Fibers made by assembly of emulsion droplets

Fibers are interesting. They are made by a spinning process in which a liquid based mixture, referred to as spinning dope, is extruded through an orifice hereby generating a jet, which subsequently is solidified through either coagulation/precipitation and/or gelation. Two extreme fibers found in Nature are spidersilk, a super strong and extensible liquid-crystalline fiber, and the soft hydrogel double-strings of toad eggs, as spawn by the common toad (Bufo bufo). The production of manmade fibers using dry and wet spinning techniques – both starting from a liquid mixture – goes back to the 19th century. An early example is the development of Rayon fibers initiated by the discovery of Schweizer in 1857, who found that cellulose could be dissolved in and re-precipitated from an aqueous solution of ammonia and copper (II) hydroxide (coined Schweizer’s reagent (dry or wet)). Examples of wet-spun high performance fibers include ultrahigh molecular weight poly(ethylene) fibers, and polyaramid fibers.

An emerging trend is to make soft, hydrogel-based, fibers wet spun into water. Applications for example are in the area of tissue engineering. Microfluidic technologies are often employed to manufacture these fibers.

 

We asked ourselves whether it would be possible to fabricate fibers through assembly of thousands of emulsion droplets? We call these HIPE (High Internal Phase Emulsion) fibers.

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     Fig.  (a) Schematic representation of the fabrication of microfluidically spun HIPE fiber. The diagram shows coaxial flow channels in the microfluidic device, where the inner and outer capillaries contain concentrated emulsion and acidic water, respectively, in a continuous flow. A continuous HIPE fiber is produced upon exposure of the emulsion to the acidic water. The acidic conditions allow the formation of multiple hydrogen bonds between emulsion droplets, initiating them to assemble into a macroscopic supracolloidal fiber. (b) Photograph of a HIPE fiber in acidic aqueous solution (top left), and disintegration into individual dispersed emulsion droplets upon addition of base (top right). Scale bars represent 1 cm. Light micrographs of the HIPE fiber in acidic condition (bottom left) and disintegrated HIPE fiber in basic condition (bottom right). Scale bars represent 50 µm and 25 µm, respectively. (c) Photograph of HIPE fibers with uniform length. The HIPE fibers with uniform length were fabricated by utilizing air bubbles as a cutting mechanism. Scale bar represents 0.5 cm. (d) Photograph of asymmetric Janus HIPE fiber. Scale bars represent 0.1 cm (top) and 300 µm (bottom). (e) Photograph of asymmetric HIPE fiber consisting of three different sections ‘toothpaste’. Scale bars represent 0.1 cm (top) and 300 µm (bottom). (f) Photograph of magnetic HIPE fiber attracted by an external magnet (fiber with a slight yellow color - left hand side), and no magnetic response with the non-magnetic HIPE fiber (white color fiber - right hand side). Scale bar represents 1 cm.

Fig. (a) Schematic representation of the fabrication of microfluidically spun HIPE fiber. The diagram shows coaxial flow channels in the microfluidic device, where the inner and outer capillaries contain concentrated emulsion and acidic water, respectively, in a continuous flow. A continuous HIPE fiber is produced upon exposure of the emulsion to the acidic water. The acidic conditions allow the formation of multiple hydrogen bonds between emulsion droplets, initiating them to assemble into a macroscopic supracolloidal fiber. (b) Photograph of a HIPE fiber in acidic aqueous solution (top left), and disintegration into individual dispersed emulsion droplets upon addition of base (top right). Scale bars represent 1 cm. Light micrographs of the HIPE fiber in acidic condition (bottom left) and disintegrated HIPE fiber in basic condition (bottom right). Scale bars represent 50 µm and 25 µm, respectively. (c) Photograph of HIPE fibers with uniform length. The HIPE fibers with uniform length were fabricated by utilizing air bubbles as a cutting mechanism. Scale bar represents 0.5 cm. (d) Photograph of asymmetric Janus HIPE fiber. Scale bars represent 0.1 cm (top) and 300 µm (bottom). (e) Photograph of asymmetric HIPE fiber consisting of three different sections ‘toothpaste’. Scale bars represent 0.1 cm (top) and 300 µm (bottom). (f) Photograph of magnetic HIPE fiber attracted by an external magnet (fiber with a slight yellow color - left hand side), and no magnetic response with the non-magnetic HIPE fiber (white color fiber - right hand side). Scale bar represents 1 cm.

