Out-of-equilibrium dynamics driven by photoinduced charge transfer in CsCoFe Prussian blue analogue nanocrystals.

In this paper we study the out-of-equilibrium dynamics associated with photoinduced charge-transfer (CT) in cyanide-bridged Co-Fe Prussian blue analogue nanocrystals. In these coordination networks, the structural trapping of the photoinduced CT polaron involves local electronic and structural reorganizations. Femtosecond X-ray and optical absorption spectroscopies show that the local structural trapping process occurs on similar timescale for particles with 11 nm and 70 nm sizes. The local photoinduced spin transition, elongating the Co-N bonds and driving the CoIIIFeII → CoIIFeIII CT, activates coherent lattice torsion modes. The elastic deformation waves, launched by these bond elongations, drive macroscopic volume expansion and breathing of the particles. The timescale of this macroscopic deformation depends strongly on the size of the particle, which is more evidence of the multiscale nature of photoinduced phenomena in molecular materials.

Strain wave pathway to semiconductor-to-metal transition revealed by time-resolved X-ray powder diffraction.

One of the main challenges in ultrafast material science is to trigger phase transitions with short pulses of light. Here we show how strain waves, launched by electronic and structural precursor phenomena, determine a coherent macroscopic transformation pathway for the semiconducting-to-metal transition in bistable Ti3O5 nanocrystals. Employing femtosecond powder X-ray diffraction, we measure the lattice deformation in the phase transition as a function of time. We monitor the early intra-cell distortion around the light absorbing metal dimer and the long range deformations governed by acoustic waves propagating from the laser-exposed Ti3O5 surface. We developed a simplified elastic model demonstrating that picosecond switching in nanocrystals happens concomitantly with the propagating acoustic wavefront, several decades faster than thermal processes governed by heat diffusion.

1 kHz fixed-target serial crystallography using a multilayer monochromator and an integrating pixel detector.

Reliable sample delivery and efficient use of limited beam time have remained bottlenecks for serial crystallography (SX). Using a high-intensity polychromatic X-ray beam in combination with a newly developed charge-integrating JUNGFRAU detector, we have applied the method of fixed-target SX to collect data at a rate of 1 kHz at a synchrotron-radiation facility. According to our data analysis for the given experimental conditions, only about 3 000 diffraction patterns are required for a high-quality diffraction dataset. With indexing rates of up to 25%, recording of such a dataset takes less than 30 s.

Observing heme doming in myoglobin with femtosecond X-ray absorption spectroscopy.

We report time-resolved X-ray absorption measurements after photolysis of carbonmonoxy myoglobin performed at the LCLS X-ray free electron laser with nearly 100 fs (FWHM) time resolution. Data at the Fe K-edge reveal that the photoinduced structural changes at the heme occur in two steps, with a faster (∼70 fs) relaxation preceding a slower (∼400 fs) one. We tentatively attribute the first relaxation to a structural rearrangement induced by photolysis involving essentially only the heme chromophore and the second relaxation to a residual Fe motion out of the heme plane that is coupled to the displacement of myoglobin F-helix.

Unveiling the timescale of the R-T transition in human hemoglobin.

Time-resolved wide-angle X-ray scattering, a recently developed technique allowing to probe global structural changes of proteins in solution, was used to investigate the kinetics of R-T quaternary transition in human hemoglobin and to systematically compare it to that obtained with time-resolved optical spectroscopy under nearly identical experimental conditions. Our data reveal that the main structural rearrangement associated with the R-T transition takes place approximately 2 mus after the photolysis of hemoglobin at room temperature and neutral pH. This finding suggests that the 20-mus step observed with time-resolved optical spectroscopy corresponds to a small and localized structural change.

Structure and dynamics of water confined in silica hydrogels: X-ray scattering and dielectric spectroscopy studies.

