Neutron spectroscopy as a tool in catalytic science

Catalytic science currently has access to a range of advanced experimental methods for the study of molecular behaviour in chemical processes. Neutron spectroscopy, however, is uniquely placed to gain detailed insight into such systems, particularly through techniques such as vibrational spectroscopy with neutrons (INS) which gives access to vibrational modes unavailable to conventional spectroscopy techniques, and quasielastic neutron scattering (QENS) which studies molecular motion on a range of timescales. The present article illustrates the role of these techniques in advancing the field of catalysis. We first provide a brief introduction to the basic principles of the techniques, and then discuss their use in the study of three key catalytic systems: the behaviour of hydrocarbons confined in zeolite catalysts; the methanol-to-hydrocarbons process; and methane reforming. We demonstrate the importance of neutron spectroscopy in understanding established catalytic processes, but also consider its role in the design of future catalytic systems

Population Trends and Variation in Body Mass Index from 1971 to 2008 in the Framingham Heart Study Offspring Cohort

Objective: We examined body mass index (BMI) across place and time to determine the pattern of BMI mean and standard deviation trajectories. Methods: We included participants in the Framingham Heart Study (FHS) Offspring Cohort over eight waves of follow-up, from 1971 to 2008. After exclusions, the final sample size was 4569 subjects with 28,625 observations. We used multi-level models to examine population means and variation at the individual and neighborhood (census tracts) levels across time with measured BMI as the outcome, controlling for individual demographics and behaviors and neighborhood poverty. Because neighborhoods accounted for limited BMI variance, we removed this level as a source of variation in final models. We examined sex-stratified models with all subjects and models stratified by sex and baseline weight classification. Results: Mean BMI increased from 24.0 kg/m2 at Wave 1 to 27.7 at Wave 8 for women and from 26.6 kg/m2 to 29.0 for men. In final models, BMI variation also increased from Waves 1 to 8, with the standard deviation increasing from 4.18 kg/m2 to 6.15 for women and 3.31 kg/m2 to 4.73 for men. BMI means increased in parallel across most baseline BMI weight classifications, except for more rapid increases through middle-age for obese women followed by declines in the last wave. BMI standard deviations also increased in parallel across baseline BMI classifications for women, with greater divergence of BMI variance for obese men compared to other weight classifications. Conclusion: Over nearly 40 years, BMI mean and variation increased in parallel across most baseline weight classifications in our sample. Individual-level characteristics, especially baseline BMI, were the primary factors in rising BMI. These findings have important implications not only for understanding the sources of the obesity epidemic in the United States but also for the targeting of interventions to address the epidemic

Modelling metal centres, acid sites and reaction mechanisms in microporous catalysts

We discuss the role of QM/MM (embedded cluster) computational techniques in catalytic science, in particular their application to microporous catalysis. We describe the methodologies employed and illustrate their utility by briefly summarising work on metal centres in zeolites. We then report a detailed investigation into the behaviour of methanol at acidic sites in zeolites H-ZSM-5 and H-Y in the context of the methanol-to-hydrocarbons/olefins process. Studying key initial steps of the reaction (the adsorption and subsequent methoxylation), we probe the effect of framework topology and Brønsted acid site location on the energetics of these initial processes. We find that although methoxylation is endothermic with respect to the adsorbed system (by 17–56 kJ mol−1 depending on the location), there are intriguing correlations between the adsorption/reaction energies and the geometries of the adsorbed species, of particular significance being the coordination of methyl hydrogens. These observations emphasise the importance of adsorbate coordination with the framework in zeolite catalysed conversions, and how this may vary with framework topology and site location, particularly suited to investigation by QM/MM technique

How important is on-site adequacy assessment for thyroid FNA? An evaluation of 883 cases

Immediate adequacy assessment (IADA) during fine-needle aspiration (FNA) is not universal and the optimal numberof passes has not been well determined. The aim of this study was to evaluate the nondiagnostic rates (NDR) with and without the IADA forthyroid aspirates. Subsequent cytological and surgical follow-upwere reviewed for nondiagnostic cases. In addition, we evaluated the numberof passes performed in each FNA to determine the optimal number. Retrospective analysis of NDR was performed on 883 thyroid FNA specimens retrievedthrough a Computer SNOMED Search from our files between January 2001 toDecember 2003. For FNAs with IADA, one Diff-Quick and one fixedsmear for each pass were prepared, and the needle was rinsed in CytoLytsolution for a ThinPrep and/or a cell-block. FNAs without IADAwere received in CytoLyt solution, from which a ThinPrep and a cell-block were prepared for each case. Of the total 883 cases, 443 wereperformed with IADA, of which 417 cases were diagnostic. The remaining440 cases were performed without IADA, of which 300 cases were diagnostic.NDR for IADA was 5.9% (26 cases-group-I)compared to 31.8% (140 cases-group-II)without IADA. In group-I, 5 cases were followed-upby repeat FNA, 10 cases by surgical resection, and 11 cases received notissue follow-up. In group-II, 23 cases were followed-up by repeat FNA, 36 by surgical resection, and 82 cases received notissue follow-up. Interestingly, follow-up in group-Idid not reveal any missed malignancy, while that in group-II resultedin a malignant diagnosis in 13.8% (8 cases). We alsofound that the optimal number of passes with least NDR was 4–6 passes.NDR was 25% for < 3 passes, 11% for 4 passes, 5.2% for 5 passes, 1.4% for 6 passes, and 2.5% for 7 passesor more. IADA significantly reduces the NDR and increases the sample adequacy for diagnosis. Optimal number of passes is 4–6 passes, and additionalpasses did not improve the diagnostic rate. Our study also emphasizesthe significance of repeat FNA or histological follow-up for nondiagnostic cases, especially for those without IADA. Diagn. Cytopathol. 2007;35:183–186. © 2007 Wiley-Liss, Inc.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/55982/1/20552_ftp.pd

Complement Activation in Patients With Probable Systemic Lupus Erythematosus and Ability to Predict Progression to American College of Rheumatology-Classified Systemic Lupus Erythematosus.