In our paper published in the Journal of Materials Chemistry A we show the fabrication of fibers from emulsion droplets. We use flow-focussing microfluidic set-up whereby a generated jet of emulsion droplets stabilized by amphiphilic pH-responsive branched copolymers (pH-BCP) and reinforced by Laponite clay discs is exposed to an external surrounding liquid flow of lower pH. Proton diffusion into the stream of emulsion droplets induces the self-assembly process leading to the formation of a continuous supracolloidal fiber. We demonstrate that the fiber can disintegrate back into an oil-in-water emulsion. We discuss control of fiber composition hereby using two and three combined streams of emulsion droplets to generate Janus fibers, and using ferrofluids to produce magnetic fibers. We show control of fiber length by employing air bubbles as a mean to produce short fibers of discrete length.  Looking towards applications we demonstrate the use of our supracolloidal emulsion droplet fibers as a material to control the delivery of volatile compounds through evaporation, and we show that the dried fibers are a nanocomposite highly porous and light material.

 

You can read the paper here: http://dx.doi.org/10.1039/C5TA08917D

Corinna Preuss awarded Newton International Fellowship

Dr Corinna Preuss has been awarded a Newton International Fellowship to conduct research at the University of Warwick’s Department of Chemistry.

Corinna Preuss

Corinna Preuss

Jointly run by The British Academy, The Academy of Medical Sciences and the Royal Society, the Fellowship is for non-UK scientists who are at an early stage of their research career and provides the opportunity for the best early stage post-doctoral researchers from all over the world to work at UK research institutions for a period of two years.

Speaking after being awarded the Fellowship Dr Preuss said:

I’m very honoured and delighted to be awarded the Newton International Fellowship. Not only will it support my personal development but is also emphasises the novelty and importance of our proposed research project.

Dr Preuss will work as part of a team led by Professor Stefan Bon to mimic the motional behaviour of zooplankton by fabricating artificial jelly-objects that have the capability to transform shape, swim, and – as an additional feature – release payloads. Dr Preuss says these hydrogel objects will have these three pre-programmed functions “which can be triggered on demand in a controlled fashion”. For this purpose, recent scientific advances in polymer and colloid chemistry will be merged with soft matter physics and robotics in order to create a promising and interdisciplinary research program

Further to the research with Professor Bon, Dr Preuss is keen to use the Fellowship to teach undergraduate chemists and to create a network with other fellow scientists, saying that: “In my opinion, exchanging knowledge and listening to different opinions is essential for the formation of a highly efficient scientific society”.

Discussing why she chose the University of Warwick Dr Preuss said:

I met Professor Stefan Bon during a conference in Mexico.I was impressed by his research and the passion he presented it with. Later on, whilst I was presenting my research at the poster session, we got the chance to chat more and discovered that our interests in each other’s research would create a promising base for a further collaboration. In working with Stefan and coming to the University of Warwick, I’m taking the chance of changing my field of research to colloidal chemistry and engineering, which provides a new, challenging and fascinating area for me”.

Contacts:

Tom Frew - International Press Officer

Email: a.t.frew@warwick.ac.uk

Tel: +44 (0)247 657 5910

Mob: +44 (0)7785 433 155

Ross Jaggers invited to participate in the Stonewall Young Leaders Programme

Ross Jaggers, a second year PhD student in the research group of prof.dr.ir. Stefan Bon (BonLab) in the Department of Chemistry at the University of Warwick, has been invited to attend the Stonewall Young Leaders Programme in London this coming September. The programme, sponsored by Bank of America Merrill Lynch, explores how sexual orientation and gender identity relates to the workplace and career aspirations, as well as inspiring participants to think about their impact on others as young LGBT leaders and role models.