We have used a sol-gel technique to obtain optically transparent hydrogels in which water is confined within a 3D silica matrix. In this work we report X-ray scattering and dielectric spectroscopy measurements on samples having different aging times and compare them with previously obtained results with near-infrared (NIR) absorption spectroscopy. X-ray scattering at room temperature enables to characterize the structure and size of the matrix pores and the non-uniform distribution of water inside the hydrogel. Broad band dielectric spectroscopy in the temperature range 130-280 K enables to study water dynamics. In aged hydrogels two relaxations are clearly evident and show characteristic temperature dependence. The faster relaxation has an Arrhenius behavior in the whole temperature range investigated with an activation enthalpy of approximately 50 kJ/mol; it is attributed to water molecules strongly interacting with the silica matrix. The slower relaxation has a markedly non-Arrhenius behavior which can be fitted with a Vogel-Fulcher-Tamman (VFT) relation with critical temperature of approximately 100 K and activation enthalpies of 35 and 95 kJ/mol at 300 and 170 K respectively; it is attributed to water molecules within the pores that do not interact strongly with the matrix and behave collectively. The VFT temperature dependence of the dielectric relaxation time suggests that this water does not crystallize, in agreement with previous results from NIR spectroscopy.

Symptomatic improvement after transmyocardial laser revascularization: how long does it last?

BACKGROUND: The aim of this study was to determine whether short-term clinical improvement after isolated transmyocardial holmium laser revascularization (TMLR) in patients with coronary artery disease not amenable to traditional treatment is maintained through a longer follow-up. METHODS: Between November 1995 and June 1999 34 patients underwent TMLR (mean age, 67+/-7 years); previous revascularization procedures had been performed in 76%. Preoperatively, mean angina class was 3.6+/-0.5 in 12 patients with unstable angina; mean left ventricular ejection fraction was 47%+/-9%. RESULTS: There was 1 early death due to low cardiac output. Mean duration of TMLR and of the entire operation was 25+/-12 minutes and 125+/-43 minutes, respectively. There were no major postoperative complications; mean hospital stay was 8+/-4 days. There were 8 late deaths caused by stroke (2 patients), cardiac failure (1 patient), and myocardial infarction (5 patients). Follow-up of current survivors ranges from 4 to 48 months (mean, 32+/-12 months). At 1-year follow-up mean angina class was 1.8+/-0.8; but at a later follow-up (mean, 35+/-10 months) it significantly increased to 2.2+/-0.7 (p = 0.005). Three-year actuarial survival was 76%+/-8% and freedom from cardiac events 44%+/-10%. CONCLUSIONS: Our results show that after initial clinical improvement many patients experience return of angina or cardiac events; this questions the long-term symptomatic benefit of TMLR.

[Myocardial revascularization with arterial conduits: comparison of bilateral internal mammary artery and single internal mammary artery]. / Rivascolarizzazione miocardica con condotti arteriosi: confronto tra arteria mammaria interna bilaterale e arteria mammaria interna singola.

The use of bilateral internal mammary artery (BIMA) grafting for myocardial revascularization has been demonstrated to provide long-term benefits compared to revascularization using single left internal mammary artery (SIMA) and venous conduits. However, it is still controversial whether the use of BIMA is associated with a higher hospital mortality and morbidity. The present study retrospectively evaluated the possible advantages related to the use of BIMA at 3-year follow-up and whether the presence of operative risk factors in patients with BIMA could limit the application of the procedure in myocardial revascularization. We compared two groups of 100 patients matched for preoperative clinical characteristics, who underwent myocardial revascularization on the left coronary system with BIMA (93 males and 7 females, mean age 59 +/- 4 years) or with SIMA and venous conduits (86 males and 14 females, mean age 63 +/- 6 years). Hospital mortality rate was 2% in both groups, the use of BIMA being not a significant risk factor for hospital mortality and morbidity. The mean follow-up was 36 +/- 6 months for the BIMA group and 40 +/- 10 months for the SIMA group. At 3 years, there was no significant differences in the actuarial freedom from cardiac death (96 +/- 2% for BIMA vs 94 +/- 2% for SIMA patients), myocardial infarction (98 +/- 2 vs 97 +/- 2%), angina (93 +/- 2 vs 91 +/- 2%), symptomatic heart failure (92 +/- 3 vs 92 +/- 2%), coronary angioplasty/reoperation (96 +/- 2 vs 97 +/- 2% ), and total cardiac events (80 +/- 4 vs 76 +/- 4%). BIMA grafting was not an independent predictor of late cardiac events. In 66 patients who underwent a late angiographic or echo-Doppler study, the patency rate was 100% for the left mammary artery, 94% for the right mammary artery and 69% for venous conduits. In conclusion, myocardial revascularization with BIMA in situ is associated with low hospital mortality and morbidity, good clinical outcome and excellent patency rate at 3 years, with apparently no significant differences when compared to the use of SIMA and venous conduits. The low hospital mortality and morbidity and the satisfactory medium-term results in our opinion justify a more extensive use of BIMA in myocardial revascularization.

