A self-immolative spacer that enables tunable controlled release of phenols under neutral conditions

Kyle M. Schmid, Lasse Jensen, Scott T. Phillips

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

A current challenge in the area of responsive materials is the design of reagents and polymers that provide controlled release of phenols in environments that are less polar than water. In these contexts, a molecular strategy that enables release of nearly any phenol with predictable and tunable rates and without complication from background hydrolysis would substantially increase the precision with which materials can be designed to respond to a particular signal. This Article addresses this problem at the fundamental level by describing the design, synthesis, and physical-organic characterization of two small molecule self-immolative spacers that are capable of releasing phenols in organic and mixed organic-aqueous solutions. The rate of release from these small molecule model systems is predictable and tunable, such that nearly any type of phenol, regardless of pK a value, can be released in neutral solutions without complications from nonspecific background release due to hydrolysis. Furthermore, the release properties of the spacers can be predicted from bond length and conformation data (obtained from crystal structures). On the basis of these results, it should now be possible to incorporate these design elements into materials to enable precise response properties in environments that are not 100% aqueous.

Original languageEnglish (US)
Pages (from-to)4363-4374
Number of pages12
JournalJournal of Organic Chemistry
Volume77
Issue number9
DOIs
StatePublished - May 4 2012

Fingerprint

Phenols
Phenol
Hydrolysis
Molecules
Bond length
Conformations
Polymers
Crystal structure
Water

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

@article{97280974f4f64924b9b6d776863f1542,
title = "A self-immolative spacer that enables tunable controlled release of phenols under neutral conditions",
abstract = "A current challenge in the area of responsive materials is the design of reagents and polymers that provide controlled release of phenols in environments that are less polar than water. In these contexts, a molecular strategy that enables release of nearly any phenol with predictable and tunable rates and without complication from background hydrolysis would substantially increase the precision with which materials can be designed to respond to a particular signal. This Article addresses this problem at the fundamental level by describing the design, synthesis, and physical-organic characterization of two small molecule self-immolative spacers that are capable of releasing phenols in organic and mixed organic-aqueous solutions. The rate of release from these small molecule model systems is predictable and tunable, such that nearly any type of phenol, regardless of pK a value, can be released in neutral solutions without complications from nonspecific background release due to hydrolysis. Furthermore, the release properties of the spacers can be predicted from bond length and conformation data (obtained from crystal structures). On the basis of these results, it should now be possible to incorporate these design elements into materials to enable precise response properties in environments that are not 100{\%} aqueous.",
author = "Schmid, {Kyle M.} and Lasse Jensen and Phillips, {Scott T.}",
year = "2012",
month = "5",
day = "4",
doi = "10.1021/jo300400q",
language = "English (US)",
volume = "77",
pages = "4363--4374",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "9",

}

A self-immolative spacer that enables tunable controlled release of phenols under neutral conditions. / Schmid, Kyle M.; Jensen, Lasse; Phillips, Scott T.

In: Journal of Organic Chemistry, Vol. 77, No. 9, 04.05.2012, p. 4363-4374.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A self-immolative spacer that enables tunable controlled release of phenols under neutral conditions

AU - Schmid, Kyle M.

AU - Jensen, Lasse

AU - Phillips, Scott T.

PY - 2012/5/4

Y1 - 2012/5/4

N2 - A current challenge in the area of responsive materials is the design of reagents and polymers that provide controlled release of phenols in environments that are less polar than water. In these contexts, a molecular strategy that enables release of nearly any phenol with predictable and tunable rates and without complication from background hydrolysis would substantially increase the precision with which materials can be designed to respond to a particular signal. This Article addresses this problem at the fundamental level by describing the design, synthesis, and physical-organic characterization of two small molecule self-immolative spacers that are capable of releasing phenols in organic and mixed organic-aqueous solutions. The rate of release from these small molecule model systems is predictable and tunable, such that nearly any type of phenol, regardless of pK a value, can be released in neutral solutions without complications from nonspecific background release due to hydrolysis. Furthermore, the release properties of the spacers can be predicted from bond length and conformation data (obtained from crystal structures). On the basis of these results, it should now be possible to incorporate these design elements into materials to enable precise response properties in environments that are not 100% aqueous.

AB - A current challenge in the area of responsive materials is the design of reagents and polymers that provide controlled release of phenols in environments that are less polar than water. In these contexts, a molecular strategy that enables release of nearly any phenol with predictable and tunable rates and without complication from background hydrolysis would substantially increase the precision with which materials can be designed to respond to a particular signal. This Article addresses this problem at the fundamental level by describing the design, synthesis, and physical-organic characterization of two small molecule self-immolative spacers that are capable of releasing phenols in organic and mixed organic-aqueous solutions. The rate of release from these small molecule model systems is predictable and tunable, such that nearly any type of phenol, regardless of pK a value, can be released in neutral solutions without complications from nonspecific background release due to hydrolysis. Furthermore, the release properties of the spacers can be predicted from bond length and conformation data (obtained from crystal structures). On the basis of these results, it should now be possible to incorporate these design elements into materials to enable precise response properties in environments that are not 100% aqueous.

UR - http://www.scopus.com/inward/record.url?scp=84860648744&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84860648744&partnerID=8YFLogxK

U2 - 10.1021/jo300400q

DO - 10.1021/jo300400q

M3 - Article

C2 - 22494313

AN - SCOPUS:84860648744

VL - 77

SP - 4363

EP - 4374

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 9

ER -