Ross Jaggers

Ross Jaggers

 

For more information on Stonewall, the UK’s leading LGBT rights charity, visit www.stonewall.org.uk.

 

Control of vesicle membrane permeability with catalytic particles

The ability to control membrane permeability in vesicles allows for regulated transport of matter across the vesicular wall. Vesicles can be seen as microscopic sacs containing a compartmentalized volume of liquid dispersed in a bulk liquid environment. Compartmentalization of small and finite volumes of liquid and consecutive the emergence of membrane bioenergetics are identified as being of key importance in the evolution of cells, and hence the origin of life. Nature has devised sophisticated strategies to accomplish control of transmembrane transport, including endo- and exocytosis as well as the incorporation of transmembrane proteins into cell membranes. A variety of synthetic approaches have been explored by scientists in order to accomplish such control in manmade systems. Examples include hybrid systems whereby transmembrane proteins were incorporated as part of synthetic vesicles, and the use of responsive macromolecular building blocks to regulate membrane porosity upon an external trigger in polymer vesicles, also referred to as polymersomes.

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	mso-fareast-language:ZH-CN;}     Dark field microscopy image of polymer vesicles which contain manganese oxide colloidal particles in their membranes, pre-loaded with barium ions and dispersed in water (containing sulfate anions)  after their exposure to a low external concentration of hydrogen peroxide. The white haze surrounding the vesicles and the white tails are the result of the precipitation of barium sulfate crystals upon release of the barium cations from the vesicles.  Scale bar: 100 μm 

Dark field microscopy image of polymer vesicles which contain manganese oxide colloidal particles in their membranes, pre-loaded with barium ions and dispersed in water (containing sulfate anions)  after their exposure to a low external concentration of hydrogen peroxide. The white haze surrounding the vesicles and the white tails are the result of the precipitation of barium sulfate crystals upon release of the barium cations from the vesicles.  Scale bar: 100 μm 

In our recent paper published in Materials Horizons we show for the first time that the permeability of the membrane of polymer vesicles can be controlled by membrane-embedded catalytically active manganese oxide particles. The ability to chemically trigger activity of the catalytic particle, hereby inducing a temporary increase of membrane permeability, offers precise time-specific control of transmembrane transport. It is our belief that this concept can be applied to a wide variety of membrane-based systems. At the end of the paper we open a disccusion for the origins of life and protocell communities  that a hybrid vesicular structure, which has “active” colloidal particles as part of its membrane, may have regulated permeability in primitive cells.

to read the paper: http://dx.doi.org/10.1039/C5MH00093A

A Mechanistic Insight into the Synthesis of Silica-Based “Matchstick” Colloids

In the field of colloid science the ability to fabricate particles with a defined shape, other than a sphere, has gained attention. The reason is that anisotropy in shape and/or chemical composition can lead to interesting physical properties when these particles are dispersed in a liquid, or when they form part of a product formulation. We report an insight into the synthesis of silica-based “matchstick”-shaped colloidal particles, which are of interest in the area of self-propulsion on small length scales. The generation of aqueous emulsion droplets dispersed in an n-pentanol-rich continuous phase and their use as reaction centers allows for the fabrication of siliceous microparticles that exhibit anisotropy in both particle morphology, that is, a “matchstick” shape, and chemistry, that is, a transition-metal oxide-enriched head. We provide a series of kinetic studies to gain a mechanistic understanding and unravel the particle formation and growth processes. Additionally, we demonstrate the ability to select the aspect ratio of the “matchstick” particle in a straightforward manner.