Aortic valve replacement for quadricuspid aortic valve incompetence.

Quadricuspid aortic valve is an uncommon cause of aortic regurgitation. We report two patients who underwent aortic valve replacement because of severe aortic incompetence; the presence of a quadricuspid aortic valve was an accidental surgical finding. In one patient the aortic valve comprised two equal-sized larger cusps and two equal-sized smaller cusps, while in the other it comprised three cusps of similar size and a small accessory cusp between the right and non-coronary cusps. This report confirms the rarity of the disease and the fact that patients with quadricuspid aortic valves characterized by cusps of different sizes are more prone to develop progressive aortic incompetence because of unequal distribution of stresses on the valve. Therefore, such patients should undergo periodic, life-time echocardiographic assessment once this malformation is detected.

[Myocardial revascularization with both internal mammary arteries]. / Rivascolarizzazione miocardica con entrambe le arterie mammarie interne.

BACKGROUND: The excellent results obtained with the use of the left internal mammary artery (IMA) for myocardial revascularization have led to the simultaneous use of other arterial conduits, particularly the right IMA. METHODS: The present study includes the first 100 consecutive patients with ischemic heart disease who underwent myocardial revascularization with in situ bilateral IMA grafted to branches of the left coronary artery, performed at our center. Ninety-six (96%) were males and four (4%) were females, with a mean age of 58 +/- 8 years (range, 35-75 years). The main indication for myocardial revascularization was angina in 83 patients (83%) and heart failure in 17 (17%). Seventy patients had three-vessel disease. RESULTS: Hospital mortality was 1%, with one death due to left ventricular failure. Three patients had perioperative myocardial infarction, six experienced ventricular arrhythmia, two had acute renal failure and nine respiratory insufficiency. Dehiscence of the sternal wound occurred in four patients, evolving in mediastinitis in one. All discharged patients were checked after 26 +/- 6 months (range, 12-38 months). There were two deaths, one because of cardiac failure and one sudden death, with a two-year survival rate of 97 +/- 2%. Five patients (5%) required hospitalization because of angina, and the angiographic study showed stenosis/occlusion of one or both IMAs in four cases. Thirty-five (38%) of the remaining patients underwent a coronarographic (25 patients) or transthoracic Doppler study (10 patients) to evaluate patency of the IMAs. The patency index was 100% for the left IMA and 94% for the right IMA. CONCLUSIONS: Myocardial revascularization with bilateral IMA in situ can be performed with low hospital mortality and morbidity. Sternal dehiscence is the worst complication and appears to be more frequent in diabetic and elderly patients. Mid-term results are satisfactory, with a good survival rate and freedom from major cardiac events. However, a longer follow-up is necessary to better appreciate the advantages of myocardial revascualarization with in situ bilateral IMAs.

Surgical angioplasty for isolated coronary ostial stenosis.

