The full spectrum tuning of fluorescent molecules via a one-pot multicomponent reaction.

Fluorogenic probes for imaging enable visualization and analysis of difficult-to-reach cells and organelles. However, there are limited efficient examples of tuning these fluorescent molecules to higher wavelengths. This is vital since different tissues are sensitive to varying wavelength emissions. To address this need, we report the discovery, tuning, structure-photophysical property relationships (SPPR), and time-dependent DFT (TD-DFT) computations of 400-700+ nm fluorescent pyrido[2',1':2,3]imidazo[4,5-c]isoquinolines and substituted imidazo[1,2-a]pyridin-3-amines. The syntheses involve the trimethylsilylcyanide (TMSCN) modified Groebke-Blackburn-Bienaymé (GBB) multicomponent reaction as well as the TMSCN modified GBB combined with subsequent condensation of an aldehyde, and Aza-Friedel-Crafts-Intramolecular Cyclization-Oxidation all in one pot. The SPPR reveals that electron-withdrawing strength in the para-position of the aminopyridine starting material has direct control over the absorption and fluorescence emission wavelengths of these molecules. The TD-DFT computations show the changes in the natural transition orbitals (NTOs) with differing substitutions to the parent molecule that dictate the observed excitations, emissions, and fluorescence intensities. These findings give insights and directions for tuning the fluorescent properties of these motifs for various uses as probes and imaging agents.

Sequential Knoevenagel [4+1] Cycloaddition-Condensation-Aza-Friedel-Crafts Intramolecular Cyclization: A 4-Center-3-Component Reaction Toward Tunable Fluorescent Indolizine Tetracycles.

A two-step multicomponent reaction oxidation protocol is reported herein, which affords novel tunable fluorescent tetracyclic indolizines. The procedure involves a novel 4-center-3-component reaction, which proceeds via a sequential Knoevenagel condensation, [4+1] cycloaddition, and imine condensation to afford imino-indolizines. Products then undergo cyclization and are oxidized in situ to afford fluorescent tetracycles, which are readily tunable through modification of diversity elements.

Oxidations of pyrrolidines and piperidines to afford CH-functionalized isopropyl-1-carboxylate congeners.

This article describes the action of iodine(III) reagents [diacetoxyiodobenzene, PhI(OAc)2, and iodosobenzene, (PhIO)n] in conjunction with TMSBr which act as functional bromine equivalents in unique oxidations of saturated, carbamate protected N-heterocycles. Interestingly, during this work, treatment of the same carbamates with molecular bromine alone afforded similar products, which were sequestered by the solvent methanol.

Systemic inflammatory response syndrome in patients with spinal cord injury: does its presence at admission affect patient outcomes? Clinical article.

OBJECT: The object in this study was to determine whether the presence of systemic inflammatory response syndrome (SIRS) in patients with traumatic spinal cord injury (SCI) on admission is related to subsequent clinical outcome in terms of length of stay (LOS), complications, and mortality. METHODS: The authors retrospectively reviewed the charts of 193 patients with acute traumatic SCI who had been hospitalized at their institution between 2006 and 2012. Patients were excluded from analysis if they had insufficient SIRS data, a cauda equina injury, a previous SCI, a preexisting neurological condition, or a condition on admission that prevented appropriate neurological assessment. Complications were counted only once per patient and were considered minor if they were severe enough to warrant treatment and major if they were life threatening. Demographics, injury characteristics, and outcomes were compared between individuals who had 2 or more SIRS criteria (SIRS+) and those who had 0 or 1 SIRS criterion (SIRS-) at admission. Multivariate logistic regression (enter method) was used to determine the relative contribution of SIRS+ at admission in predicting the outcomes of mortality, LOS in the intensive care unit (ICU), hospital LOS, and at least one major complication during the acute hospitalization. The American Spinal Injury Association Impairment Scale grade and patient age were included as covariates. RESULTS: Ninety-three patients were eligible for analysis. At admission 47.3% of patients had 2 or more SIRS criteria. The SIRS+ patients had higher Injury Severity Scores (24.3 ±10.6 vs. 30.2 ±11.3) and a higher frequency of both at least one major complication during acute hospitalization (26.5% vs. 50.0%) and a fracture-dislocation pattern of injury (26.5% vs. 59.1%) than the SIRS- patients (p < 0.05 for each comparison). The SIRS+ patients had a longer median hospital stay (14 vs 18 days) and longer median ICU stay (0 vs. 5 days). However, mortality was not different between the groups. Having SIRS on admission predicted an ICU LOS > 10 days, hospital LOS > 25 days, and at least one complication during the acute hospitalization. CONCLUSIONS: A protocol to identify SCI patients with SIRS at admission may be beneficial with respect to preventing adverse outcomes and decreasing hospital costs.