The present partial report of the research project documents the basic resin tests made. During a first test section, the softening temperatures of potentially suitable resin/hardener systems were determined by means of torsional oscillation tests. As a result of these tests, 4 systems were selected for more detailed investigations in the second test section. These additional tests comprised the determination of strength (tensile, compression, and shear) and determination of the associated elongations and elastic moduli in the tensile and compression tests. (orig./RHM)Der vorliegende Teilbericht des Forschungsvorhabens dokumentiert Harzgrundlagenuntersuchungen. In einem ersten Versuchsabschnitt wurden mit Hilfe von Torsionsschwingversuchen die Erweichungstemperaturen geeignet erscheinender Harz/Haertersysteme ermittelt. Als Ergebnis dieser Versuche wurden 4 Systeme fuer die weitergehende Untersuchung im zweiten Versuchsabschnitt ausgewaehlt. Diese weiteren Versuche umfassten die Ermittlung der Festigkeiten (Zug-, Druck-und Scherfestigkeit) sowie bei den Zug- und Druckversuchen die zugehoerigen Dehnungen und der Elastizitaetsmodule. (orig./RHM)Available from TIB Hannover: RO 5657(87-11)+a / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEBundesministerium fuer Forschung und Technologie (BMFT), Bonn (Germany)DEGerman

Jeffery E. Raymond (1279776)

Mathew
P. Robin (1293354)

Rachel K. O’Reilly (1293360)

Shani A. M. Osborne (1422709)

Zoe Pikramenou (796791)

PubMed

Block copolymer micelles have been prepared with a dithiomaleimide (DTM) fluorophore located in either the core or shell. Poly(triethylene glycol acrylate)-b-poly(tertbutyl acrylate) (P(TEGA)-b-P(tBA)) was synthesized by RAFT polymerization, with a DTM-functional acrylate monomer copolymerized into either the core forming P(tBA) block or the shell forming P(TEGA) block. Self-assembly by direct dissolution afforded spherical micelles with Rh of ca. 35 nm. Core-labeled micelles (CLMs) displayed bright emission (Φf = 17%) due to good protection of the fluorophore, whereas shell-labeled micelles (SLMs) had lower efficiency emission due to collisional quenching in the solvated corona. The transition from micelles to polymer unimers upon dilution could be detected by measuring the emission intensity of the solutions. For the core-labeled micelles, the fluorescence lifetime was also responsive to the supramolecular state, the lifetime being significantly longer for the micelles (τAv,I = 19 ns) than for the polymer unimers (τAv,I = 9 ns). The core-labeled micelles could also self-report on the presence of a fluorescent hydrophobic guest molecule (Nile Red) as a result of Förster resonance energy transfer (FRET) between the DTM fluorophore and the guest. The sensitivity of the DTM fluorophore to its environment therefore provides a simple handle to obtain detailed structural information for the labeled polymer micelles. A case will also be made for the application superiority of core-labeled micelles over shell-labeled micelles for the DTM fluorophore

Robin, Mathew

Osborne, Shani

Pikramenou, Zoe

Raymond, Jeffery E.