ObjectiveTo evaluate the frequency of cell-bound complement activation products (CB-CAPs) as a marker of complement activation in patients with suspected systemic lupus erythematosus (SLE) and the usefulness of this biomarker as a predictor of the evolution of probable SLE into SLE as classified by the American College of Rheumatology (ACR) criteria.MethodsPatients in whom SLE was suspected by lupus experts and who fulfilled 3 ACR classification criteria for SLE (probable SLE) were enrolled, along with patients with established SLE as classified by both the ACR and the Systemic Lupus International Collaborating Clinics (SLICC) criteria, patients with primary Sjögren's syndrome (SS), and patients with other rheumatic diseases. Individual CB-CAPs were measured by flow cytometry, and positivity rates were compared to those of commonly assessed biomarkers, including serum complement proteins (C3 and C4) and autoantibodies. The frequency of a positive multianalyte assay panel (MAP), which includes CB-CAPs, was also evaluated. Probable SLE cases were followed up prospectively.ResultsThe 92 patients with probable SLE were diagnosed more recently than the 53 patients with established SLE, and their use of antirheumatic medications was lower. At the enrollment visit, more patients with probable SLE were positive for CB-CAPs (28%) or MAP (40%) than had low complement levels (9%) (P = 0.0001 for each). In probable SLE, MAP scores of &gt;0.8 at enrollment predicted fulfillment of a fourth ACR criterion within 18 months (hazard ratio 3.11, P &lt; 0.01).ConclusionComplement activation occurs in some patients with probable SLE and can be detected with higher frequency by evaluating CB-CAPs and MAP than by assessing traditional serum complement protein levels. A MAP score above 0.8 predicts transition to classifiable SLE according to ACR criteria

Investigation of the dynamics of 1-octene adsorption at 293 K in a ZSM-5 catalyst by inelastic and quasielastic neutron scattering

The properties of 1-octene adsorbed in zeolite ZSM-5 at 293 K are studied by means of inelastic and quasielastic neutron scattering (INS and QENS) in order to investigate interactions relevant to the zeolite solid acid catalysis of fluidised catalytic cracking reactions. The INS spectrum is compared to that recorded for the solid alkene and reveals significant changes of bonding on adsorption at ambient temperatures; the changes are attributed to the oligomerization of the adsorbed 1-octene to form a medium chain n-alkane or n-alkane cation. QENS analysis shows that these oligomers are immobilised within the zeolite pore structure but a temperature-dependant fraction is able to rotate around their long axis within the pore channels

Octane isomer dynamics in H-ZSM-5 as a function of Si/Al ratio:a quasi-elastic neutron scattering study

Dynamical behaviour of n-octane and 2,5-dimethylhexane in H-ZSM-5 zeolite catalysts of differing Si/Al ratios (15 and 140) was probed using quasi-elastic neutron scattering, to understand molecular shape and Brønsted acid site density effects on the behaviour of common species in the fluid catalytic cracking (FCC) process, where H-ZSM-5 is an additive catalyst. Between 300 and 400 K, n-octane displayed uniaxial rotation around its long axis. However, the population of mobile molecules was larger in H-ZSM-5(140), suggesting that the lower acid site concentration allows for more molecules to undergo rotation. The rotational diffusion coefficients were higher in H-ZSM-5(140), reflecting this increase in freedom. 2,5-dimethylhexane showed qualitative differences in behaviour to n-octane, with no full molecule rotation, probably due to steric hindrance in the constrictive channels. However, methyl group rotation in the static 2,5-dimethylhexane molecules was observed, with lower mobile fractions in H-ZSM-5(15), suggesting that this rotation is less hindered when fewer Brønsted sites are present. This was further illustrated by the lower activation barrier calculated for methyl rotation in H-ZSM-5(140). We highlight the significant immobilizing effect of isomeric branching in this important industrial catalyst and show how compositional changes of the zeolite can affect a range of dynamical behaviours of common FCC species upon adsorption

Comprehensive Vibrational Spectroscopic Characterization of Nylon-6 Precursors for Precise Tracking of the Beckmann Rearrangement

As a key step in nylon‐6 synthesis, the Beckmann rearrangement is an ongoing target of catalytic studies that seek to improve the sustainability of polymer manufacture. Whilst solid‐acid catalysts (predominantly zeotypes) have proven effective for this transformation, the development of more active and selective systems demands an understanding of fundamental catalytic mechanisms. In this undertaking, in situ and operando characterization techniques can be informative, provided rigorous spectroscopic groundwork is in place. Thus, to facilitate mechanistic studies we present a detailed investigation of the vibrational spectra of cyclohexanone, cyclohexanone oxime, ϵ‐caprolactam and their D10‐isotopomers, in the solid state. Variable‐temperature infrared (150–300 K) and Raman (10–300 K) spectra are reported alongside inelastic neutron scattering data. Moreover, where key vibrational modes have been assigned with the aid of periodic density functional theory calculations, it has been possible to include hydrogen‐bonding interactions explicitly