Evaluation of crystallographic strain, rotation and defects in functional oxides by the moiré effect in scanning transmission electron microscopy.

Moiré patterns in scanning transmission electron microscopy (STEM) images of epitaxial perovskite oxides are used to assess strain and defect densities over fields of view extending over several hundred nanometers. The patterns arise from the geometric overlap of the rastered STEM electron beam and the samples' crystal periodicities and we explore the emergence and application of these moiré fringes for rapid strain analysis. Using the epitaxial functional oxide perovskites BiFeO3 and Pr1-x Ca x MnO3, we discuss the impact of large degrees of strain on the quantification of STEM moiré patterns, identify defects in the fringe patterns and quantify strain and lattice rotation. Such a wide-area analysis of crystallographic strain and defects is crucial for developing structure-function relations of functional oxides and we find the STEM moiré technique to be an attractive means of structural assessment that can be readily applied to low dose studies of damage sensitive crystalline materials.

Aberration corrected Lorentz scanning transmission electron microscopy.

We present results from an aberration corrected scanning transmission electron microscope which has been customised for high resolution quantitative Lorentz microscopy with the sample located in a magnetic field free or low field environment. We discuss the innovations in microscope instrumentation and additional hardware that underpin the imaging improvements in resolution and detection with a focus on developments in differential phase contrast microscopy. Examples from materials possessing nanometre scale variations in magnetisation illustrate the potential for aberration corrected Lorentz imaging as a tool to further our understanding of magnetism on this lengthscale.

Age-related hearing loss, vitamin B-12, and folate in elderly women.

BACKGROUND: Hearing impairment is 1 of the 4 most prevalent chronic conditions in the elderly. However, the biological basis of age-related hearing loss is unknown. OBJECTIVE: The objective was to test the hypothesis that age-related hearing loss may be associated with poor vitamin B-12 and folate status. DESIGN: A thorough audiometric assessment was conducted in 55 healthy women aged 60-71 y. Hearing function was determined by the average of pure-tone air conduction thresholds at 0.5, 1, 2, and 4 kHz and was categorized into 2 groups for logistic regression analyses: normal hearing (<20 dB hearing level; n = 44) and impaired hearing (> or = 20 dB hearing level; n = 11). RESULTS: Mean age was the same (65 y) for the normal hearing and impaired hearing groups. Pure-tone averages were inversely correlated with serum vitamin B-12 (r = -0.58, P = 0.0001) and red cell folate (r = -0.37, P = 0.01). Women with impaired hearing had 38% lower serum vitamin B-12 (236 compared with 380 pmol/L, respectively, P = 0.008) and 31% lower red cell folate (425 compared with 619 nmol/L, respectively, P = 0.02) than women with normal hearing. Among participants who did not take supplements containing vitamin B-12 or folate, women with impaired hearing had 48% lower serum vitamin B-12 (156 compared with 302 pmol/L, respectively, P = 0.0007) and 43% lower red cell folate (288 compared with 502 nmol/L, respectively, P = 0.001) than women with normal hearing. CONCLUSION: Poor vitamin B-12 and folate status may be associated with age-related auditory dysfunction.

Vinyl imidates in cycloaddition reactions: a formal synthesis of (+/-)-reserpine.

[reaction: see text] The intramolecular Diels-Alder reaction of N-acylvinylimidates provides an efficient entry into cis-fused perhydroisoquinoline ring systems. This is demonstrated by the preparation of isoquinoline 2, an intermediate, which has been previously transformed to reserpine.

1-Boraadamantane blows its top, sometimes. The mono- and polyhomologation of 1-boraadamantane.

[reaction: see text] 1-Boraadamantane.THF (3) reacts with 1 equiv of dimethylsulfoxonium methylide (4) to afford a monohomologated product. The polyhomologation of 1-boraadamantane.THF by ylide 4 followed by oxidative cleavage generates star polymethylene polymers incorporating a cyclohexane core. However, only one-third of the initiators lead to product formation, resulting in an observed degree of polymerization three times higher than expected. The polyhomologation of 3 was found to contain branch points after the fourth and fifth methylene insertions. At the branch points, the propagating species either terminate in tricyclic trialkylborane cages with collapsed, pyramidal inverted boron centers that are unreactive toward ylide or they continue in uninterrupted polymerization and eventually result in the formation of giant "tube-like" structures such as 5.

Tandem hetero diels-alder reaction: synthesis of oxygenated macrocycles.

[structure: see text]. C2-symmetric, oxygenated macrocycles have been synthesized from simple acyclic precursors in a single step by a tandem hetero Diels-Alder reaction. Thermolysis and Lewis acid catalysis can effect this novel transformation. The tandem reaction product is formed in preference to the intramolecular cycloaddition product, and an explanation for this result is proposed.