O'Reiley, Rachel

University of Birmingham Research Portal

  Fluorescent block copolymer micelles that can self-report on their assembly and small moleculeencapsulationPikramenou, Zoe; Osborne, Shani; Robin, Mathew; O'Reiley, RachelDOI:10.1021/acs.macromol.5b02152License:None: All rights reservedDocument VersionPeer reviewed versionCitation for published version (Harvard):Pikramenou, Z, Osborne, S, Robin, M & O'Reiley, R 2016, 'Fluorescent block copolymer micelles that can self-report on their assembly and small molecule encapsulation', Macromolecules, vol. 49, pp. 653.https://doi.org/10.1021/acs.macromol.5b02152Link to publication on Research at Birmingham portalPublisher Rights Statement:Eligibility for repository: Checked on 4/5/2016General rightsUnless a licence is specified above, all rights (including copyright and moral rights) in this document are retained by the authors and/or thecopyright holders. The express permission of the copyright holder must be obtained for any use of this material other than for purposespermitted by law.•	Users may freely distribute the URL that is used to identify this publication.•	Users may download and/or print one copy of the publication from the University of Birmingham research portal for the purpose of privatestudy or non-commercial research.•	User may use extracts from the document in line with the concept of ‘fair dealing’ under the Copyright, Designs and Patents Act 1988 (?)•	Users may not further distribute the material nor use it for the purposes of commercial gain.Where a licence is displayed above, please note the terms and conditions of the licence govern your use of this document.When citing, please reference the published version.Take down policyWhile the University of Birmingham exercises care and attention in making items available there are rare occasions when an item has beenuploaded in error or has been deemed to be commercially or otherwise sensitive.If you believe that this is the case for this document, please contact UBIRA@lists.bham.ac.uk providing details and we will remove access tothe work immediately and investigate.Download date: 01. Feb. 2019 S1 Supporting Information Fluorescent block copolymer micelles that can self-report on their assembly and small molecule encapsulation Mathew P. Robin,† Shani A. M. Osborne,‡ Zoe Pikramenou,‡ Jeffery E. Raymond,§ and Rachel K. O’Reilly*† † University of Warwick, Department of Chemistry, Gibbet Hill Road, Coventry, CV4 7AL, UK ‡ School of Chemistry, The University of Birmingham, Edgbaston, B15 2TT, UK § Department of Chemistry and Laboratory for Synthetic-Biologic Interactions, Texas A&M University, College Station, Texas 77842-3012, USA     S2 TABLE OF CONTENTS TITLE …………………………………………………………………………………………...1 LIST OF AUTHORS ……………………………………………………………………………1 TABLE OF CONTENTS ................................................................................................................ 2 SUPPLEMENTARY TABLES ...................................................................................................... 3 SUPPLEMENTARY FIGURES ..................................................................................................... 4 Figure S1. .................................................................................................................................... 4 Figure S2. .................................................................................................................................... 5 Figure S3. .................................................................................................................................... 6 Figure S4. .................................................................................................................................... 7 Figure S5. .................................................................................................................................... 8 Figure S6. .................................................................................................................................... 9 Figure S7. .................................................................................................................................. 10 Figure S8. .................................................................................................................................. 11 Figure S9. .................................................................................................................................. 12 Figure S10. ................................................................................................................................ 12 REFERENCES ............................................................................................................................. 13     S3 SUPPLEMENTARY TABLES  Table S1. Composition of solutions for FRET experiments shown in Figure 8. Figure 8a 5 NR H2O 1,4-dioxane Time after mixing CLMs (t = 0) 82.8 µg, 2.5 nmol - 2.5 ml -a - CLMs + NR (t = 1) 82.8 µg, 2.5 nmol 80 ng, 0.25 nmol 2.5 ml 2.5 µl 1 min CLMs + NR (t = 60) 82.8 µg, 2.5 nmol 80 ng, 0.25 nmol 2.5 ml 2.5 µl 60 min NR - 80 ng, 0.25 nmol 2.5 ml 2.5 µl - Figure 8c 3 NR H2O 1,4-dioxane Time after mixing NLMs (t = 0) 79.9 µg, 2.5 nmol - 2.5 ml - - NLMs + NR (t = 1) 79.9 µg, 2.5 nmol 80 ng, 0.25 nmol 2.5 ml 2.5 µl 1 min NLMs + NR (t = 60) 79.9 µg, 2.5 nmol 80 ng, 0.25 nmol 2.5 ml 2.5 µl 60 min NR - 80 ng, 0.25 nmol 2.5 ml 2.5 µl - Figure 8d 5 RhB H2O Time after mixing  CLMs (t = 0) 82.8 µg, 2.5 nmol - 2.5 ml -  CLMs + RhB (t = 1) 82.8 µg, 2.5 nmol 120 ng, 0.25 nmol 2.5 ml 1 min  CLMs + RhB (t = 60) 82.8 µg, 2.5 nmol 120 ng, 0.25 nmol 2.5 ml 60 min  RhB - 120 ng, 0.25 nmol 2.5 ml -  a The addition of 2.5 µl of 1,4-dioxane to CLMs was found to have no effect on the emission spectrum (see Figure S10).   S4 SUPPLEMENTARY FIGURES  Figure S1. 1H NMR spectrum (400 MHz, CDCl3) of P(tBA) (1). Integration of H1 was set to be equal to 3.00.      S5 Figure S2. 1H NMR spectrum (400 MHz, CDCl3) of P(tBA-co-DTMA) (2). Integration of H1 was set to be equal to 3.00.      S6 Figure S3. Three-dimensional chromatogram of 2 obtained by SEC using a PDA detector and THF as eluent.     S7 Figure S4. 1H NMR spectrum (400 MHz, CDCl3) of P(TEGA)-b-P(tBA) (3). Combined integration of H2,3,5,5’,6,6’,12,13 was set to be equal to the combined integration of H4&11 + (558.5-7.8-2).     S8 Figure S5. 1H NMR spectrum (400 MHz, CDCl3) of P(TEGA-co-DTMA)-b-P(tBA) (4). Integration of H1 was set to be equal to 3.00.     S9 Figure S6. 1H NMR spectrum (400 MHz, CDCl3) of P(TEGA-co-DTMA)-b-P(tBA) (5). Combined integration of H1&H4 was set to be equal to 8.95.     S10 Figure S7. Plots to determine D (left hand side) and plots to determine Mw (right hand side) for; a & b) SLMs; c & d) CLMs; e & f) NLMs.     S11 Figure S8. FLIM image of the thin film formed from a) 4 micelles (SLMs); and b) 5 micelles (CLMs). Scale bars = 200 µm.      S12 Figure S9. Emission at 515 nm and 610 nm of CLMs for the first 30 s after addition of NR. λex = 422 nm.   Figure S10. Emission spectra of CLMs (2.5 ml, [DTM] =1 µM) before and after the addition of 2.5 µl 1,4-dioxane.     S13 REFERENCES  (1) Hua, F.; Jiang, X.; Li, D.; Zhao, B. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 2454.  (2) Robin, M. P.; O'Reilly, R. K. Chem. Sci. 2014, 5, 2717.  (3) Nicolai, T.; Brown, W.; Johnsen, R. M.; Stepanek, P. Macromolecules 1990, 23, 1165.  (4) Colombani, O.; Ruppel, M.; Burkhardt, M.; Drechsler, M.; Schumacher, M.; Gradzielski, M.; Schweins, R.; Müller, A. H. E. Macromolecules 2007, 40, 4351.  (5) Esker, A. R.; Mengel, C.; Wegner, G. Science 1998, 280, 892.  

