An assessment of the resolution limitation due to radiation-damage in x-ray diffraction microscopy.

X-ray diffraction microscopy (XDM) is a new form of x-ray imaging that is being practiced at several third-generation synchrotron-radiation x-ray facilities. Nine years have elapsed since the technique was first introduced and it has made rapid progress in demonstrating high-resolution three-dimensional imaging and promises few-nm resolution with much larger samples than can be imaged in the transmission electron microscope. Both life- and materials-science applications of XDM are intended, and it is expected that the principal limitation to resolution will be radiation damage for life science and the coherent power of available x-ray sources for material science. In this paper we address the question of the role of radiation damage. We use a statistical analysis based on the so-called "dose fractionation theorem" of Hegerl and Hoppe to calculate the dose needed to make an image of a single life-science sample by XDM with a given resolution. We find that for simply-shaped objects the needed dose scales with the inverse fourth power of the resolution and present experimental evidence to support this finding. To determine the maximum tolerable dose we have assembled a number of data taken from the literature plus some measurements of our own which cover ranges of resolution that are not well covered otherwise. The conclusion of this study is that, based on the natural contrast between protein and water and "Rose-criterion" image quality, one should be able to image a frozen-hydrated biological sample using XDM at a resolution of about 10 nm.

Atomic-resolution in situ transmission electron microscopy of a promoter of a heterogeneous catalyst.

Insight into the location, state, and function of a promoter in heterogeneous catalysis was obtained through atomic-resolution in situ transmission electron microscopy. In the most active ruthenium catalyst for ammonia synthesis known so far, the barium promoter is shown to be located in two different phases in the catalyst. The increased activity is suggested to be related to a two-dimensional barium-oxygen overlayer on the ruthenium crystals. The possibility for conducting such studies for other reactions could add substantially to our current understanding of heterogeneous catalysis. Heterogeneous catalysis plays an increasingly important role in environmental protection processes, in fuel upgrading, and in providing the majority of the chemical building blocks required by contemporary society. Most heterogeneous catalysts of industrial importance are multicomponent materials that are designed by trial-and-error experimentation. Application of even the most sophisticated physical-chemical characterization techniques is usually not sufficient to obtain a complete understanding of the structure of the active site, the reaction mechanism and kinetics, the structural dynamics, and the specific roles of all catalyst components.

Preparation and crystal structures of formato complexes of the [MIV3O4]4+ and [MIV3S4]4+ (M = Mo, W) clusters. Convenient precursors to the corresponding aqua complexes.

In the aqueous chemistry of molybdenum(IV) and tungsten(IV), trinuclear, incomplete cubane-like, oxo and sulfido clusters of the type [M3E4]4+ (M = Mo, W; E = O, S) play a central role. We here describe how formato complexes of all these cluster cores can be prepared in high yields by crystallization from methanol-water or ethanol-water mixtures. Since potassium and ammonium formate are very soluble in these alcohol-water mixtures, high formate concentrations could be accomplished in the solutions from which the corresponding salts of cluster formato complexes crystallized. The [Mo3O4]4+ compounds could be synthesized without requiring the use of noncomplexing acids in the process. Some [M3E4]4+ compounds were characterized by single-crystal structure determinations. [NH4]3.20[K]0.80[H3O][Mo3O4(HCO2)8][HCO2].H2O was triclinic, space group P1 (No. 2) with a = 11.011(2) A, b = 13.310(2) A, c = 9.993(1) A, alpha = 106.817(7) degrees, beta = 91.651(9) degrees, gamma = 88.340(9) degrees, and two formula units per cell. [K]6[W3S4(HCO2)9][HCO2].2.27H2O.0.73CH3OH was monoclinic, space group C2/m (No. 12) with a = 19.605(6) A, b = 14.458(7) A, c = 13.627(5) A, beta = 118.94(2) degrees, and four formula units per cell. Generally, the nine coordination sites of [M3E4]4+ were occupied either by a mixture of monodentate and mu 2-bridging formato ligands or by monodentate formato ligands only. By dissolution in noncomplexing strong acid, all the formato complexes immediately hydrolyzed to form [M3E4(H2O)9]4+ aqua complexes. This allows, for example, high concentrations of [Mo3S4(H2O)9]4+ in CF3SO3H to be obtained and these solutions to be used for the synthesis of bimetallic clusters containing the cubane-like motif Mo3M'S4.

Confined space synthesis. A novel route to nanosized zeolites.

