Diaryliodonium salts as hydrosilylation initiators for the surface functionalization of silicon nanomaterials and their collaborative effect as ring opening polymerization initiators.

Diaryliodonium salts were found to initiate hydrosilylation reactions on the surface of silicon nanosheets as well as silicon nanocrystals of different sizes. A variety of different functional substrates can be used to stabilize the surface of the photoluminescent materials. Additionally, the combination of hydride terminated silicon nanomaterials with diaryliodonium salts was found to initiate cationic ring opening polymerization, demonstrating the potential of silicon based nanomaterials as coinitiators and enabling a mild, straightforward reaction method.

CO2 to methanol conversion using hydride terminated porous silicon nanoparticles.

Porous silicon nanoparticles (Si-NPs) prepared via magnesiothermic reduction were used to convert carbon dioxide (CO2) into methanol. The hydride surface of the silicon nanoparticles acted as a CO2 reducing reagent without any catalyst at temperatures above 100 °C. The Si nanoparticles were reused up to four times without significant loss in methanol yields. The reduction process was monitored using in situ FT-IR and the materials were characterized using SEM, TEM, NMR, XPS, and powder XRD techniques. The influence of reaction temperature, pressure, and Si-NP concentration on CO2 reduction were also investigated. Finally, Si particles produced directly from sand were used to convert CO2 to methanol.

Silicon 1s near edge X-ray absorption fine structure spectroscopy of functionalized silicon nanocrystals.

Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3-100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed silicon nanocrystals that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.

Uptake and depuration of gold nanoparticles in Daphnia magna.

This study presents a series of short-term studies (total duration 48 h) of uptake and depuration of engineered nanoparticles (ENP) in neonate Daphnia magna. Gold nanoparticles (Au NP) were used to study the influence of size, stabilizing agent and feeding on uptake and depuration kinetics and animal body burdens. 10 and 30 nm Au NP with different stabilizing agents [citrate (CIT) and mercaptoundecanoic acid (MUDA)] were tested in concentrations around 0.5 mg Au/L. Fast initial uptake was observed for all studied Au NP, with CIT stabilized Au NP showing similar rates independent of size and MUDA showing increased uptake for the smaller Au NP (MUDA 10 nm > CIT 10 nm, 30 nm > MUDA 30 nm). However, upon transfer to clean media no clear trend on depuration rates was found in terms of stabilizing agent or size. Independent of stabilizing agent, 10 nm Au NP resulted in higher residual whole-animal body burdens after 24 h depuration than 30 nm Au NP with residual body burdens about one order of magnitude higher of animals exposed to 10 nm Au NP. The presence of food (P. subcapitata) did not significantly affect the body burden after 24 h of exposure, but depuration was increased. While food addition is not necessary to ensure D. magna survival in the presented short-term test design, the influence of food on uptake and depuration kinetics is essential to consider in long term studies of ENP where food addition is necessary. This study demonstrates the feasibility of a short-term test design to assess the uptake and depuration of ENP in D. magna. The findings underlines that the assumptions behind the traditional way of quantifying bioconcentration are not fulfilled when ENPs are studied.

Cholesterol efflux capacity, carotid atherosclerosis, and cerebrovascular symptomatology.

