Solvent structure and dynamics over Brønsted acid MWW zeolite nanosheets.

In the liquid phase of heterogeneous catalysis, solvent plays an important role and governs the kinetics and thermodynamics of a reaction. Although it is often difficult to quantify the role of the solvent, it becomes particularly challenging when a zeolite is used as the catalyst. This difficulty arises from the complex nature of the liquid/zeolite interface and the different solvation environments around catalytically active sites. Here, we use ab initio molecular dynamics simulations to probe the local solvation structure and dynamics of methanol and water over MWW zeolite nanosheets with varying Brønsted acidity. We find that the zeolite framework and the number and location of the acid sites in the zeolite influence the structure and dynamics of the solvent. In particular, methanol is more likely to be in the vicinity of the aluminum (Al3+) at the T4 site than at T1 due to easy accessibility. The methanol oxygen binds strongly to the Al at the T4 site, weakening the Al-O for the bridging acid site, which results in the formation of the silanol group, significantly reducing the acidity of the site. The behavior of methanol is in direct contrast to that of water, where protons can easily propagate from the zeolite to the solvent molecules regardless of the acid site location. Our work provides molecular-level insights into how solvent interacts with zeolite surfaces, leading to an improved understanding of the catalytic site in the MWW zeolite nanosheet.

Insights into Sorption and Molecular Transport of Aqueous Glucose into Zeolite Nanopores.

Liquid-phase heterogeneous catalysis using zeolites is important for biomass conversion to fuels and chemicals. There is a substantial body of work on gas-phase sorption in zeolites with different topologies; however, studies investigating the diffusion of complex molecules in liquid medium into zeolitic nanopores are scarce. Here, we present a molecular dynamics study to understand the sorption and diffusion of aqueous ß-d-glucose into ß-zeolite silicate at T = 395 K and P = 1 bar. Through 2-µs-long molecular dynamics trajectories, we reveal the role of the solvent, the kinetics of the pore filling, and the effect of the water model on these properties. We find that the glucose and water loading is a function of the initial glucose concentration. Although the glucose concentration increases monotonically with the initial glucose concentration, the water loading exhibits a nonmonotonic behavior. At the highest initial concentration (∼20 wt %), we find that the equilibrium loading of glucose is approximately five molecules per unit cell and displays a weak dependence on the water model. Glucose molecules follow a single-file diffusion in the nanopores due to confinement. The dynamics of glucose and water molecules slows significantly at the interface. The average residence time for glucose molecules is an order of magnitude larger than that in the bulk solution, while it is about twice as large for the water molecules. Our simulations reveal critical molecular details of the glucose molecule's local environment inside the zeolite pore relevant to catalytic conversion of biomass to valuable chemicals.

Solvation effect on binding modes of model lignin dimer compounds on MWW 2D-zeolite.

Lignin as a potential renewable source of biofuels, chemicals, and other value-added products has gained much attention. However, the complexity of lignin structure poses a significant challenge for developing efficient valorization techniques. As most processes involve solvothermal conditions to minimize energy cost, lignin depolymerization is governed by reaction conditions (temperature and pressure) and solvents. In this work, binding of ß-O-4 linkage consisting lignin dimers on MWW two-dimensional (2D) zeolite is investigated using periodic density functional theory. Furthermore, the effect of different terminated surfaces (H:OH% = 100:0; 50:50; 0:100%), different temperatures (323, 353, 373 K), and different solvents (water and methanol) on the binding modes is quantified. Our work shows that in the gas phase the binding strength increases 10-15 kcal/mol upon increasing the number of hydroxyl groups on the surface. Also, the phenolic dimer binds more strongly than the nonphenolic dimer, and the binding strength of model compounds increases in the presence of the solvent. Analysis of structural changes in the presence of the solvent reveals that the aromatic rings are parallel to the zeolite surface and primary interaction with zeolite is through the hydroxyl groups near the ß-O-4 linkage. Furthermore, while the solvation energy decreases with increasing temperature, the opposite trend is observed for the binding energy with the surface.

Meeting the challenge of interpreting high-resolution single nucleotide polymorphism array data in prenatal diagnosis: does increased diagnostic power outweigh the dilemma of rare variants?