Confined space synthesis is a novel method in zeolite synthesis. It involves crystallization of the zeolite inside the pore system of an inert mesoporous matrix. In this way it is possible to prepare nanosized zeolites with a controlled size distribution by proper choice of the inert matrix. Here, confined space synthesis was adopted to prepare nanosized ZSM-5, zeolite Beta, zeolite X, and zeolite A with tailored crystal size distributions using mesoporous carbon blacks as inert matrices. All zeolites were characterized by X-ray powder diffraction, transmission electron microscopy, and nitrogen adsorption/desorption prior to and after removal of the carbon matrix. ZSM-5 with Si/Al ratios of 50, 100, and infinity (silicalite-1) were synthesized with controlled average crystal sizes in the range 20-75 nm. Nanosized zeolite Beta (7-30 nm), zeolite X (22-60 nm), and zeolite A (25-37 nm) were prepared similarly. Removal of the carbon matrix by controlled combustion allows a convenient method for isolation of the pure and highly crystalline zeolites. Therefore, confined space synthesis appears to be an attractive method for preparation of zeolites with a controlled size distribution.

[Chronic thromboembolic pulmonary hypertension]. / Kronisk tromboembolisk pulmonal hypertension.

Acute pulmonary hypertension has a high mortality at the onset. Patients surviving the first phase will usually recanalize the pulmonary arteries through intrinsic thrombolytic mechanisms and medical treatment. However, in some cases there is insufficient resolution of the emboli with subsequent thrombotic and fibrotic reorganization, leading to a worsening of the pulmonary obstruction. In the open pulmonary arteries the disease may lead to hypertrophy of the media and intimal proliferation, thus leading to a further increase in the pulmonary vascular resistance. This again leads to hypertrophy of the right ventricle and ultimately to right-sided heart failure. Untreated, chronic thromboembolic pulmonary hypertension has a five-year mortality approaching 100%, but extensive pulmonary thrombendarterectomy using extracorporeal circulation and deep hypothermia has been shown to lower the pulmonary vascular resistance and thereby improve the prognosis significantly. Operative treatment can now be offered in Denmark, and the purpose of this review is to draw attention to the disease, its symptoms, diagnosis and the surgical treatment.

Premature atrial beat eliciting atrial fibrillation after coronary artery bypass grafting.

Of patients undergoing coronary artery bypass grafting 30% develop atrial fibrillation (AF) or flutter. To determine if AF is initiated from the right or left atrium, atrial electrograms were continuously recorded in patients undergoing this procedure. In addition, to study whether the prematurity index of premature atrial contractions (PACs) eliciting AF differs from PACs not provoking AF, the distribution of prematurity indices was evaluated from R-R interval analysis. The right and left atrial recording electrodes were first activated by the ectopic beat provoking AF in six and eight patients, respectively. The prematurity index of the PAC eliciting AF was located in the middle (in half of the patients) or to the left of the median distribution of prematurity indices. The variability in activation of the atrial electrodes suggests that the PAC provoking AF can have its origin in the right, the septal, or the left region of the atrium. The initiation of AF depends on the prematurity index of the PAC.

The effect of ketanserin upon postoperative blood pressure, cerebral blood flow and oxygen metabolism in patients subjected to craniotomy for cerebral tumours.

Hypertension and cerebral hyperperfusion are often seen in the immediate postoperative period after craniotomy for supratentorial tumours. This study was performed to evaluate the effect of ketanserin, given at the end of the peroperative period, upon cerebral blood flow (CBF), and cerebral metabolic rate of oxygen (CMRO2) before extubation. Mean arterial blood pressure (MABP), cerebral arterio-venous oxygen content difference (AVDO2), PaO2, and PaCO2 were repeatedly measured during the operation, and 180 minutes after extubation. Ten patients were included in this study. The results were compared to those from a recent study in which ten patients served as control. All patients were anaesthetized with thiopentone, fentanyl, nitrous oxide 67%, halothane 0.5% anesthesia. Ten patients were given ketanserin 10-20 mg (mean 18.5 mg) before extubation. There was no significant difference in CBF- and CMRO2 values between the two groups. During the period between closure of the dura and 5 minutes after extubation, an increase in MABP was observed in the control group (P < 0.05) but not in the ketanserin group. During the same period, a decrease in AVDO2 was observed in both groups (P < 0.05) and during the next 10 minutes an increase was observed. However, no difference in AVDO2 values between the two groups was found. These findings suggest that peroperative treatment with ketanserin reduces postoperative hypertension without influencing the cerebral blood flow or metabolism.

