Development of automated detection of radiology reports citing adrenal findings.

The aim of this study was to determine the feasibility of automated detection of adrenal nodules, a common finding on CT, using a newly developed search engine that mines dictated radiology reports. To ensure Health Insurance Portability and Accountability Act compliance, we utilized a preexisting de-identified database of 32,974 CT reports from February 1, 2009 to February 28, 2010. Common adrenal descriptors from 29 staff radiologists were used to develop an automated rule-based algorithm targeting adrenal findings. Each sentence within the free text of reports was searched with an adapted NegEx negation algorithm. The algorithm was refined using a 2-week test period of reports and subsequently validated using a 6-week period. Manual review of the 3,693 CT reports in the validation period identified 222 positive reports while the algorithm detected 238 positive reports. The algorithm identified one true positive report missed on manual review for a total of 223 true positive reports. This resulted in a precision of 91% (217 of 238) and a recall of 97% (217 of 223). The sensitivity of the query was 97.3% (95% confidence interval (CI), 93.9-98.9%), and the specificity was 99.3% (95% CI, 99.1-99.6%). The positive predictive value of the algorithm was 91.0% (95% CI, 86.6-94.3%), and the negative predictive value was 99.8% (95% CI, 99.6-99.9%). The prevalence of true positive adrenal findings identified by the query (7.1%) was nearly identical to the true prevalence (7.2%). Automated detection of language describing common findings in imaging reports, such as adrenal nodules on CT, is feasible.

Water-soluble calix[4]resorcarenes as enantioselective NMR shift reagents for aromatic compounds.

A tetra L-prolinylmethyl derivative of a tetra-sulfonated calix[4]resorcarene (1) is an effective chiral NMR solvating agent for water-soluble compounds with phenyl, pyridyl, bicyclic aromatic, or indole rings. These aromatic compounds form host-guest complexes with the calix[4]resorcarene in water. Complexation of substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects, and bicyclic substrates have association constants with the calix[4]resorcarene larger than those of similar phenyl-containing compounds. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the 1H NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The effectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine (2) as a chiral NMR discriminating agent is compared to the L-prolinylmethyl derivative.

An enantioselective NMR shift reagent for cationic aromatics.

[structure: see text] The water-soluble tetra l-prolinylmethyl derivative of a tetrasulfonated calix[4]resorcarene is an effective chiral NMR solvating agent for compounds with bicyclic aromatic or indole rings. Complexation of bicyclic substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects. The bicyclic substrates have larger association constants with the calix[4]resorcarene than similar phenyl-containing compounds. Substantial enantiomeric discrimination is observed for several resonances in the (1)H NMR spectra of these substrates.

Chiral recognition in NMR spectroscopy using crown ethers and their ytterbium(III) complexes.

Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in 1H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown-substrate mixtures in methanol-d4 causes shifts in the spectra of substrates and often enhances the chiral discrimination in the 1H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1.