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1.
Org Lett ; 20(3): 788-791, 2018 02 02.
Article in English | MEDLINE | ID: mdl-29337569

ABSTRACT

The first total synthesis of the highly N-methylated acetylene-containing lipopeptide jahanyne, an apoptosis-inducing natural product from marine cyanobacteria, is reported. A late-stage solution-phase coupling enabled introduction of the C-terminal ketone pyrrolidine moiety. A modified Fmoc solid-phase synthesis strategy was adopted to effectively couple multiple sterically hindered N-methylated amino acids while suppressing epimerization. The total synthesis has enabled confirmation of the proposed absolute configuration of natural jahanyne.


Subject(s)
Lipopeptides/chemical synthesis , Acetylene , Amino Acids , Molecular Structure , Solid-Phase Synthesis Techniques
2.
Org Biomol Chem ; 15(30): 6302-6305, 2017 Aug 02.
Article in English | MEDLINE | ID: mdl-28678242

ABSTRACT

We developed a novel methodology using cyclic α,α-disubstituted α-amino acids (dAAs) with an acetal-side chain to control peptide secondary structures. The introduction of cyclic dAAs into peptides contributed to the stabilization of peptide secondary structures as a helix, while an acidic treatment of peptides resulted in a marked conformational change.


Subject(s)
Oligopeptides/chemistry , Acetals/chemistry , Hydrogen-Ion Concentration , Protein Structure, Secondary
3.
Open AIDS J ; 8: 7-16, 2014.
Article in English | MEDLINE | ID: mdl-24707325

ABSTRACT

Population-based surveys with HIV testing in settings with low testing coverage provide opportunities for participants to learn their HIV status. Survey participants (15-64 years) in a 2007 nationally representative population-based HIV serologic survey in Kenya received a voucher to collect HIV test results at health facilities 6 weeks after blood draw. Logistic regression models were fitted to identify predictors of individual and couple collection of results. Of 15,853 adults consenting to blood draw, 7,222 (46.7%) collected HIV test results (46.5% men, 46.8% women). A third (39.5%) of HIV-infected adults who were unaware of their infection and 48.2% of those who had never been tested learned their HIV status during KAIS. Individual collection of HIV results was associated with older age, with the highest odds among adults aged 60-64 years (adjusted odds ratio [AOR], 1.6, 95% confidence interval [CI] 1.2-2.1); rural residence (AOR 1.8, 95%CI 1.2-2.6); and residence outside Nairobi, with the highest odds in the sparsely populated North Eastern province (AOR 8.0, 95%CI 2.9-21.8). Of 2,685 married/cohabiting couples, 18.5% collected results as a couple. Couples in Eastern province and in the second and middle wealth quintiles were more likely to collect results than those in Nairobi (AOR 3.2, 95%CI 1.1-9.4) and the lowest wealth quintile (second AOR 1.5, 95%CI 1.1-2.3; middle AOR 1.6, 95% CI 1.2-2.3, respectively. Many participants including those living with HIV learned their HIV status in KAIS. Future surveys need to address low uptake of results among youth, urban residents, couples and those with undiagnosed HIV infection.

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