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A copolymer consisting of acrylamide (AAm) and acrylonitrile (AN) in aqueous solution was investigated using broadband dielectric spectroscopy at frequencies between 10⁻¹ Hz and 10⁶ Hz in the temperature range from 2 °C to 60 °C. This system shows an UCST phase behavior. The phase transition and aggregation behavior is monitored by both the temperature and frequency dependence of the complex conductivity σ*(f, T), where the AN fraction and the concentration of the solution were varied.
Additionally, the dielectric data are compared with the results obtained from dynamic light scattering measurements. The temperature dependence of the DC conductivity (σDC) of the copolymer solution is monitored and the phase transition temperature (PTT) of the poly(AAm-co-AN) copolymer is deduced from a change in the T-dependence of the DC conductivity. The change in σDC can be explained by decreased effective charge carrier mobility and a reduction of the effective charge number density at temperatures below the phase Transition temperature of the poly(AAm-co-AN) solution. A pronounced interfacial polarization effect on the frequency dependence of the real part of the conductivity (σ') is observed at temperatures below the phase Transition temperature. The charge carriers are blocked at the formed aggregates giving rise to this interfacial polarization. The dependence of the interfacial polarization on the acrylonitrile fraction in the copolymer and the concentration of the solution is studied in detail and conclusions concerning the internal structures of the copolymer aggregates are drawn.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the right side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
Unilamellar vesicles self-assembled in water from natural and synthetic phospholipids (liposomes), amphiphilic block copolymers (polymersomes), and more recently amphiphilic Janus dendrimers (dendrimersomes) as hollow soft structures in the nano size regime have attracted increasing interest as they can mimic primitive and contemporary biological membranes, and can be configured into biomimetic nanocapsules with application in nanomedicine such as gene, proteins and drug carriers or theranostics. Compared to other amphiphilic structures, the molecular structure of Janus dendrimers can be precisely controlled: by using the vast range of tools from organic chemistry their size, architecture, density, generation as well as the number of endgroups of the individual dendrons can be modified as desired. Unfortunately, the controlled production of the supramolecular aggregates made thereof is still a challenging task. Conventional batch-based techniques such as the solvent injection method or the film hydration method typically go along with a lack of control over mixing and thus over size, morphology and size distribution. The micromixer technology is a promising method for the controlled preparation of supramolecular assemblies as it allows control of mixing at microscale level. In addition, such microfluidic systems benefit from a high mixing efficiency, a low mixing time as well as from a reproducible and continuous synthesis.
Herein, we report on the microfluidic-controlled self-assembly of Janus dendrimers as dendrimersomes and the impact of the mixing parameters on the self-assembly process.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the appropriate side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
Vesicles self-assembled in water from natural and synthetic phospholipids (liposomes), amphiphilic block copolymers (polymersomes), and more recently amphiphilic Janus dendrimers (dendrimersomes) -5 as hollow soft structures in the nano size regime have attracted increasing interest as they can mimic primitive and contemporary biological membranes, and can be configured into biomimetic nanocapsules with application in nanomedicine such as gene, proteins and drug carriers or theranostics.
Compared to other amphiphilic structures, the molecular structure of Janus dendrimers can be precisely controlled: by using the vast range of tools from organic chemistry their size, architecture, density, generation as well as the number of end groups of the individual dendrons can be modified as desired.
Unfortunately, the controlled production of the supramolecular aggregates made thereof is still a challenging task. Conventional batch-based techniques such as the solvent injection method or the film hydration method typically go along with a lack of control over mixing and thus over size, morphology and size distribution. The micromixer technology is a promising method for the controlled preparation of supramolecular assemblies as it allows control of mixing at microscale level. In addition, such microfluidic systems benefit from a high mixing efficiency, a low mixing time as well as from a reproducible and continuous synthesis.
Herein, we report on the microfluidic-controlled self-assembly of Janus dendrimers as dendrimersomes and the impact of the mixing parameters on the self-assembly process.
The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment) on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size.
The phase behavior of a dendritic amphiphile containing a Newkome-type dendron as the hydrophilic moiety and a cholesterol unit as the hydrophobic segment is investigated at the air–liquid interface. The amphiphile forms stable monomolecular films at the air–liquid interface on different subphases. Furthermore, the mineralization of calcium Phosphate beneath the monolayer at different calcium and phosphate concentrations versus mineralization time shows that at low calcium and Phosphate concentrations needles form, whereas flakes and spheres dominate at higher concentrations. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron diffraction confirm the formation of calcium phosphate. High-resolution transmission electron microscopy and electron diffraction confirm the predominant formation of octacalcium phosphate and hydroxyapatite.