The paper is recently published in Langmuir. DOI:10.1021/acs.langmuir.5b02645

Fabrication of calcium phosphate microcapsules using emulsion droplets stabilized with branched copolymers as templates

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	mso-hansi-theme-font:minor-latin;}     SEM micrographs illustrating the mineralization of CaP at the surface of oil droplets stabilized with BCP. (A) Incubation periods of 0 hours (scale bar = 37 µm), (B) 48 hours (scale bar = 16 µm), (C) 60 hours (scale bar = 7 µm), (D and E) 72 hours (scale bars = 23 µm and 7 µm, respectively), (F) surface morphology of CaP capsule (scale bar = 704 nm), (G) CaP capsules annealed at 600 oC (scale bar = 2 µm), (H) surface morphology of CaP capsule after annealing at 600 oC (scale bar = 648 nm), and (I and J) shell thickness of the CaP capsules before annealing (scale bars = 1 µm and 540 nm, respectively).

SEM micrographs illustrating the mineralization of CaP at the surface of oil droplets stabilized with BCP. (A) Incubation periods of 0 hours (scale bar = 37 µm), (B) 48 hours (scale bar = 16 µm), (C) 60 hours (scale bar = 7 µm), (D and E) 72 hours (scale bars = 23 µm and 7 µm, respectively), (F) surface morphology of CaP capsule (scale bar = 704 nm), (G) CaP capsules annealed at 600 oC (scale bar = 2 µm), (H) surface morphology of CaP capsule after annealing at 600 oC (scale bar = 648 nm), and (I and J) shell thickness of the CaP capsules before annealing (scale bars = 1 µm and 540 nm, respectively).

Calcium phosphate based hybrid materials are of great interest for bio-related science, for example our bones and teeth contain mineral components made from calcium phosphate. One class of materials of great interest are microcapsules, as these can store and release active ingredients. Calcium phosphate microcapsules have been made before via a number of synthetic pathways. Key drawbacks however are tedious and long (up to a month) fabrication methods. In our paper published recently in the Journal of Materials Chemistry B we report on a versatile and time-efficient method to fabricate calcium phosphate (CaP) microcapsules by utilizing oil-in-water emulsion droplets stabilized with synthetic branched copolymer (BCP) as templates. The BCP was designed to provide a suitable architecture and functionality to produce stable emulsion droplets, and to permit the mineralization of CaP at the surface of the oil droplet when incubated in a solution containing calcium and phosphate ions. The CaP shells of the microcapsules were established to be calcium deficient hydroxyapatite with incorporated chlorine and carbonate species. These capsule walls were made fluorescent by decoration with a fluorescein-bisphosphonate conjugate.

To read the paper: DOI: 10.1039/C5TB00893J


IPCG 2015 Conference New Hampshire

Stefan Bon was the organising chair of the 2015 International Polymer Colloids Group Conference (IPCG) in New Hampshire (jun 28-jul 3). 110 conference delegates listened to and discussed a very exciting set of talks and posters. We would like to thank everybody for their contribution, as together we made it a fantastic event! 


The conference program was:


Monday, June 29 (NOTE: all talks will be at Paul College, G75 Auditorium)


6:30 - 8:00: BREAKFAST (Philbrook Dining Hall)

Conference Welcome

8:30 - 9:00: Introduction to Conference by Chairs
Stefan Bon (University of Warwick, UK), Chair 
Jose Ramon Leiza (University of the Basque Country, Spain), Co-Chair
Willie Lau (Oriental Yuhong, China), Co-Chair
John Tsavalas (University of New Hampshire, USA), Local Organizer

9:00 - 10:00: Carbon Dioxide Switchable Polymer Colloids
Michael Cunningham (Department of Chemical Engineering, Queen’s University, Canada)

10:00 - 10:30: Coffee Break

10:30 - 11:30: Guided Assembly of Polymer Nanoparticles in Soft Adhesives and Functional Coatings with Designed Structures
Joe Keddie (Department of Physics, University of Surrey, Guilford, UK)