Hemodynamic predictors of atrial fibrillation or flutter after coronary artery bypass grafting.

The cumulated incidence of atrial fibrillation or flutter after coronary artery bypass grafting is 30%. The causes of these arrhythmias have not yet been sufficiently identified. We therefore undertook the present study to analyze the possible association of hemodynamic function during the various phases of coronary artery bypass grafting and the later development of atrial fibrillation/flutter. Hemodynamic function was measured with a pulmonary artery catheter in 120 consecutive patients undergoing elective coronary artery bypass surgery. Thirty-five (29%) of the patients developed atrial fibrillation/flutter. Logistic regression analysis identified independent predictors of atrial fibrillation/flutter. After induction of general anesthesia, the relative risk (95% confidence interval) of older age was 1.09/year (1.03-1.16), and the reduction in relative risk by an increase in left ventricular stroke work was 0.96/gm (0.93-0.99). After weaning from the extracorporeal circulation the independent significant predictors were age, relative risk 1.07/year (1.01-1.13), and increased central venous pressure, relative risk 1.12/mm Hg (1.00-1.26). At the time of admission to the intensive care unit, the relative risk of age was 1.10/year (1.03-1.18), and the relative risk of an increased central venous pressure was 1.26/mm Hg (1.06-1.49). However, the best prediction model (prediction after induction of general anesthesia) only provided a median predicted probability of atrial fibrillation/flutter of 0.37 for the patients who had atrial fibrillation/flutter, and a median predicted probability of atrial fibrillation/flutter of 0.20 for the patients without these arrhythmias. We identified possible hemodynamic predictors of atrial fibrillation/flutter after coronary bypass surgery, but the use of a risk stratification for development of atrial fibrillation/flutter based on hemodynamic function cannot be recommended.

Atrial ectopic activity and atrial fibrillation/flutter after coronary artery bypass surgery. A case-base study controlling for confounding from age, beta-blocker treatment, and time distance from operation.

To evaluate the impact of ectopic atrial activity and cardiac autonomic function for development of atrial fibrillation or flutter we studied 128 consecutive patients undergoing elective coronary artery bypass grafting. The patients were Holter monitored during a 96-h postoperative period. Autonomic balance was estimated by heart rate variability measurement. Thirty-eight (30%) patients developed sustained atrial fibrillation or flutter. Holter recordings were analyzed in a case-base design matching for age, beta-blocker treatment, and time elapsed after the operation. The number of supraventricular ectopic beats/h was increased (P < 0.01) in the case group during each of the last 7 h before onset of atrial fibrillation or flutter. Episodes of supraventricular tachycardia 62% vs. 26%; cases vs. controls (P = 0.007), episodes of non-sustained atrial fibrillation 29% vs. 0% (P = 0.0009), and episodes of non-sustained atrial flutter 15% vs. 0% (P = 0.05) were significant predictors of atrial fibrillation or flutter. Mean heart rate/h was increased in each of the 24 h preceding the arrhythmia. However, indexes of autonomic heart function did not differ significantly between groups. Patients developing atrial fibrillation or flutter after coronary artery bypass surgery present 'warning' atrial arrhythmias: numerous supraventricular ectopic beats, paroxysmal supraventricular tachycardia, and episodes of nonsustained atrial fibrillation and flutter.

Low vagal tone and supraventricular ectopic activity predict atrial fibrillation and flutter after coronary artery bypass grafting.

To investigate the impact of pre-operative autonomic balance and atrial ectopic activity on the risk of atrial fibrillation or flutter after aorto-coronary artery bypass surgery 24-h Holter monitoring was analysed in 102 patients before coronary artery bypass grafting. Index for vagal tone was calculated as % successive RR interval differences > 6%. Twenty-nine (28%) of the 102 patients developed atrial fibrillation or flutter. Independent predictors (90% confidence interval) of postoperative atrial fibrillation or flutter were identified by logistic regression analysis: the independent predictors were older age, relative risk 1.07.year-1 (1.02-1.12), vagal index < 10%, relative risk 4.50 (1.40-14.5), > or = 10 ectopic supraventricular beats . 24 h-1, relative risk 3.03 (1.05-8.72), and one or more events of non-sustained supraventricular tachycardia, relative risk 3.02 (1.11-8.22). Thus, age of the patient, attenuated pre-operative cardiac vagal modulation, ectopic supraventricular beats, and paroxysmal non-sustained supraventricular tachycardia are independent risk factors for the development of atrial fibrillation or flutter after coronary artery bypass surgery.