Patch angioplasty has been reported as a suitable surgical option for patients with isolated coronary ostial stenosis, but controversy still exists concerning its effectiveness. We report the cases of 4 additional patients in whom this procedure was performed, including that of a patient with bilateral ostial stenosis; and we review the literature pertaining to bilateral ostial stenosis. Four patients, 3 with isolated stenosis of the left main coronary ostium and 1 with bilateral ostial stenosis, had direct surgical ostioplasty from January through November 1994. We considered the cause of ostial stenosis to be aortitis (of suspected syphilitic origin) in 1 patient, atherosclerotic plaque in 2 patients, and a fibrous membrane in the 4th. Ostioplasty was performed with a patch of autologous pericardium in 3 patients (fresh pericardium in 2 and glutaraldehyde-fixed in 1) and a patch of saphenous vein in 1. There were no operative deaths. One patient underwent successful reoperation for left main coronary artery restenosis after 3 months. All other patients are asymptomatic at 16, 18, and 24 months postoperatively. In the patient who underwent bilateral ostioplasty, coronary angiography showed patent ostia at 1 year. Surgical ostioplasty should be considered in the treatment of patients who have isolated ostial stenosis but no distal coronary disease. Careful patient selection seems to be a prerequisite for surgical success.

Entrapment of a coronary stent in the left main trunk: an easy method for surgical removal.

The use of an intracoronary stent is usually indicated after the acute closure of a coronary vessel following percutaneous transluminal coronary angioplasty. Plaque disruption and dissection, with subsequent spasm and thrombosis, can be contained by this device. In the reported case, acute closure of the left anterior descending coronary artery and of a diagonal branch were caused by the entrapment of a stent proximal to the coronary lesion that it was supposed to treat. An emergency coronary artery bypass graft procedure was required together with removal of the device because of the impending closure of the left main trunk (the site of the stent entrapment). This was successfully performed by means of an easy method, which did not require direct incision of the left main trunk. The less invasive procedure described simplified the operation and probably played an important role in its favorable outcome.

Survival despite almost complete occlusion by chronic thrombosis of a Björk-Shiley mitral prosthesis.

We report a patient who was successfully reoperated because of almost complete thrombosis of a Björk-Shiley tilting disc mitral prosthesis. Considering the usually acute presentation and the frequently catastrophic consequences of most similar cases in the literature, the unusual feature of this case is that the patient survived until reoperation with minimal symptoms despite almost total prosthetic occlusion by a chronic thrombus.

Role of dipyridamole-echocardiography test in the evaluation of coronary reserve after coronary artery bypass grafting.

The object of this study was to assess the usefulness of the dipyridamole-echocardiography test in the early evaluation of coronary artery bypass grafting, when the use of an exercise stress test is precluded. We studied 39 consecutive patients (37 men and two women, mean age 57.3 years) referred to our institute for elective coronary artery bypass. Five patients had single, 12 patients double, 20 patients triple vessel disease, and two had left main stem disease. Nineteen left internal mammary artery grafts, 20 sequential grafts, and 39 single vein grafts were performed. All the patients were subjected to the test before (time range 1 to 3 days) and after (time range 6 to 10 days) the operation in the absence of therapy. Dipyridamole was administered intravenously 0.56 mg/kg over 4 minutes (low dose); if no effect was apparent, an additional 0.28 mg/kg over 2 minutes (high dose) was given. During the test, blood pressure and a twelve-lead electrocardiogram were monitored. An arbitrary wall motion score was derived by dividing the left ventricle into six regions and grading from 0 to 3-normokinetic, hypokinetic, akinetic, and dyskinetic zones. Preoperatively the test was positive in 38 patients as evidenced by wall motion abnormalities (36 patients had electrocardiographic changes) and in one patient by electrocardiographic changes and chest pain; 22 tests were positive after the low dose and 17 after the high dose. Angina was present in 33 patients. Mean wall motion score was 1.64 per patient in the basal condition and 4.03 per patient after the test (p less than 0.001). After coronary bypass in three patients the test was positive at the same dosage that was used preoperatively, as shown by wall motion abnormalities (in two patients by electrocardiographic changes, as well). Four patients had symptoms. Furthermore, at 6 months' follow-up, a treadmill stress test performed in these three patients was positive for ischemia and angina. The wall motion score was 1.25 per patient in the basal condition and 1.53 per patient after the test (no significant difference). When the preoperative wall motion score obtained after dipyridamole echocardiography was compared with the postoperative score, a statistically significant difference was seen: 4.03 per patient versus 1.53 per patient (p less than 001). In eight patients we observed an improvement of basal myocardial contractility after the operation, which indicates the reversibility of wall motion abnormalities observed before coronary bypass. In conclusion our data show that the dipyridamole-echocardiography test is a suitable method for the early assessment of bypass grafting when other methods, exercise dependent, are not indicated.(ABSTRACT TRUNCATED AT 400 WORDS)

