Gabit Nurumbetov - Academia.edu (original) (raw)

Papers by Gabit Nurumbetov

Chemical reviews, Jan 30, 2015

ABSTRACT Table of Contents 1. Introduction 1.1. From Free Radical Polymerization to Living Radica... more ABSTRACT Table of Contents 1. Introduction 1.1. From Free Radical Polymerization to Living Radical Polymerization 1.2. Scope of the Review 2. Introduction to SET-LRP 2.1. SET-LRP: A Rapidly Developing Area 2.2. Attractive and Unattractive Characteristics of SET-LRP 2.3. Introduction to Organic SET-LRP 2.4. Guidelines for Conducting Organic SET-LRP 2.5. Introduction to Aqueous SET-LRP 2.6. Guidelines for Aqueous SET-LRP 3. Dynamics of SET-LRP 3.1. Monomer Compatibility 3.1.1. Acrylates 3.1.2. Methacrylates 3.1.3. Acrylamides 3.1.4. Methacrylamides 3.1.5. Styrene and Other Monomers 3.2. Solvent Compatibility 3.2.1. Aqueous and Organic Solvents 3.2.2. Complex Solvents 3.2.3. Solvents That Induce Phase Separation 3.3. Initiator Compatibility 3.3.1. Monofunctional Initiators 3.3.2. Bifunctional Initiators 3.3.3. Multifunctional Initiators 3.4. Ligand Compatibility 3.5. Catalyst Compatibility 3.5.1. Forms of Cu(0) Catalyst 3.5.2. Activation Methods for Copper 3.5.3. Other Zerovalent Metals 3.5.4. Compatibility of SET-LRP with Other Polymerization Techniques 4. Touching the Mechanistic Debate 5. Complex Architectures via SET-LRP 5.1. Multiblock Copolymers: Sequence Control 5.1.1. Multiblock Copolymers in Organic Media 5.1.2. Multiblock Copolymers in Aqueous Media 5.2. Surface Initiated SET-LRP 5.3. Nanoreactors 5.4. Cyclic Polymers 5.5. Branched and Dendritic Macrostructures 5.6. Star Polymers 6. Applications 6.1. Bioapplications 6.1.1. Glycopolymers 6.1.2. Timed Release of siRNA 6.1.3. Amplification-Free DNA Detection 6.1.4. Nuclear Delivery of Plasmid DNA 6.1.5. Antibacterial Agents 6.1.6. Iron Oxide Nanoparticles (IONPs) as MRI Contrast Agents 6.1.7. Foldamer-Linked Polymers 6.1.8. Polymer–Protein Conjugates 6.1.9. Photopatterning of Nonfouling Polymers and Biomolecules on Paper 6.2. Technological Applications 6.2.1. SET-LRP in a Continuous Flow Process 6.2.2. Mechanophore Containing Polymers 6.2.3. Oil Absorbing Materials 6.2.4. Photoresist Materials 6.3. Other Applications 7. Conclusions

Macromolecules, 2015

ABSTRACT Herein we report the photoinduced living radical polymerization of acrylates in a variet... more ABSTRACT Herein we report the photoinduced living radical polymerization of acrylates in a variety of ionic liquids (ILs). 1-Ethyl-3-methylimidazolium ethyl sulfate [emim][EtSO4], 1-heptyl-3-methylimidazolium bromide [C7mim][Br], 1-hexyl-3-methylimidazolium tetrafluoroborate [C6mim][BF4], 1-hexyl-3-methylimidazolium hexafluorophosphate [C6mim][PF6], and 1-octyl-3-methylimidazolium hexafluorophosphate [C8mim][PF6] were employed as solvents for the homopolymerization of a variety of acrylates including methyl acrylate (MA), n-butyl acrylate (n-BA), ethylene glycol methyl ether acrylate (EGA), and poly(ethylene glycol) methyl ether acrylate (PEGA, Mn ≈ 480). Polymerization of MA, EGA, and PEGA in [C6mim][BF4], [C6mim][PF6], and [C8mim][PF6] proceeded in a controlled manner, as evidenced by kinetic studies, narrow molecular weight distributions (Đ ≈ 1.1), and quantitative conversions (>99%) within 30 min. MALDI-ToF-MS and 1H NMR confirmed very high end-group fidelity, which was further exemplified by in situ chain extensions and block copolymerizations, yielding well-defined block copolymers in a quantitative manner. While polymerization of n-BA in [C6mim][BF4] and [C6mim][PF6] yielded polymers with bimodal molecular weight distribution (potentially due to poor solubility), polymerization of the same monomer in [C8mim][PF6] was well-controlled yielding materials with a monomodal polymer peak distribution and low dispersity. Interestingly, all polymerizations in ILs experienced a significant acceleration on the rate of polymerization without compromising the end-group fidelity, as opposed to the slower rates observed when DMSO was used as the solvent. The versatility of the approach was also demonstrated by polymerization of MA to a number of chain lengths (Mn ≈ 4500–40 000 g mol–1) furnishing poly(acrylates) with low dispersities in all cases (Đ ≈ 1.1). Importantly, extraction of the obtained polymer with toluene allowed the IL/catalyst solution to be reused as the solvent for further polymerizations without affecting the living nature of the polymerization. Moreover, the polymer extracted into the toluene (copper-free) can be used directly for post-polymerization modifications (e.g., click reactions)

