Learning the chemistry of compounds containing carbonyl groups is difficult for undergraduate students partly because of a convolution of multiple possible reaction sites, competitive reactions taking place at those sites, different criteria needed to discern between the mechanisms of these reactions, and no straightforward selection method applicable to all. Factual inaccuracies in some recently used comprehensive introductory organic chemistry textbooks can distract and confuse students. Student interest, combined with some inconsistencies, prompted a systematic comparison of these textbooks, enabling some suggestions for improvement. Students also selected a preferred order of presentation in which carbonyl chemistry should appear for optimal learning: carboxylic acids, aldehydes, ketones, carboxylic acid derivatives, α,β-unsaturated carbonyls, and carbonyl compounds that undergo enol chemistry. This ordering is generally based on a combination of (1) grouping according to the purpose of the functional group, (2) increasing complexity of reactions with a nucleophile, and (3) decreasing carbonyl compound reactivity. In order to facilitate solving carbonyl chemistry problems and understanding these competing factors, information about the reactions is presented in three forms: a text discussion, a Summary Sheet, and a Decision Tree. The recommendations are consistent, descriptive, and pedagogically useful, and they should remedy many discrepancies.

In order to quantify and study the complexation of small organic amine molecules with SWCNTs, the effect of SWCNT association upon their proton NMR spectra was studied. Results reveal that (1) a greater magnitude of chemical shift change for α protons to the amino group upon SWCNT association suggests close proximity of the amine nitrogen to SWCNTs except for the pyridines, (2) tertiary amines associate strongly with SWCNTs due to the inductive effect outweighing the steric effect of their alkyl parts, (3) in secondary amines, the steric effect overpowers the inductive effect resulting in their weaker interaction than tertiary amines with SWCNTs, (4) introduction of an alkyl substituent at the α position in primary amines results in more effective SWCNT association than at the amino nitrogen in secondary amines, (5) aromatic amines associate more strongly than aliphatic ones due to availability of more points of association, and (6) pyridines seem to interact via their π-electron cloud.

We report the synthesis and characterization of a tamoxifen-tethered single-walled carbon nanotube (SWCNT) conjugate, in which tamoxifen is covalently attached to the single-walled carbon nanotube via oxidation and esterification reactions for the first time. The functionalized SWCNT derivative was characterized by using spectroscopic techniques: IR, UV–vis, Raman, and 1H NMR Spectroscopy. The attachment of the drug tamoxifen to SWCNTs is analogous to the gold conjugate, which provided an endocrine treatment for breast cancer.

Proper purity characterization of single-walled carbon nanotubes (SWCNTs) is an increasingly hot topic in the area of carbon nanotechnology. There are inconsistencies in purity characterization of SWCNT from manufacturers and in the literature. Purity of “as received,” oven dried, and NaHCO3-washed SWCNTs of three commercially available brands (NanoLab, SWeNT, and HiPco) is explored by using a consistent methodology via proton nuclear magnetic resonance (1H NMR) spectroscopy comparison, across three NMR solvents: DMSO-d6, CDCl3, and D2O. Important insights into the purity of commercially available SWCNT and the importance of washing (cleaning) samples before use are offered.

This report is important to achieving single-walled carbon nanotube (SWCNT) solvation, understanding adsorption of molecules on SWCNT surfaces, and SWCNT characterization by NMR. Complexation of 1-methyl-2-pyrrolidone and other selected organonitrogens with SWCNTs was studied by proton NMR. The magnitude of 1H NMR chemical shift change upon SWCNT:organonitrogen complex formation represents the strength of the association. Magnitudes of changes in NMR signals of different protons in the organonitrogen reveal which protons are in close proximity to SWCNTs. Results reveal that (1) in amides and aminoketones SWCNT association with carbonyls is stronger than with nitrogen, (2) in aminoalcohols SWCNT association with nitrogen is stronger than with oxygen, and (3) protons bonded to heteroatoms have greater changes in their chemical shifts than those bonded to carbons. Changes (broadening and downfield shifts) in 1H NMR signals of the organonitrogen compounds, which accompany SWCNT:organonitrogen association, are dependent upon (1) type of proton within R (α, β, etc.), (2) proximity to the carbonyl (R-CO versus NR2), (3) steric effects of alkyls, (4) electronic effects of alkyls, and (5) effects of tethering two ends of a molecule.

Select amides have been widely used to suspend nanoarchitectures in organic solvents. In order to determine factors enabling these suspensions, interactions of single-walled carbon nanotubes (SWCNTs) with representative amides 1 were examined—R(C═O)NMe2, when R = H, Me, Et, i-Pr, t-Bu, Ph. 1H NMR spectra gave evidence for two types of SWCNT: amide associations, formed after evaporation of the reaction mixture to either a concentrated solution or a wet paste, followed by sonication in NMR solvent. NMR spectra of SWCNTs associated with 1 (SWCNT:1) after evaporation to concentrated solution show broadening and small downfield changes, suggesting weak interactions. Evaporation of SWCNT:1 to a wet paste causes larger spectral changes, predominantly in aldehydic and α proton signals. These are often 10 times those in concentrated solution, especially when R has small steric requirements, which suggests a stronger interaction of 1 with SWCNTs under wet paste conditions. 1H NMR signal changes of 1, which accompany SWCNT:1 association, depend upon (1) degree of evaporation of residual amide and organic solvent, (2) organic and NMR solvent combination, (3) type of proton in R, (4) proximity effects to the carbonyl (R versus NMe2), and (5) steric requirements of R.