovine loading test. These findings suggested that microvascular thrombi and disturbance of dilatation caused myocardial ischemia in this patient. We treated the patient with ticlopidine and nicorandil. Following treatment left ventricle wall motion, 99mTc-tetrofosmin and 123I-BMIPP myocardial SPECT findings were improved.

Aged↗

Chemical ionization mass spectrometric determination of acrolein in human breast cancer cells.

A selected ion flow tube-chemical ionization mass spectrometric method is presented for the first determination of acrolein metabolically produced in biological tissues. Acrolein in aqueous samples (2.5 ml) is preconcentrated by distillation and directly analyzed using gas-phase proton transfer from H3O+. This method provides sensitive detection of acrolein with the method detection limit of 15 nM at the 99% confidence level. Detection is linear up to the highest concentration studied (13.5 microM, R2 = 0.998). Acrolein levels are determined in doxorubicin-sensitive (MCF-7) and doxorubicin-resistant (MCF-7/Adr) human breast cancer cells in vitro. The intracellular acrolein concentrations differ insignificantly: 0.61 microM for sensitive cells and 0.54 microM for resistant cells. Treatment with a physiological concentration of doxorubicin (0.5 microM) for 24 h at 37 degrees C increased acrolein levels by factors of 2.6 and 1.9 for MCF-7 and MCF-7/Adr cells, respectively. The differential enhancement observed is consistent with the lower levels of enzymes that neutralize oxidative stress in sensitive MCF-7 cells and overexpression of an active drug efflux pump P-170 glycoprotein in resistant MCF-7/Adr cells.

Acrolein↗