Type 2 intramolecular nitroso Diels-Alder reaction. Synthesis and structure of bridgehead oxazinolactams.

[reaction--see text] The type 2 intramolecular Diels-Alder cycloaddition utilizing N-acylnitroso dienophiles provides an efficient entry into bridged oxazinolactams. In contrast to the bimolecular counterpart, the reaction is completely regioselective. Structural characterization of the cycloadducts allows for evaluation of the olefin distortion and the degree of pyramidalization of the bridgehead oxazinolactam.

Bridged to Fused Ring Interchange. Methodology for the Construction of Fused Cycloheptanes and Cyclooctanes. Total Syntheses of Ledol, Ledene, and Compressanolide.

The type two intramolecular Diels-Alder reaction (T2IMDA) is an efficient method for the formation of medium rings. The methodology is particularly effective for the construction of seven- and eight-membered rings. A strategy for the synthesis of functionalized cycloheptanes and cyclooctanes has been developed that involves a bridged to fused ring interchange. The T2IMDA provides a synthesis for rigid bridged bicyclic molecules that can be stereoselectively elaborated before ozonolysis of the bridgehead double bond. Following oxidative cleavage, aldol condensation provides fused bicyclic ring systems that otherwise are difficult to synthesize. This methodology is amenable to the synthesis of terpene natural products. This is demonstrated here through total syntheses of (+/-)-ledol and (+/-)-ledene and a formal synthesis of (+/-)-compressanolide.

Chiral ion-exchange chromatography. Correlation between solute retention and a theoretical ion-exchange model using imprinted polymers.

Mobile phase effects were studied in the separation of D- and L-phenylalanine anilide (D,L-PA) on an imprinted chiral stationary phase (CSP). Using an aqueous-organic mobile phase, an improved column performance was seen, reflected in a two-fold decrease in the reduced plate height and an almost doubling of the resolution as compared to when a pure organic mobile phase was used. A strong dependence of retention (k') and enantiomer selectivity (alpha) on mobile phase pH was observed. k' reached a maximum at a pH close to the pKa value of the solute and alpha was high at low pH value but decreased when pH exceeded the solute pKa. Potentiometric titration data allowed estimation of the state of protonation of both the carboxylic acid containing CSP and the amino group containing solutes. The data are analyzed using a simple cation-exchange model to allow simulation of the retention as a function of mobile phase pH. The close agreement between the simulated and experimental curves for retention versus pH suggests that a simple cation-exchange mechanism controls the retention in this system. Moreover, the slightly lower average pKa of the imprinted polymer compared to that of a corresponding blank polymer explains the high selectivity seen at low pH values. Based on these findings, a model describing the events controlling binding and selectivity as a function of pH is proposed.

The diagnostic accuracy of history, physical examination, and radiographs in the evaluation of traumatic knee disorders.

We prospectively looked at the diagnostic accuracy of clinical examination of the knee in patients with arthroscopically documented knee injuries. The study included 156 patients with 156 knee injuries (72 acute and 84 chronic) who were seen during 1 year at Martin Army Hospital at Fort Benning Georgia. All patients were given a primary diagnosis based on their history, physical examination, and routine radiographs. Fifty-seven patients were also given one or more secondary diagnoses. Magnetic resonance imaging scans and arthrograms were not used in the evaluation of these patients. The primary diagnosis was correct in 83% of the knees. Of 57 secondary diagnoses given, 54% were correct and 31% were incomplete. An incorrect diagnosis was made in 14% of knees for both primary and secondary diagnoses. There were four patients with no identifiable lesion other than synovitis. With the increasing cost of medical care, the need for expensive diagnostic studies such as magnetic resonance imaging needs to be evaluated. The cost of a magnetic resonance image scan ranges between $600 to $1200 depending on the institution. The use of magnetic resonance imaging as a routine diagnostic aid in the clinical examination of the knee is unnecessary. Arthroscopic surgery of the knee should be based on the patient's history, physical examination, and radiographs.

Fabrication of high quality plan-view TEM specimens using the focused ion beam.

We describe a technique using a focused ion beam instrument to fabricate high quality plan-view specimens for transmission electron microscopy studies. The technique is simple, site-specific and is capable of fabricating multiple large, >100 µm(2) electron transparent windows within epitaxially grown thin films. A film of La0.67Sr0.33MnO3 is used to demonstrate the technique and its structural and functional properties are surveyed by high resolution imaging, electron spectroscopy, atomic force microscopy and Lorentz electron microscopy. The window is demonstrated to have good thickness uniformity and a low defect density that does not impair the film's Curie temperature. The technique will enable the study of in-plane structural and functional properties of a variety of epitaxial thin film systems.

