The 126 possible conformations of 1,2,3-propanetriol (glycerol) have been studied by ab initio molecular orbital and density functional theory calculations in the gas and aqueous phases at multiple levels of theory and basis sets. The partial potential energy surface for glycerol as well as an analysis of the conformational properties and hydrogen-bonding trends in both phases have been obtained. In the gas phase at the G2(MP2) and CBS-QB3 levels of theory, the important, low-energy conformers are structures 100 and 95. In the aqueous phase at the SM5.42/HF/6-31G* level of theory, the lowest energy conformers are structures 95 and 46. Boltzmann distributions have been determined from these high-level calculations, and good agreement is observed when these distributions are compared to the available experimental data. These calculations indicate that the enthalpic and entropic contributions to the Gibbs free energy are important for an accurate determination of the conformational and energetic preferences of glycerol. Different levels of theory and basis sets were used in order to understand the effects of nonbonded interactions (i.e., intramolecular hydrogen bonding). The efficiency of basis set and level of theory in dealing with the issue of intramolecular hydrogen bonding and reproducing the correct energetic and geometrical trends is discussed, especially with relevance to practical computational methods for larger polyhydroxylated compounds, such as oligosaccharides.

The swift conversion of chemistry courses to various online formats has presented challenges for students and instructors alike, with one of the most significant challenges being the logistics concerning online testing. At our institution, instructors of general, organic, and physical chemistry courses sought to balance issues of exam access, exam security, and continuity with a traditional test format when switching to unproctored online exams. Different approaches were utilized for exam delivery with varying success. Common challenges arose in several courses, such as the need to train students to use new technology, and the threat of online information for compromising exam security. The most successful attempts to meet these challenges, such as use of a test-bank, are consistent with reported best practices and suggest a way to maximize access, security, and continuity, while working to diminish technological and ethical pitfalls that accompany unproctored online exams.

The ever-increasing discovery of biologically important events mediated by carbohydrates has generated great interest in the synthesis of oligosaccharides and the development of new methods for glycosidic bond formation. In this paper, we report that 2,3-anhydrofuranose thioglycosides (1, 5) and glycosyl sulfoxides (2, 6), in which the hydroxyl groups C-2 and C-3 are "protected" as an epoxide, glycosylate alcohols with an exceptionally high degree of stereocontrol. The predominant or exclusive product of reactions with this fundamentally new class of glycosylating agent is that in which the newly formed glycosidic bond is cis to the epoxide moiety. We further demonstrate that subsequent nucleophilic opening of the epoxide moiety proceeds under basic conditions to give products in high yield and with good to excellent regioselectivity. The major ring-opened products possess the arabino stereochemistry, and thus this methodology constitutes a new approach for the synthesis of arabinofuranosides. In the epoxide opening reactions of glycosides with the 2,3-anhydro-beta-D-lyxo stereochemistry (e.g., 73), the addition of (-)-sparteine (78) to the reaction mixture dramatically enhanced the regioselectivity in favor of the arabino product. This represents the first example of the use of 78 to influence the regioselectivity of an epoxide ring opening reaction with a non-carbon nucleophile. We have demonstrated the utility of this methodology through the efficient synthesis of an arabinofuranosyl hexasaccharide, 7, which is a key structural motif in two mycobacterial cell wall polysaccharides.

In memory of Dr.D ouglas Cerasoli, ab eloved colleague and friend, who worked tirelessly to improve medical countermeasures against organophosphorus chemicaln erve agentsa tt he US Army MedicalR esearch Institute of ChemicalD efense and who left his family, friends and colleagues too early in life