An investigation of imidazole and oxazole syntheses using aryl-substituted TosMIC reagents.

This article describes efficient and mild protocols for preparing polysubstituted imidazoles in a single pot from aryl-substituted tosylmethyl isocyanide (TosMIC) reagents and imines generated in situ. Traditional imine-forming reactions employing virtually any aldehyde and amine followed by addition of the TosMIC reagent delivers 1,4,5-trisubstituted imidazoles with predictable regiochemistry. Employing chiral amines and aldehydes, particularly those derived from alpha-amino acids, affords imidazoles with asymmetric centers appended to N-1 or C-5 with excellent retention of chiral purity. 1,4-Disubstituted imidazoles are also readily prepared by a simple variant of the above procedure. Selecting glyoxylic acid as the aldehyde component of this procedure leads to intermediates such as 48, which readily undergo decarboxylation and elimination of the tosyl moiety to deliver 1,4-disubstituted imidazoles in high yields. Alternatively, using NH(4)OH as the amine component in conjunction with a variety of aldehydes delivers 4, 5-disubstituted imidazoles in moderate to good yields in a single pot while avoiding the need for protecting groups. Finally, the facile preparation of mono- and disubstituted oxazoles from these TosMIC reagents and aldehydes is described.

Comparison of three videokeratoscopes in measurement of toric test surfaces.

PURPOSE: We compared the accuracy of the Computed Anatomy TMS-1 (1.41), the EyeSys Laboratories Corneal Analysis System (2.1), and the Visioptic EH-270 (3.0) videokeratoscopes in measuring toric surfaces. These non-rotationally symmetric aspheric surfaces served as models of corneal astigmatism. METHODS: Precision diamond-turned toric surfaces modeling 0.00 diopter (D) to 7.00 D of astigmatism were fabricated. A three-dimensional contact profiler was developed to calibrate the aspheric surfaces. Videokeratoscopic data taken at "best focus" were compared to the theoretical shape to quantify device measurement errors. RESULTS: The Computed Anatomy system measurement accuracy shows no statistically significant correlation between measurement error and surface toricity (r2 < 0.13). Measurement error increased linearly with surface astigmatism for the EyeSys Laboratories system (0.12 D rms error per D of astigmatism, r2 > 0.96, p < 0.001 and the Visioptic system (0.03 D error per D of astigmatism, r2 = 0.88, p < 0.001). CONCLUSIONS: This study found systematic performance differences among the three machines. Under ideal alignment conditions, the Computed Anatomy TMS-1 is more accurate at detecting astigmatism. The EyeSys Laboratories Corneal Analysis System apparently underestimates the amount of surface astigmatism because of excessive data smoothing. The Visioptic EH-270 errors are primarily in the central zones and may be due to ring localization errors.

Visual acuity modeling using optical raytracing of schematic eyes.

PURPOSE: We developed a methodology to predict changes in visual performance that result from changes in the optical properties of the eye. METHODS: Exact raytracing of schematic eyes was used to calculate the point spread function and the modulation transfer function of the visual system. The Stiles-Crawford effect, photopic response, diffraction, and the retinal contrast sensitivity are included in the model. Visual acuity was predicted by examining the modulation of the resultant retinal image of a bar target and by determining when the modulation falls below a threshold value. Visual acuity was predicted for refractive errors ranging from 0 to 5 diopters and for pupil diameters ranging from 0.5 to 8 mm. RESULTS: Visual acuity predictions were compared to clinically found Snellen visual acuities and were found to be highly correlated (r2 = .909). CONCLUSIONS: This modeling technique shows promise as a means of evaluating clinical and surgical procedures before undertaking clinical trails.

Videographic Hirschberg measurement of simulated strabismic deviations.

PURPOSE: To demonstrate the potential use of subpixel image processing methods to perform automated Hirschberg measurements of strabismic deviations using relatively inexpensive personal computer hardware; to determine if the method might allow screening for strabismus using full-face video images obtained from a distance of 1 meter. METHODS: Strabismic deviations (< 25 prism diopters) were simulated by means of induced asymmetric fixation. A ring of coaxial infrared light-emitting diodes (LED) were used to generate first Purkinje reflexes. Computerized image analysis with subpixel processing was used to measure the locations of the first Purkinje reflexes and pupil centers of video images of 10 normal subjects, following the technique of the clinical Hirschberg test. The apparent strabismic deviation was calculated from the relative asymmetry of the center of the corneal reflex ring to the pupil center in each eye. RESULTS: In 10 normal subjects, there was a statistically significant linear correlation of Hirschberg horizontal reflex deviation with asymmetric fixation pseudo-esotropia (0.85 > or = r2 > or = 0.99, P < 0.05). CONCLUSIONS: The Hirschberg test is used manually to detect strabismus in infants and children but requires a highly skilled examiner. The image processing method described here requires no operator interpretation and may make the test more applicable. The results suggest that this technology may be appropriate for a screening instrument.

Epidemiological and clinical approach to the study of candidiasis caused by Candida albicans in heroin addicts in the Paris region: analysis of 35 observations.

A study of 35 cases of deep-seated Candida albicans candidiasis, affecting heroin addicts in the Paris region, revealed that the lesions observed were mainly cutaneous (88 per cent) and ocular (65 per cent), along with a number of instances of osteoarticular and pleuropulmonary attacks. The clinical and epidemiological findings indicated the possibility that Candida albicans might be transmitted through the heroin. This paper also presents the diagnostic techniques, and the novelty of the clinical picture, in which cutaneous and ocular lesions are frequently associated (57 per cent).

Stability and diversity at three trophic levels in terrestrial successional ecosystems.

An ecosystem perturbation experiment in which inorganic fertilizer was added to two successional old fields of different ages indicated that stability, expressed as resistance to modification by enrichment, increased during succession only at the primary trophic level. The perturbation was propagated throughout the arthropod herbivores and carnivores. Both herbivores and carnivores were less stable in the older field. In contrast to current ecological theory, greater diversity at a trophic level was accompanied by lower stability at the next higher level.