A mechanistic investigation of gelation. The sol-gel polymerization of precursors to bridged polysilsesquioxanes.

The study of a homologous series of precursors to bridged polysilsesquioxanes has uncovered striking discontinuities in gelation behavior. An investigation of the chemistry during the early stages of the polymerization has provided a molecular basis for these observations. Monomers containing from one to four bridging carbon atoms exhibit a pronounced tendency to undergo rapid intra- or bimolecular cyclization. The cyclic and bicyclic intermediates have been characterized by (29)Si NMR spectroscopy, chemical ionization mass spectrometry, and isolation from the reaction solution. These carbosiloxanes are local thermodynamic sinks that produce kinetic bottlenecks in the production of high-molecular-weight silsesquioxanes. The formation of cyclic carbosiloxanes results in slowing, or in some cases completely shutting down, gelation. An additional finding is that the cyclic structures are incorporated intact into the final xerogel.

Enantioselective ester hydrolysis catalyzed by imprinted polymers.

Highly cross-linked network polymers prepared by molecular imprinting catalyzed enantioselectively the hydrolysis of N-tert-butoxycarbonyl phenylalanine-p-nitrophenyl ester (BOCPheONP). The templates were designed to allow incorporation of the key catalytic elements, found in the proteolytic enzyme chymotrypsin, into the polymer active sites. Three model systems were evaluated. These were constructed from a chiral phosphonate analogue of phenylalanine (series A, C) or L-phenylalanine (series B) attached by a labile ester linkage to an imidazole-containing vinyl monomer. Free radical copolymerization of the template with methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDMA) gave a highly cross-linked network polymer. The templates could be liberated from the polymers by hydrolysis, giving catalytically active sites envisaged to contain an enantioselective binding site, a site complementary to a transition state like structure (series A, C), and a hydroxyl, imidazole, and carboxylic acid group at hydrogen bond distance. As predicted, the enantiomer of BOCPheONP complementary to the configuration of the template was preferentially hydrolyzed with D-selectivity for the series A polymers (kD/kL = 1.9) and L-selectivity for the series B polymers (kL/kD = 1.2). The maximum rate enhancement, when compared with a control polymer, prepared using a benzoyl-substituted imidazole monomer as template, was 2.5, and comparing with the imidazole monomer in solution, a maximum rate enhancement of 10 was observed. The catalytic activity was higher for polymers subjected to the nucleophilic treatment. This was explained by a higher site density and flexibility of the polymer matrix caused by this treatment. In a comparison of template rebinding to polymers imprinted with a template containing either a carboxylate (planar ground state structure) or a phosphonate (tetrahedral transition state like structure) functionality, it was observed that imprinted polymers are able to discriminate between a transition state like and a ground state structure for transesterification. However the influence of transition state stabilization on the observed rate enhancements remains obscure. Only at acidic pH's was catalysis observed, whereas at basic pH's the polymers inhibit the reaction. At a later stage, the catalytic activity of the polymers for nonactivated D- and L-phenylalanine ethyl esters was investigated. A rate enhancement of up to 3 was observed when compared to the blank. Most important, however, the polymers imprinted with a D template preferentially hydrolyzed the D-ethyl ester and exhibited saturation kinetics.

Consonant recognition for spectrally degraded speech as a function of consonant-vowel intensity ratio.

Normal-hearing subjects' recognition of spectrally degraded speech was evaluated under conditions in which the consonant-vowel (C-V) intensity ratio was modified. Subjects identified 22 consonants presented in an /a-Consonant-a/ format at suprathreshold and near threshold conditions. Prior to C-V ratio modification, the stimuli were processed to limit spectral information. In the suprathreshold experiment, stimuli were presented at the natural C-V ratio and at six modified C-V ratios. C-V ratio manipulations had dramatic effects on recognition scores for some groups of consonants. Scores for glides and sibilant fricatives increased with increasing C-V ratio, while scores for nasals and weak fricatives were best at low C-V ratios. Recognition scores for the stops and affricates were generally independent of C-V ratio. For nearly all consonants, changes in recognition scores as a function of C-V ratio were associated with changes in a general response bias toward those sounds. Performance was poor when the spectrally smeared VCVs were presented at low SN ratios in a second experiment. The influence of C-V ratio on percent correct scores was generally similar to the suprathreshold results, but consonant audibility, which was not a factor in the suprathreshold experiment, appeared to alter the effect of C-V ratio modification for some consonants.