Early assessment of coronary reserve after bypass surgery by dipyridamole transesophageal echocardiographic stress test.

The evaluation of coronary reserve within a few hours of aortocoronary bypass surgery could be of extreme utility for the follow-up or therapeutical management of these patients. In 11 men patients who underwent aortocoronary bypass surgery, a dipyridamole echocardiography stress test was carried out before (1 to 3 days), early after (68 to 130 minutes), and 1 week after surgery. The first and third tests were performed using a standard transthoracic approach, while the second was performed by a transesophageal approach. Dipyridamole was administered intravenously at a dose of 0.56 mg/kg body weight (low dose) and eventually adding 0.28 mg/kg body weight (high dose), always in the absence of antiischemic therapy. An arbitrary wall motion score (0 = eukinesia; 1 = hypokinesia; 2 = akinesia; 3 = dyskinesia) was assigned to the seven different myocardial regions in which the left ventricle was divided in order to have a semiquantitative score. Under basal conditions wall motion score per patient in the three series of tests did not change significantly (1.6, 1.4, and 1.5, respectively), while the mean score during dipyridamole administration showed significant differences (3.6, 1.9, and 1.9, respectively), indicative of the results obtained by surgical repair. The test, positive in all patients before surgery, showed wall motion abnormalities and ischemic ECG changes in two patients immediately after surgery by the transesophageal approach. One patient who had a normal basal contraction pattern and an abnormal response after the test developed in the following days a perioperative myocardial infarction, while a second patient in the follow-up period developed low-level effort angina.(ABSTRACT TRUNCATED AT 250 WORDS)

Evaluation of in vivo morphological results of balloon mitral valvotomy.

Percutaneous valvotomy is now more often considered for the treatment of mitral stenosis in poor risk patients. The aim of this study was the evaluation of the morphological changes produced by a similar procedure on the mitral valves of nine nonconsecutive patients undergoing a mitral valve replacement because of calcific isolated or prevalent mitral stenosis. The mitral valve was dilated through the left atriotomy before the valve excision with the same balloon catheter used in the percutaneous procedure. The pathological condition of the valve had been studied before dilatation by means of doppler echocardiography, cardiac catheterization and a visual examination performed by the surgeon before insertion of the balloon. At that time, the orifice area was measured with a Hegar dilator. A new measurement was performed after one or two dilatations performed at a balloon pressure of 2.7 atm. After excision, the valve was examined, photographed and X-rays were taken for evaluation of valve calcification. The pre-dilatation mean mitral valve orifice area was 1.3 +/- 0.4 cm2 and after the procedure was 2.8 +/- 0.3 cm2. In only one patient did the orifice area, originally 2.4 cm2, not increase. There was only one fused and calcified commissure, the other was normal. Before dilatation, the two commissures were fused in 17/18 cases and in 9/18, calcified. After dilatation, 5/17 commissures were completely open (not all were calcified), 10/17 incompletely opened and 2/17 remained fused (one in the above-mentioned patient).(ABSTRACT TRUNCATED AT 250 WORDS)