OBJECTIVE: To investigate the association of cholesterol efflux capacity with carotid atherosclerosis and cerebrovascular disease. APPROACH AND RESULTS: Patients with high-grade carotid stenosis (n=154) were recruited from Vascular Surgery clinics and 9 healthy controls from the McGill University Health Network, Montreal, Canada. Cerebrovascular symptomatology history was obtained. Stenosis was assessed by carotid ultrasound. Fasting blood samples were collected and depleted of apolipoprotein B particles by polyethylene glycol precipitation from serum. Cholesterol efflux was determined by incubating apolipoprotein B-depleted serum in cAMP-stimulated J774 cells for 6 hours. Carotid specimens were classified by 2 vascular pathologists using the American Heart Association atheromatous plaque classification. Differences in efflux were assessed according to (1) stenosis, (2) American Heart Association classification, and (3) cerebrovascular symptomatology. Normalized efflux was significantly lower in patients with carotid atherosclerosis compared with controls (0.97±0.16 versus 1.5±0.46; P<0.0001). Efflux was inversely associated with stenosis; the odds ratio for 80% to 99% versus 50% to 79% stenosis of tertile 1 (lowest) versus tertile 3 (highest) of efflux was 3.78 (95% confidence interval, 1.18-12.06) after adjusting for age, sex, low-density lipoprotein, and high-density lipoprotein. There were significant differences in cholesterol efflux between American Heart Association fibroatheroma (Va, 0.91±0.13), mainly calcific (Vb, 0.97±0.15), and mainly fibrotic (Vc, 1.03±0.21; P=0.05). There were no significant differences in efflux according to symptomatology. CONCLUSIONS: Cholesterol efflux capacity is inversely associated with increasing carotid stenosis and is associated with more advanced carotid plaque morphology, suggesting that cholesterol efflux capacity may be a biomarker for severity of carotid atherosclerotic burden. Whether therapies targeting high-density lipoprotein quality could be useful for stabilizing carotid atherosclerosis needs to be assessed.

Doping and quantum confinement effects in single Si nanocrystals observed by scanning tunneling spectroscopy.

We have applied scanning tunneling spectroscopy in studies of the electronic level structure of surface-functionalized colloidal Si nanocrystals (Si-NCs) as a function of their size for various capping ligands. The energy gaps extracted from the tunneling spectra increase with decreasing NC size, manifesting the effect of quantum confinement. This is consistent with the blueshift revealed by photoluminescence (PL) from dodecene functionalized Si-NCs. The tunneling spectra measured on NCs functionalized with NH4Br or allylamine show band-edge shifts toward higher energies, akin to p-type doping. This behavior can be accounted for by the combined contributions of the ligands' dipole moments and charge transfer between a Si-NC and its surface groups. Concomitantly, size-independent PL spectra, which cannot be associated with NC band gap variations, were observed for the latter Si-NCs.

Refractometric sensing with fluorescent-core microcapillaries.

Capillaries present a promising structure for microfluidic refractive index sensors. We demonstrate a capillary-type fluorescent core microcavity sensor based on whispering gallery mode (WGM) resonances. The device consists of a microcapillary having a layer of fluorescent silicon quantum dots (QDs) coated on the channel surface. The high effective index of the QD layer confines the electric field near the capillary channel and causes the development of WGM resonances in the fluorescence spectrum. Solutions consisting of sucrose dissolved in water were pumped through the capillary while the fluorescence WGMs were measured with a spectrometer. The device showed a refractometric sensitivity of 9.8 nm/RIU (up to 13.8 nm/RIU for higher solution refractive index) and a maximum detection limit of ~7.2 x 10(-3) RIU. Modeling the field inside the capillary structure, which is analogous to a layered hollow ring resonator, shows that sensitivities as high as 100 nm/RIU and detection limits as low as ~10(-5) RIU may be achievable by optimizing the QD film thickness.

Silicon nanocrystals on bottle resonators: mode structure, loss mechanisms and emission dynamics.

Bottle resonators can support high Q-factor whispering gallery modes (WGMs) and demonstrate a rich mode spectrum. Resonators were fabricated using a fiber tapering apparatus and were coated with a thin, smooth layer of luminescent silicon nanocrystals. The photoluminescence spectrum showed WGM peaks with Q-factors near 2,500; however, evanescent measurements showed that these modes are a composite of many modes with Q-factors exceeding 106, the highest yet seen for a silicon-nanocrystalcoated microresonators. The mode structure showed strong polarization and sensitivity to position within the bottle resonator. An analysis of loss mechanisms establishes surface roughness scattering as the limiting factor in these nanocrystal-coated bottle resonators in the absence of excited carriers.