Fluorescent block copolymer micelles that can self-report on their assembly and small molecule encapsulation

Block copolymer micelles have been prepared with a dithiomaleimide (DTM) fluorophore located in either the core or shell. Poly(triethylene glycol acrylate)-b-poly(tert-butyl acrylate) (P(TEGA)-b-P(tBA)) was synthesized by RAFT polymerization, with a DTM-functional acrylate monomer copolymerized into either the core forming P(tBA) block or the shell forming P(TEGA) block. Self-assembly by direct dissolution afforded spherical micelles with Rh of ca. 35 nm. Core-labeled micelles (CLMs) displayed bright emission (Φf = 17%) due to good protection of the fluorophore, whereas shell-labeled micelles (SLMs) had lower efficiency emission due to collisional quenching in the solvated corona. The transition from micelles to polymer unimers upon dilution could be detected by measuring the emission intensity of the solutions. For the core-labeled micelles, the fluorescence lifetime was also responsive to the supramolecular state, the lifetime being significantly longer for the micelles (τAv,I = 19 ns) than for the polymer unimers (τAv,I = 9 ns). The core-labeled micelles could also self-report on the presence of a fluorescent hydrophobic guest molecule (Nile Red) as a result of Förster resonance energy transfer (FRET) between the DTM fluorophore and the guest. The sensitivity of the DTM fluorophore to its environment therefore provides a simple handle to obtain detailed structural information for the labeled polymer micelles. A case will also be made for the application superiority of core-labeled micelles over shell-labeled micelles for the DTM fluorophore

Robin, Mathew P.

Osborne, Shani A. M.

O’Reilly, Rachel K.

Warwick Research Archives Portal Repository

Block copolymer micelles have been
prepared with a dithiomaleimide
(DTM) fluorophore located in either the core or shell. Poly­(triethylene
glycol acrylate)-b-poly­(tert-butyl
acrylate) (P­(TEGA)-b-P­(tBA)) was
synthesized by RAFT polymerization, with a DTM-functional acrylate
monomer copolymerized into either the core forming P­(tBA) block or the shell forming P­(TEGA) block. Self-assembly by direct
dissolution afforded spherical micelles with Rh of ca. 35 nm. Core-labeled micelles (CLMs)
displayed bright emission (Φf = 17%) due to good
protection of the fluorophore, whereas shell-labeled micelles (SLMs)
had lower efficiency emission due to collisional quenching in the
solvated corona. The transition from micelles to polymer unimers upon
dilution could be detected by measuring the emission intensity of
the solutions. For the core-labeled micelles, the fluorescence lifetime
was also responsive to the supramolecular state, the lifetime being
significantly longer for the micelles (τAv,I = 19
ns) than for the polymer unimers (τAv,I = 9 ns).
The core-labeled micelles could also self-report on the presence of
a fluorescent hydrophobic guest molecule (Nile Red) as a result of
Förster resonance energy transfer (FRET) between the DTM fluorophore
and the guest. The sensitivity of the DTM fluorophore to its environment
therefore provides a simple handle to obtain detailed structural information
for the labeled polymer micelles. A case will also be made for the
application superiority of core-labeled micelles over shell-labeled
micelles for the DTM fluorophore

FigShare

Fluorescent Block Copolymer Micelles That Can Self-Report
on Their Assembly and Small Molecule Encapsulation

Mathew P. Robin

Shani A. M. Osborne

Zoe Pikramenou

Jeffery E. Raymond

Rachel K. O’Reilly

Crossref

Macromolecules

Fluorescent Block Copolymer Micelles That Can Self-Report on Their Assembly and Small Molecule Encapsulation

Kossira, H.

Pohl, H.W.

Technische Univ. Braunschweig (Germany). Inst. fuer Flugzeugbau und Leichtbau

OpenGrey Repository