11:30 - 12:30: Amphiphilic Core-Shell Latex Particles: Synthesis and Applications
Pauline Pei Li (Department of Applied Biology and Chemical Technology, the Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong)

12:30 - 1:30: LUNCH (Philbrook Dining Hall)

19:00 - 19:30: Controlling and understanding macromolecular and colloidal architectures
Nicholas Ballard (POLYMAT, University of the Basque Country UPV/EHU, Donostia-San Sebastián, Spain)

19:30 - 20:00: Directed Bimodal Synthesis: One reactor, two polymers
Gary Dombrowski (Principal Research Scientist, Dow Coating Materials, The Dow Chemical Company, Collegeville, PA USA)

20:00 - 21:00: Nanomaterials interfacing with the immune system
Darrell Irvine (Massachusetts Institute of Technology, Cambridge, MA USA)

21:30+: Socializing (Scorpions Bar & Grill, Main Street)


Tuesday, June 30 (NOTE: all talks will be at Paul College, G75 Auditorium)


6:30 - 8:00: BREAKFAST (Philbrook Dining Hall) 

8:30 - 9:30: Active and adaptive peptide nanostructures
Rein Ulijn (Director of the Nanoscience Initiative, CUNY Advanced Science Research Center, Department of Chemistry, Hunter College, New York, USA)

9:30 - 10:30: Macromolecular self-assembly based on carbohydrates
Gousong Chen (Department of Macromolecular Science, Fudan University, Shanghai, China)

10:30: Coffee Break

11:00 - 12:00: On-Line Monitoring and Study on Structural Evolution of Core/Shell Latex Particles during Synthesis Process
Xiaoyu Li (State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, China)

12:30 - 1:30: LUNCH (Phlibrook Dining Hall)

16:00 - 19:00: Poster Session, Wine Tasting Event, & Dinner (Huddleston Hall) 

19:30 - 20:00: Pickering (Mini)Emulsion Polymerization Using Graphene Oxide as Stabilizer: A Route to Hybrid Nanomaterials
Stuart Thickett (School of Physical Sciences, The University of Tasmania, Hobart, Australia)

20:00 - 20:30: A Model for the Evaporation of Water from Dispersions
Jim Taylor (BASF Advanced Materials and Systems Research, Wyandotte, MI USA)

20:30 - 21:30: Static and Dynamic Colloid-Based Bioinspired Materials
Andreas Walther (DWI- Leibniz-Institute for Interactive Materials, Aachen, Germany)

22:00+: Socializing (Scorpions Bar & Grill, Main Street)


Wednesday, July 1 (NOTE: all talks will be at Paul College, G75 Auditorium)


6:30 - 8:00: BREAKFAST (Philbrook Dining Hall) 

8:30 - 9:30: Designing self-regulating, self-propelled microcapsules
Anna Balazs (Chemical Engineering Department, University of Pittsburgh, Pittsburgh, USA)

9:30 - 10:30: Engineering shape: the novel geometries of colloidal self-assembly
Stefano Sacanna (Molecular Design Institute, Department of Chemistry, New York University, New York, USA)

10:30: Coffee Break

11:00 - 12:00: Janus Particles as Solid Surfactants
Daeyeon Lee (School of Engineering and Applied Sciences, University of Pennsylvania, Philadelphia, USA)

12:30 - 1:30: LUNCH (Philbrook Dining Hall)

16:00 - 18:00: IPCG Member Meeting


19:00 - 19:30: Colloidal particles at liquid interfaces: tuning interactions for self assembly
Adam Law (Max-Planck-Institut für Intelligente Systeme, Stuttgart, Germany)

19:30 - 20:00: Unresolved issues in the industrial application of polymer colloids in DSM
Ad Overbeek (Corporate Scientist, Polymer and Resin Chemistry, DSM Coating Resins, Waalwijk, Netherlands )

