Mechanistic insight into the fluorescence activity of forensic fingerprinting reagents.

Fingerprint detection is still the primary investigative technique for deciphering criminal inquiries and identifying individuals. The main forensic fingerprinting reagents (FFRs) currently in use can require multiple treatment steps to produce fingerprints of sufficient quality. Therefore, the development of new, more effective FFRs that require minimal chemical treatment is of great interest in forensic chemistry. In this work, prudently crafted density functional theory and time-dependent density functional theory calculations are utilized to derive mechanistic insight into the optical activity of the non-fluorescent product of ninhydrin, diketohydrindylidenediketohydrindamine (DYDA), and fluorescent product of DFO (1,8-diazafluoren-9-one). We investigate various protonation sites to gain an understanding of isomeric preference in the solid-state material. A relaxed scan of a single torsion angle rotation in the S1 minimized geometry of the O-protonated DYDA isomer suggests a conical intersection upon ∼10° rotation. We show that the absence of a rigid hydrogen-bonded network in the crystal structure of DYDA supports the hypothesis of torsion rotation, which leads de-excitation to occur readily. Conversely, for the fluorescent DFO product, our calculations support an avoided crossing suggestive of a non-radiative mechanism when the torsion angle is rotated by about ∼100°. This mechanistic insight concurs with experimental observations of fluorescence activity in DFO and may aid the photophysical understanding of poorly visualized fingerprints due to weak fluorescence. We show that identifying suggestive avoided crossings via the method described here can be used to initialize thoughts toward the computational design of FFRs.

Birth defects after maternal exposure to corticosteroids: prospective cohort study and meta-analysis of epidemiological studies.

BACKGROUND: Corticosteroids are first-line drugs for the treatment of a variety of conditions in women of childbearing age. Information regarding human pregnancy outcome with corticosteroids is limited. METHODS: We collected prospectively and followed up 184 women exposed to prednisone in pregnancy and 188 pregnant women who were counseled by Motherisk for nonteratogenic exposure. The primary outcome was the rate of major birth defects. A meta-analysis of all epidemiological studies was conducted. The Mantel-Haenszel summary odds ratio was calculated for the pooled studies with 95% confidence intervals. A cumulative summary odds ratio was also calculated by combining studies in chronological order. Chi-squared for homogeneity was determined to establish the comparability of the studies. RESULTS: In our prospective study, there was no statistical difference in the rate of major anomalies between the corticosteroid-exposed and control groups. In the meta-analysis, the Mantel-Haenszel summary odds ratio for major malformations with all cohort studies was 1.45 [95% CI 0.80, 2.60] and 3.03 [95% CI 1.08, 8. 54] when Heinonen et al. ('77) was removed. This suggests a marginally increased risk of major malformations after first-trimester exposure to corticosteroids. In addition, summary odds ratio for case-control studies examining oral clefts was significant (3.35 [95% CI 1.97, 5.69]). CONCLUSIONS: Although prednisone does not represent a major teratogenic risk in humans at therapeutic doses, it does increase by an order of 3.4-fold the risk of oral cleft, which is consistent with the existing animal studies.

Hydroxyurea use during pregnancy: a case report in sickle cell disease and review of the literature.

A patient being treated for sickle cell disease with hydroxyurea (1 g/d) conceived, and drug treatment was discontinued at nine weeks gestational age. The pregnancy and delivery were complicated by vaso-occlusive crises. A healthy male infant was born at 39 weeks with no evidence of congenital malformations. A literature review, including this case, suggests that the risk of hydroxyurea exposure during in pregnancy may have been overestimated. Further studies are required to determine its safety in pregnancy.