Whipple's disease with constrictive pericarditis: a rare disease with a rare presentation.

Whipple's disease is a multisystem disease that can affect the heart with predominantly endocardial and pericardial involvement and, less often, myocardial inflammation. Previously diagnosed at autopsy, cardiac involvement in Whipple's disease is being recognized clinically more often. A 58-year-old man with Whipple's-related constrictive pericarditis, arthralgias and lymphadenopathy is described. He underwent antibiotic treatment and pericardiectomy with improvement in his clinical state.

Assessment of cyclosporine pharmacokinetic parameters to facilitate conversion from C0 to C2 monitoring in heart transplant recipients.

BACKGROUND: Cyclosporine (CsA) 2-hour postdose (C2) monitoring is recommended to assess CsA exposure and predict clinical outcomes among heart transplant recipients. We correlated pharmacokinetic parameters and clinical outcomes in stable long-term heart transplant recipients monitored with C0 to develop an algorithm to convert patients from C0 to C2 monitoring. METHODS: Paired CsA C0-C2 measurements and serum creatinine levels were obtained from 35 heart transplant recipients more than 2 years posttransplantation (mean 8.8+/-4.7 years). RESULTS: The mean CsA dose and C0, C2, and C0/C2 ratio were 85+/-23 mg/12 hours, 123+/-41 ng/mL, 572+/-274 ng/mL and 4.8+/-2.1, respectively. C0 correlated weakly with C2 (r=.42, P=.011). The CsA dose correlated better with C2 (r=.58; P<.001) than with C0 (r=.37; P=.026). A good correlation was noted between C2 and the C2/C0 ratio (r=.73; P<.001), but none between C0 and the C2/C0 ratio. A borderline significant inverse correlation was noted between C0 and the worst endomyocardial biopsy score (r=-.34; P=.045), whereas none was noted with C2. Serum creatinine level did not correlate with either C2 or C0. Among patients with C0 within our target of 100 to 150 ug/L, six had C2 above 300 to 600 ug/L as suggested by the literature. CONCLUSIONS: In long-term heart transplant recipients, we could not identify a single pharmacokinetic parameter that could be used to develop an algorithm to convert from C0 to C2 monitoring; however, C2 may be better than C0 for identifying patients at risk of overexposure to CsA.

An approach to endomyocardial biopsy interpretation.

The endomyocardial biopsy (EMB) remains the gold standard mode of investigation for diagnosing many primary and secondary cardiac conditions. Through a percutaneous and transvenous route, tissue fragments are generally procured from the right ventricular septum, with very few complications. Widespread use of EMB followed the development of heart transplantation as a means to follow allograft rejection. It has since been useful in helping to diagnose conditions affecting the heart, including cardiomyopathies, myocarditis, infiltrative lesions, arrhythmias, and drug toxicities. The procedure has also been used as a research tool to investigate the natural history of disease and the cardiotoxicity of new medications. This review presents an approach to the evaluation of the EMB, which is particularly directed towards those who may be asked to interpret such biopsies, but are not dedicated cardiovascular pathologists. Through a systematic evaluation of the endocardium, myocardium, interstitium, and intramural vessels, in the context of a complete clinical history, enough information can be deduced to diagnose or exclude specific conditions of clinical value.

In vivo and in vitro examination of the functional significances of novel lamin gene mutations in heart failure patients.