20:00 - 21:00: Organically-capped Metal Nanoparticles for Soft Plasmonic/Electronic Devices
Wenlong Cheng (Department of Chemical Engineering, Monash University, Clayton, Australia)

21:30+: Socializing (Scorpions Bar & Grill, Main Street)


Thursday, July 2 (NOTE: all talks will be at Paul College, G75 Auditorium)


6:30 - 8:00: BREAKFAST (Philbrook Dining Hall) 

8:30 - 9:30: Controlled radical polymerization in emulsion polymerization: from the design of block copolymer nanoparticles to the formation of surfactant-free latexes
Muriel Lansalot (C2P2 Chemistry, Catalysis, Polymers and Processes, Claude Bernard University, Lyon, France)

9:30 - 10:30: Convective self-assembly: a versatile method towards novel light- and heat management structures and beyond
Natalie Stingelin (Faculty of Engineering, Department of Materials, Imperial College London, London, UK)

10:30: Coffee Break

11:00 - 12:00: Colloidal building blocks using hydrogen bonding interactions between stabilizers
Hideto Minami (Graduate School of Engineering, Kobe University, Kobe, Japan)

12:00 - 12:30: Election of Next IPCG Vice Chair 2017

12:30 - 1:30: LUNCH (Philbrook Dining Hall)

16:30 - 17:00: What can polymer colloids learn from the field of small molecule semiconductors?
Luke Rochford (Department of Chemistry, University of Warwick, Warwick, UK)

17:00 - 17:30: Janus Graphene Oxide Nanosheets
Emily Pentzer (Department of Chemistry, Case Western Reserve University, Cleveland, OH USA)

17:30 - 18:00: Particle design for the synthesis of tailored polymer nano-composites
Marco Villalobos (Global Applications Development Director, Cabot Corporation, Billerica, MA USA)

19:00 - 21:00: Banquet & Lobster Dinner (Huddleston Hall) 
Including a few special presentations: (IPCG Morals Officer Report & Poster Prize Winner Announcements)

21:30+: Socializing (Scorpions Bar & Grill, Main Street)


Friday, July 3


6:30 - 8:30: BREAKFAST (A meal-card will be given to each participant to be used at local establishments)

10:00: Return Bus to Boston Logan Airport

Join the BonLab as a PostDoc


Fixed term contract for 12 months. 

Applications are invited for a Research Fellow to work in the BonLab under the supervision of prof.dr.ir. Stefan A. F. Bon. The research project will develop innovative heterogeneous polymerization methods to fabricate nanocomposite supracolloidal structures. 

Candidates must have completed (or be soon to complete) a PhD or equivalent in synthetic polymer and/or colloid science. A proven ability in innovative and effective experimental research is essential and you should be skilled in the use of techniques for synthesis and characterization of macromolecules, hybrid materials, and/or colloidal particles. An interest and aptitude for unravelling mechanistic aspects of heterogeneous polymerization processes and assembly of colloidal matter is essential. 

You will be able to work independently and as part of a research team, aiding in the supervision of junior research workers. You will have a proven track record of publications, excellent communication and scientific writing skills. 

APPLY NOW

Catch up with Warwick Chemistry students on internship in Singapore

In my schedule of my work visit to A*STAR in Singapore, i made some time to catch up with some of our 3rd year Chemistry Undergraduate students. It was great to meet up with Sarah, Victor, Shin Yiing, Shelly, Sophie, and Chloe on Friday the 17th of April 2015 in Singapore. 

As part of their MChem degree at Warwick Chemistry, they are doing an international research placement at Nanyang Technological University.


We went to Clarke Quay in the evening for a beautiful dinner at Jumbo Seafood. Yes, that chilly crab was a bit of a challenge. 

All were very excited to be at NTU. Singapore is an amazing place. The Friday evening was perfect.