Here, we investigate the kinetics of adsorption and desorption of a cationic photosensitive azobenzene-containing surfactant within anionic microgels in the dark and under continuous illumination with light of different wavelengths and show that microgels can serve as a selective absorber of one of the possible isomers of the photosensitive surfactant. The adsorption of the isomer is governed by entropic reasons at which micellization of the surfactant takes place within the microgel matrix composed of cross-linked PNIPAM and anionic poly(acryl acid) chains rendering it photoresponsive. Under irradiation with appropriate wavelength, the surfactant molecules photoisomerize from trans (hydrophobic)- to cis (hydrophilic)-state and the microgel collapses due to diffusion of the cis-isomers out of the particle interior. When the light is switched off, the microgels swell back to the equilibrium size by absorbing the rest of the trans-isomers out of solution with the characteristic time being between a few seconds and hours depending on the amount of the trans-isomers left in the solution. Measuring the kinetics of the microgel size response and knowing the exact isomer composition under light exposure, we calculate the adsorption rate of the trans-isomers. We show that depending on the intensity of the applied light, one can differentiate between two processes, i.e., at low intensities, the kinetics of the size change is mostly dominated by the photoisomerization rate of the surfactant within the interior of the particle, while at larger intensities, the process is limited by the surfactant adsorption/desorption rate. By performing temperature-dependent measurements, we also calculate the activation energy of the adsorption/desorption process.
Here we show that microgels trapped at a solid wall can issue liquid flow and transport over distances several times larger than the particle size. The microgel consists of cross-linked poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-AA) polymer chains loaded with cationic azobenzene-containing surfactant, which can assume either a trans- or a cis-state depending on the wavelength of the applied irradiation. The microgel, being a selective absorber of trans-isomers, responds by changing its volume under irradiation with light of appropriate wavelength at which the cis-isomers of the surfactant molecules diffuse out of the particle interior. Together with the change in particle size, the expelled cis-isomers form an excess of the concentration and subsequent gradient in osmotic pressure generating a halo of local light-driven diffusioosmotic (l-LDDO) flow. The direction and the strength of the l-LDDO depends on the intensity and irradiation wavelength, as well as on the amount of surfactant absorbed by the microgel. The flow pattern around a microgel is directed radially outward and can be maintained quasi-indefinitely under exposure to blue light when the trans-/cis-ratio is 2/1, establishing a photostationary state. Irradiation with UV light, on the other hand, generates a radially transient flow pattern, which inverts from inward to outward over time at low intensities. By measuring the displacement of tracer particles around neutral microgels during a temperature-induced collapse, we can exclude that a change in particle shape itself causes the flow, i.e., just by expulsion or uptake of water. Ultimately, it is its ability to selectively absorb two isomers of photosensitive surfactant under different irradiation conditions that leads to an effective pumping caused by a self-induced diffusioosmotic flow.
Bio-Based Microgels In article number 2303783, Andrij Pich and co-workers report a versatile method to tune the porosity of dextran-based microgels. The size of mesopores (≤50 nm) in diameter is regulated by the variation of the polymer concentration. For the generation of the macropores (300 to 690 nm), pH-degradable supramacromolecular nanogels are used as a sacrificial colloidal template. Different sizes of the sacrificial nanogels are synthesized via precipitation polymerization and subsequently embedded in the polymer matrix of the microgels via droplet-based microfluidics. The authors demonstrate that uniform voids in the macropore range can be realized by degrading the incorporated sacrificial nanogels.
Abstract Mechanochemical activations in Rh III ‐ and Au I ‐catalyzed C−H alkynylations lead selectively to C 2 ‐ and C 3 ‐alkynylated indoles. The processes show excellent functional group tolerance, do not require additional heating and proceed under solventless conditions. Compared to solvent‐based standard protocols, the reaction times are shorter and the catalyst quantities lower resulting in high product yields under ambient atmosphere in mixer mills.
Abstract In this report, a versatile method is demonstrated to create colloidal suprastructures by assembly and supramolecular interlinking of microgels using droplet‐based microfluidics. The behavior of the microgels is systematically investigated to evaluate the influence of their concentration on their distribution between the continuous, the droplet phase, and the interface. At low concentrations, microgels are mainly localized at the water–oil interface whereas an excess of microgels results, following the complete coverage of the water–oil interface, in their distribution in the continuous phase. To stabilize the colloidal suprastructure, on‐chip gelation is introduced by adding natural polyphenol tannic acid (TA) in the water phase. TA forms interparticle linking between the poly( N ‐vinylcaprolactam) (PVCL) microgels by supramolecular interactions. The combination of supramolecular interlinking with the variation of the microgel concentration in microfluidic droplets enables on‐chip fabrication of defined colloidal suprastructures with morphologies ranging from colloidosomes to colloidal supraballs. The obtained supracolloidal structures exhibit a pH‐responsive behavior with a disintegration at alkaline conditions within a scale of seconds. The destabilization process results from the deprotonation of phenolic groups and destruction of hydrogen bonds with PVCL chains at higher pH.
Physical material properties, such as elasticity, viscosity, or viscoelasticity, can be characterized by using rheometers or stick-type solenoid electromagnets. In this work, we developed a magnet measurement setup based on a Helmholtz arrangement of electromagnets. While applying homogeneous magnet fields to ferrofluid droplets inside a soft material of interest, the deformations of the ellipsoidal deformed droplet were measured. Kelvin-Voigt models and corresponding analytical descriptions were used to calculate the values of viscosity and Young’s modulus of materials under test. For calibration purposes of the developed setup, glycerin/water mixtures and methylcellulose/water solutions were characterized as viscous and polyacrylamide gels as elastic materials, respectively. In addition, the interfacial tensions were calculated with respect to the magnetic Bond number from the droplet deformations. For the first time, the transient rheological behavior of viscoelastic material was measured using the method of ferrofluid droplet deformation. When polyacrylamide gel with a shear modulus of 230 Pa was evacuated for less than 40 min during preparation, it showed a strong timedepending viscoelastic behavior several minutes after starting the measurements. Here, Young’s modulus increased up to the value of elastic behavior, whereas the values for viscosity decreased to a baseline. The developed setup can favorably be used in future applications to investigate local and also time-dependent rheological properties of soft materials.
We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented.
We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented.
Abstract Nature uses replication to amplify the information necessary for the intricate structures vital for life. Despite some successes with pure nucleotide structures, constructing synthetic microscale systems capable of replication remains largely out of reach. Here, a functioning strategy is shown for the replication of microscale particle assemblies using DNA‐coated colloids. By positioning DNA‐functionalized colloids using capillary forces and embedding them into a polymer layer, programmable sequences of patchy particles are created that act as a primer and offer precise binding of complementary particles from suspension. The strings of complementary colloids are cross‐linked, released from the primer, and purified via flow cytometric sorting to achieve a purity of up to 81% of the replicated sequences. The replication of strings of up to five colloids and non‐linear shapes is demonstrated with particles of different sizes and materials. Furthermore, a pathway for exponential self‐replication is outlined, including preliminary data that shows the transfer of patches and binding of a second‐generation of assemblies from suspension.