CONTEXT: Lamin A/C (LMNA) gene variations have been reported in more than one third of genotyped families with dilated cardiomyopathy (DCM). However, the relationship between LMNA mutation and the development of DCM is poorly understood. METHODS AND RESULTS: We found that end stage DCM patients carrying LMNA mutations displayed either dramatic ultrastructural changes of the cardiomyocyte nucleus (D192G) or nonspecific changes (R541S). Overexpression of the D192G lamin C dramatically increased the size of intranuclear speckles and reduced their number. This phenotype was only partially reversed by coexpression of the D192G and wild type lamin C. Moreover, the D192G mutation precludes insertion of lamin C into the nuclear envelope when co-transfected with the D192G lamin A. By contrast, the R541S phenotype was entirely reversed by coexpression of the R541S and wild type lamin C. As lamin speckle size is known to be correlated with regulation of transcription, we assessed the SUMO1 distribution pattern in the presence of mutated lamin C and showed that D192G lamin C expression totally disrupts the SUMO1 pattern. CONCLUSION: Our in vivo and in vitro results question the relationship of causality between LMNA mutations and the development of heart failure in some DCM patients and therefore, the reliability of genetic counselling. However, LMNA mutations producing speckles result not only in nuclear envelope structural damage, but may also lead to the dysregulation of cellular functions controlled by sumoylation, such as transcription, chromosome organisation, and nuclear trafficking.

Endometrioid adenocarcinoma of the uterus with a minimal deviation invasive pattern.

AIMS: Minimal deviation adenocarcinoma of endometrioid type is a rare pathological entity. We describe a variant of typical endometrioid adenocarcinoma associated with minimal deviation adenocarcinoma of endometrioid type. METHODS AND RESULTS: One 'pilot' case of minimal deviation adenocarcinoma of endometrioid type associated with typical endometrioid adenocarcinoma was encountered at our institution in 2001. A second case of same type was received in consultation. We reviewed 168 consecutive hysterectomy specimens diagnosed with 'endometrioid adenocarcinoma' specifically to identify areas of minimal deviation adenocarcinoma of endometrioid type. Immunohistochemistry was done with the following antibodies: MIB1, p53, oestrogen receptor (ER), progesterone receptor (PR), cytokeratin 7 (CK7), cytokeratin 20 (CK20), carcinoembryonic antigen (CEA), and vimentin (VIM). Four additional cases of minimal deviation adenocarcinoma of endometrioid type were identified. All six cases of minimal deviation adenocarcinoma of endometrioid type were associated with superficial endometrioid adenocarcinoma. In two cases with a large amount of minimal deviation adenocarcinoma of endometrioid type, the cervix was involved. The immunoprofile of two representative cases was ER+, PR+, CK7+, CK20-, CEA-, VIM+. MIB1 immunostaining of four cases revealed little proliferative activity of the minimal deviation adenocarcinoma of endometrioid type glandular cells (0-1%) compared with the associated 'typical' endometrioid adenocarcinoma (20-30%). The same four cases showed no p53 immunostaining in minimal deviation adenocarcinoma of endometrioid type compared with a range of positive staining in the associated endometrioid adenocarcinoma. CONCLUSIONS: Minimal deviation adenocarcinoma of endometrioid type more often develops as a result of differentiation from typical endometrioid adenocarcinoma than de novo. Due to its deceptively benign microscopic appearance, minimal deviation adenocarcinoma of endometrioid type may be overlooked and may lead to incorrect assessment of tumour depth and pathological stage. There was a tendency for tumour with a large amount of minimal deviation adenocarcinoma of endometrioid type to invade the cervix.

Residual sinus venosus atrial septal defect after surgical closure of atrial septal defect.

We describe residual atrial septal defects in 3 patients who had previous surgical repair. The residual defects were the sinus venosus type near the orifice of the inferior vena cava. Preoperative and intraoperative transesophageal echocardiography may aid in the detection and facilitate the successful repair of these defects.

The histologic estimation of coronary artery stenoses: accuracy and the effect of lumen shape.