OBJECTIVE: Several studies have already shown the superiority of chromosomal microarray analysis (CMA) compared with conventional karyotyping for prenatal investigation of fetal ultrasound abnormality. This study used very high-resolution single nucleotide polymorphism (SNP) arrays to determine the impact on detection rates of all clinical categories of copy number variations (CNVs), and address the issue of interpreting and communicating findings of uncertain or unknown clinical significance, which are to be expected at higher frequency when using very high-resolution CMA. DESIGN: Prospective validation study. SETTING: Tertiary clinical genetics centre. POPULATION: Women referred for further investigation of fetal ultrasound anomaly. METHODS: We prospectively tested 104 prenatal samples using both conventional karyotyping and high-resolution arrays. MAIN OUTCOME MEASURES: The detection rates for each clinical category of CNV. RESULTS: Unequivocal pathogenic CNVs were found in six cases, including one with uniparental disomy (paternal UPD 14). A further four cases had a 'likely pathogenic' finding. Overall, CMA improved the detection of 'pathogenic' and 'likely pathogenic' abnormalities from 2.9% (3/104) to 9.6% (10/104). CNVs of 'unknown' clinical significance that presented interpretational difficulties beyond results from parental investigations were detected in 6.7% (7/104) of samples. CONCLUSIONS: Increased detection sensitivity appears to be the main benefit of high-resolution CMA. Despite this, in this cohort there was no significant benefit in terms of improving detection of small pathogenic CNVs. A potential disadvantage is the high detection rate of CNVs of 'unknown' clinical significance. These findings emphasise the importance of establishing an evidence-based policy for the interpretation and reporting of CNVs, and the need to provide appropriate pre- and post-test counselling.

Medicolegal activity in obstetrical and gynaecological ultrasound.

We surveyed obstetricians who are members of the Australian Association of Obstetrical and Gynaecological Ultrasonologists for details of actions in which they had been asked to give an expert opinion between 1993 and 1998. We uncovered 50 cases, most of which involved missed fetal anomalies. Our findings suggest there is considerable medicolegal activity in obstetrical and gynaecological ultrasound in Australia.

Prenatal diagnosis and management of sacrococcygeal teratoma.

Five fetuses, each with a sacrococcygeal teratoma (SCT) were delivered at the Royal Women's Hospital while 2 fetuses, each with a SCT were delivered at Monash Medical Centre in 1998. The number of cases reported in this series is higher than expected but it most likely occurred due to chance. The diagnosis was made prenatally in all cases. Three of the SCT were entirely external while the remaining 4 were external with intrapelvic extension. Rapid growth of the SCT occurred in 3 fetuses. This was associated with polyhydramnios in 2 fetuses. No fetus developed nonimmune hydrops. Six infants were liveborn (perinatal mortality rate of 14%), 3 of whom were delivered prior to 37 weeks' gestation. Two infants were delivered by classical Caesarean section. The remaining 4 infants were delivered by lower uterine segment Caesarean section. There was 1 perinatal death. This stillborn infant was delivered vaginally. The 6 surgical resections were performed between the 4th and 10th postnatal days. Histological examination confirmed the diagnosis of benign SCT in each. One infant developed a recurrence at 2 months of age and required chemotherapy.

Bacterial vaginosis: its importance in obstetrics.

Bacterial vaginosis is associated with adverse sequelae, including late miscarriage, preterm prelabour rupture of the membranes, chorioamnionitis, postpartum endometritis and preterm labour and delivery. It is easy to diagnose and treat; intervention reduces the incidence of adverse sequelae. Symptomatic women and those who are at increased risk of infectious morbidity should be screened.

Mid-trimester ultrasound diagnosis of isolated talipes equinovarus: accuracy and outcome for infants.

Seventeen fetuses were diagnosed with isolated congenital talipes equinovarus (CTEV) on mid-trimester ultrasound at the Royal Women's Hospital, Melbourne, between January, 1992 and December 1995. Sixteen of the 17 cases had an amniocentesis performed and all karyotypes were normal. The remaining case was phenotypically normal, except for a clubfoot. None of the pregnancies was complicated by any of the recognized intrauterine environmental causes of CTEV. Four of the babies were delivered prematurely and all survived the neonatal period. Six (35%) infants did not have CTEV at birth, although 2 had postural varus feet. Nine of the 11 infants who did have CTEV at birth were treated within days of birth with plaster of Paris for periods of 6 to 12 weeks. Two infants required no further treatment, 5 required orthotics and 2 required surgery. The other 2 infants with CTEV at birth were treated with orthotics at 8 weeks of age. All infants were considered to have an excellent result at the 2 year follow-up. Seven (41%) of the prospective parents received antenatal counselling by an orthopaedic surgeon and the lack of study on outcome following an ultrasound diagnosis of CTEV was the impetus for our work.

Abnormal cervical cytology in pregnancy: experience of 811 cases.

This paper reviews our hospital's experience spanning 15 years and involving 811 women referred with abnormal cervical cytology in pregnancy. It supports the safety and accuracy of managing dysplasia in pregnancy with colposcopy, directed punch biopsy and deferral of treatment until the postpartum period. The histologically-proven progression in pregnancy to a higher grade of dysplasia postpartum was 7%. None of the women are known to have developed microinvasive or invasive cancer between antenatal assessment and postpartum review. Of these 811 women, 16% were lost to follow-up, 1 of whom subsequently represented 4 years later with invasive cervical cancer.