Journal of the American Chemical Society, Jan 7, 2015

The synthesis of well-defined protein/peptide-polymer conjugates with interesting self-assembly b... more The synthesis of well-defined protein/peptide-polymer conjugates with interesting self-assembly behavior via single electron transfer living radical polymerization (SET-LRP) in water is described. A range of protein/peptides with different physical and chemical properties have been modified to macroinitiators and optimized polymerization conditions ensure successful polymerization from soluble, insoluble and dispersed protein/peptide molecules or protein aggregates. This powerful strategy tolerates a range of functional monomers and mediates efficient homo or block copolymerization to generate hydrophilic polymers with controlled molecular weight (MW) and narrow MW distribution. The polymerizations from bovine insulin macroinitiators follow surface-initiated "grafting from" polymerization mechanism and may involve a series of self-assembly and disassembly processes. Synthesized insulin-polymer conjugates form spheres in water and the self-assembly behavior could be control...

ACS Symposium Series, 2015

Many polymer products are manufactured using batch and semi-batch reactors. Typically the process... more Many polymer products are manufactured using batch and semi-batch reactors. Typically the process parameters are fixed and are not varied during the reaction. Unexpected changes in operating conditions can lead to variations in polymer structure and purity, resulting in significant losses due to off-spec materials. An approach addressing the complex issues of real-time process control of large-scale emulsion polymerisation processes is to use advanced models and on-line sensors. A specific objective is to implement a model-based predictive control based on Raman spectroscopy.

Chem. Commun., 2015

A photo-polymerization protocol, utilizing a pre-formed and wellcharacterized Cu(II) formate comp... more A photo-polymerization protocol, utilizing a pre-formed and wellcharacterized Cu(II) formate complex, [Cu(Me 6 -Tren)(O 2 CH)](ClO 4 ), mediated by UV light is described. In the absence of additional reducing agents and/or photosensitizers, ppm concentrations of the oxidatively stable [Cu(Me 6 -Tren)(O 2 CH)](ClO 4 ), furnish nearquantitative conversions within 2 h, yielding poly(acrylates) with low dispersities (B1.10) and exceptional end-group fidelity, capable of undergoing in situ chain extension and block copolymerization.

Polym. Chem., 2015

The synthesis of well-defined α,ω-dihydroxyl telechelic multiblock copolymers by sequential in si... more The synthesis of well-defined α,ω-dihydroxyl telechelic multiblock copolymers by sequential in situ chain extensions via aqueous Cu(0) mediated living radical polymerization (SET-LRP) is reported. The rapid disproportionation of Cu(I)Br in the presence of Me 6 -TREN in water has been exploited to generate Cu(0) and

Macromolecules, 2014

Photoinduced living radical polymerization of acrylates is achieved upon UV irradiation (λ max ≈ ... more Photoinduced living radical polymerization of acrylates is achieved upon UV irradiation (λ max ≈ 360 nm) in the presence of an aliphatic tertiary amine ligand (Me 6 -Tren) in the presence of low concentrations of CuBr 2 , yielding poly(acrylates) with near perfect retention of end group fidelity. The effect of the nature of the solvent on the rate of polymerization was investigated in order to expand the scope and identify the limitations of the system. Subsequently, a range of acrylic monomers containing hydrophobic and hydrophilic substituents have been screened, including lauryl acrylate, octadecyl acrylate and diethylene glycol ethyl ether acrylate, all of which present low dispersities (Đ ≈ 1.1) at very high conversions. Functional monomers, including glycidyl acrylate and solketal acrylate, were also found to be tolerant to the photomediated reaction. Finally, solketal acrylate was copolymerized with methyl acrylate which, following deprotection of the pendant ketal group, furnished an amphiphilic diblock copolymer. Self-assembly of this block copolymer into polymer micelles in aqueous media was exemplified by dynamic light scattering (DLS) and transmission electron microscopy (TEM).