The data also indicate that the final products form via a complex multistep reaction, including an association step, where nano-needles aggregate into larger flake-like objects.
UCST-type thermoresponsive polymers that phase separate from solution upon cooling present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol. In this context, acrylamide-based monomers can be very useful building blocks for designing novel UCST-type polymers because of their hydrophilic nature (with the right side chain) and propensity to form hydrogen bonds.
We want to present our latest results on the copolymer poly(acrylamide-co-acrylonitrile) (P(AAm-co-AN)) that present a UCST in water as well as on two homopolymers based on an acrylamide derivative of 2,6-diaminopyridine, namely poly(N-(6-aminopyridin-2-yl)acrylamide) (PNAPAAm) and poly(N-(6-acetamidopyridin-2-yl)acrylamide) (PNAcAPAAm) that show UCST-type thermoresponsiveness in water/alcohol mixtures.
Our focus for P(AAm-co-AN)) is its aggregation behaviour above and below its phase transition temperature as the size of thermoresponsive polymeric systems is of prime importance for biomedical applications (as size dependent processes take place in the body) and is linked to the optical properties of a material that matter in materials science.
In the case of PNAPAAm and PNAcAPAAm, we focused on the co-solvency/co-non solvency effect on the phase transition temperature in water/alcohol mixture. Indeed, polymers with UCST behavior below 60°C in water/alcohol mixtures are extremely promising for the preparation of “smart” materials for sensing.
Vesicles self-assembled in water from natural and synthetic phospholipids (liposomes), amphiphilic block copolymers (polymersomes), and more recently amphiphilic Janus dendrimers (dendrimersomes) as hollow soft structures in the nano size regime have attracted increasing interest as they can mimic primitive and contemporary biological membranes, and can be configured into biomimetic nanocapsules with application in nanomedicine such as gene, proteins and drug carriers or theranostics.
Compared to other amphiphilic structures, the molecular structure of Janus dendrimers can be precisely controlled: by using the vast range of tools from organic chemistry their size, architecture, density, generation as well as the number of end groups of the individual dendrons can be modified as desired.
Unfortunately, the controlled production of the supramolecular aggregates made thereof is still a challenging task. Conventional batch-based techniques such as the solvent injection method or the film hydration method typically go along with a lack of control over mixing and thus over size, morphology and size distribution. The micromixer technology is a promising method for the controlled preparation of supramolecular assemblies as it allows control of mixing at microscale level. In addition, such microfluidic systems benefit from a high mixing efficiency, a low mixing time as well as from a reproducible and continuous synthesis.
Herein, we report on the microfluidic-controlled self-assembly of Janus dendrimers as dendrimersomes and the impact of the mixing parameters on the self-assembly process.
Thermoresponsive polymers are of great importance in numerous applications such as bioseparation, drug delivery, diagnostic and microfluidic applications. Only few thermoresponsive polymers that present an upper critical solution temperature (UCST), i.e. phase separate from solution upon cooling, in a relevant temperature range and green solvents such as water or ethanol have been reported.
In this work two novel functional polymers of based on a 2,6-diaminopyridine motif, namely poly(N-(6-aminopyridin-2-yl)acrylamide) (PNAPAAm) and poly(N-(6-acetamidopyridin-2-yl)acrylamide) (PNAcAPAAm), were synthesized by free radical polymerization. The obtained polymers displayed UCST-type reversible thermoresponsive behaviour in water/alcohol mixtures. Insights into this phenomenon will be given based on visual observations, temperature-dependent turbidimetry and dynamic light scattering as well as 1H-NMR measurements. The UCST phase transition behaviour of the polymers was tunable by varying either the concentration of the polymer solution, the nature of the alcohol or the composition of the solvent mixture. The cloud point temperature of PNAcAPAAm was found to decrease with increasing alcohol content (MeOH, EtOH and iPrOH) in water/alcohol mixtures. Past a critical amount of EtOH or iPrOH in water the cloud point temperature of PNAcAPAAm increased by further addition of EtOH or iPrOH. These polymers with UCST behavior below 60°C in water/alcohol mixtures show great promises for the preparation of smart materials for sensing.