The authors have recently investigated the histologic estimation of coronary artery stenoses (CAS) to determine its reproducibility and the effect of training on reproducibility. The present study extends this work, examining the accuracy, the sensitivity, and the specificity of the estimation of CAS. Further, the effect of one histologic variable (i.e., arterial lumen shape) on the evaluation of CAS is examined. As described previously, 20 randomly selected Movat-stained coronary artery cross-sections were reviewed three times, at 3-month intervals, by six clinical pathologists (CPs), six pathology residents (Res), seven anatomic pathologists (APs), and two cardiovascular pathologists (CVPs). Before the third iteration, training in CAS assessment was provided. In the present study, for comparison with observer estimates, image analysis was used to establish the actual percent CAS and determine observer accuracy. The results of this study showed, paradoxically, that greater experience did not correlate with greater accuracy: The CPs consistently had the highest accuracy scores and the CVPs consistently had the lowest. Training, however, improved the accuracy scores of all groups. Stenotic arterial cross-sections with residual lumens showing concentric or eccentric polymorphous shapes were consistently underestimated compared to image analysis, while lumens with a eccentric slitlike shape were consistently overestimated.

Percutaneous removal of pulmonary artery emboli with Hydrolyser catheter in pigs.

OBJECTIVE: To evaluate the efficacy and safety of the Hydrolyser catheter for percutaneous treatment of massive pulmonary embolism in pigs. MATERIALS AND METHODS: Twelve pigs, each weighing between 55 kg and 89 kg, were used. Radioopaque 9 cm x 0.8 cm and 4.5 cm x 0.8 cm clots, produced by mixing pig blood with iodinated contrast agent in vacutainers, were injected via the jugular vein until central pulmonary embolism (main and proximal lobar arteries) was obtained with significant systemic and pulmonary hemodynamic modifications. From a femoral approach, the 7-French Hydrolyser thrombectomy catheter was run over a 0.025-inch (0.64-mm) guide wire to remove the pulmonary emboli. Hemodynamic, gasometric and angiographic monitoring was performed before and after treatment. The procedure's safety and completeness of emboli removal was assessed by cardiopulmonary autopsy. RESULTS: Three of the 12 pigs died during embolization. Thrombectomy was therefore performed in 9, and central emboli could be obtained in 7 of the 9. The Hydrolyser could be manipulated only in central pulmonary arteries and could aspirate only central emboli in 5 of the 7 pigs that had them. Despite minimal angiographic improvement seen in these 5, there was no significant hemodynamic and gasometric improvement after treatment. The procedure induced an increase in free hemoglobin blood levels. Autopsies revealed an average of 2 endothelial injuries per pig (mainly adherent endocardial thrombi) in both nontreated (n = 3) and Hydrolyser-treated (n = 9) groups. CONCLUSION: The Hydrolyser thrombectomy catheter can be promptly positioned and easily steered in central pulmonary arteries. It can be used to partially remove central emboli, but not peripheral pulmonary emboli. Most of the injuries observed may not have been strictly related to Hydrolyser use. The pig might not be a suitable animal model for treatment of massive pulmonary embolism.

Abundance of plaque microvessels is associated with constrictive remodeling in angioplastied human coronary arteries.

This study investigated if specific histological features correlate with remodeling in human coronary arteries treated by balloon angioplasty (PTCA). Segments of perfusion-fixed coronary arteries that had undergone antemortem PTCA were obtained from 15 patients and primary atherosclerotic (CAD) lesions obtained from these hearts were used as control lesions. Arterial segments were serially divided to yield 108 sub-segments for PTCA lesions and 38 sub-segments for CAD lesions. A linear regression analysis was used to determine the relationship between 14 histological parameters and an arbitrary index of compensatory arterial enlargement, the external elastic lamina (EEL) index (EELI), defined as the ratio of the area encompassed by the EEL to the sum of the intimal area (IA) + medial area (MA). In PTCA arteries the abundance of plaque microvessels negatively correlated with the EELI (p=0.04), but in CAD arteries there was no relationship between histology and the EELI. The abundance of plaque microvessels correlates with the magnitude of constriction in coronary artery lesions subjected to PTCA. This study provides descriptive insights into the biology of remodeling in human coronary arteries after angioplasty, and suggests that the endothelium may play an important role.