European Polymer Journal, 2015

Telechelic poly(n-butyl acrylate) and poly[poly(ethylene glycol) methyl ether acrylate] are obtai... more Telechelic poly(n-butyl acrylate) and poly[poly(ethylene glycol) methyl ether acrylate] are obtained with high monomer conversions and narrow molecular weight distributions (Ð < 1.2) by Cu(0)-mediated living radical polymerization (SET-LRP). The high end group fidelity of the polymer is confirmed by a combination of 1 H NMR and MALDI-ToF-MS analysis. The reactivity of the telechelics is exploited to yield amphiphilic BAB triblocks, by sequential addition of a second monomer, which self-assemble in water. Furthermore, nucleophilic thiol-bromine substitution using 2-mercaptoethanol post-polymerization enables the incorporation of primary alcohols on both the aand x-polymer chain ends.

Polymer Chemistry, 2013

The controlled polymerization of N-isopropyl acrylamide (NIPAM) is reported in a range of interna... more The controlled polymerization of N-isopropyl acrylamide (NIPAM) is reported in a range of international beers, wine, ciders and spirits utilizing Cu(0)-mediated living radical polymerization (SET-LRP).

Soft Matter, 2013

Non-spherical particles have the potential to adopt multiple orientations once adhered to a liqui... more Non-spherical particles have the potential to adopt multiple orientations once adhered to a liquid-liquid interface. In this work we combine simulations and experiments to investigate the behaviour of an isolated microscopic hematite particle of superellipsoidal shape. We show that this microparticle can adopt one of three orientations when adhered to a hexadecane-water interface. Two of the orientations, and estimates for their relative populations, could be assigned to two thermodynamic minima on the energy landscape as generated through both free-energy minimization and particle trajectory simulations. The third orientation was found to correspond to a kinetically trapped state, existing on certain particle trajectories in a region of a negligible gradient in free energy. To underpin the simulations the individual orientation of a set of 100 isolated particles was explored by means of scanning electron microscopy (SEM) using the gel trapping technique as a tool. Atomic force microscopy (AFM) was additionally used to support the experimental findings. This is the first example of such a kinetic metastable state being observed for particles at liquid-liquid interfaces. ; Web: http://www.bonlab.info; Tel: +44 (0)2476 574009 † Electronic supplementary information (ESI) available: Experimental details, details on MATLAB simulations, hematite particle size distribution, and SEM images incl. of 100 isolated particles. See

Russian Journal of Applied Chemistry, 2008

Specific features of modification of an alicyclic polyimide with polyaniline were examined. The t... more Specific features of modification of an alicyclic polyimide with polyaniline were examined. The thus obtained new polymeric composites exhibit better capability for silver plating.

Polymer Chemistry, 2012

We demonstrate that by using a syringe needle, plastic tubing, two glass capillaries and epoxy gl... more We demonstrate that by using a syringe needle, plastic tubing, two glass capillaries and epoxy glue a microfluidic device can be fabricated straightforwardly that allows for the production of double emulsions, or in other words the generation of droplets-in-droplets. The device in essence is a serial combination of droplet generation by co-flow and a T-junction. To reduce potential issues with channel wetting, we established that an ''obstructed'' T-junction outperformed a conventional T-junction. We illustrate the versatility of our device through production of a range of polymer microcapsules, including ones that contain a waterborne dispersion of colour changing pigment, and microcapsules with compartmentalized ferrofluidic segments, that is capsules that contain more than one droplet of ferrofluid.

Langmuir, 2013

We describe a versatile and facile route for the preparation of Janus microbeads using single emu... more We describe a versatile and facile route for the preparation of Janus microbeads using single emulsion droplet-based microfluidics, in which water droplets that contain a mixture of branched poly(Nisopropylacrylamide)-co-(poly(ethylene glycol)diacrylate)-co-(methacrylic acid) and colloidal particles form the basis of our approach. The colloidal particles, poly(methyl methacrylate) microspheres or titanium dioxide particles, and iron oxide nanoparticles are spatially positioned within the water droplets through gravity and an externally applied magnetic force, respectively. Evaporation of water leads to gel formation of the branched copolymer matrix as a result of physical cross-linking through hydrogen bond interactions, fixing the spatial position of the colloidal particles. The thermo-and pH-responsive nature of the branched poly(N-isopropylacrylamide) (PNIPAm)-based copolymer allows for the disintegration of the polymer network of the Janus microbeads and a triggered release of the colloidal content at temperatures below the lower critical solution temperature (LCST) and at increased pH values.