Versatile and Remotely Controllable Light-Induced Coagulation of Particles Under Flow in a 2D Channel.

On-demand switch on/off blood clogging is of paramount importance for the survival of mammals, for example as a quick response to seal damage wounds to minimize their bleeding rate. This mechanism is a complex chain process from initiated red blood cell aggregation at the target location (open wound) that quickly seals on a macroscopic scale the damaged flash. Inspired by nature an on-demand switchable particle clogging mechanism is developed with high spatial resolution down to micrometer size using light as an external non-invasive stimulation. Particle clogging can be adjusted on demand strong enough to even withstand pressure-driven fluid flow, additionally building up walls of aggregated particles, which stop the momentum of big particles under shear. The principle relies on a photosensitive surfactant, which induces under light illumination a long-ranged lateral attractive phoretic-osmotic activity of silica microparticles forcing them to aggregate. The strength of aggregation and therefore motion reduction or even stop of the particles against the fluid flow depends on the ratio between the aggregation strength and the velocity of the particles. The aggregation strength can be precisely controlled by the applied light intensity and adjusted particle concentration. Increasing both parameters results in a stronger aggregation tendency.

Light-Induced Material Motion Fingerprint - A Tool Toward Selective Interfacial Sensitive Fractioning of Microparticles via Microfluidic Methods.

In this article, a novel strategy is presented to selectively separate a mixture of equally sized microparticles but differences in material composition and surface properties. The principle relies on a photosensitive surfactant, which makes particles under light illumination phoretically active. The latter hovers microparticles from a planar interface and together with a superimposed fluid flow, particles experience a drift motion characteristic to its interfacial properties. The drift motion is investigated as a function of applied wavelength, demonstrating that particles composed of different material show a unique spectrally resolved light-induced motion profile. Differences in those motion profile allow a selective fractioning of a desired particle from a complex particle mixture made out of more than two equally sized different particle types. Besides that, the influence of applied wavelength is systematically studied, and discussed the origin of the spectrally resolved chemical activity of microparticles from measured photo-isomerization rates.

Artifact Correction of Light Induced Detuning in QCM-D Experiments.

The quartz crystal microbalance with dissipation (QCM-D) has become an efficient and versatile measurement technique for investigating in situ the external stimuli responsiveness such as pH, temperature, or chemical gradients of surface-active substances at solid-liquid interfaces. However, light responsive adsorption investigation is more challenging presumably since the quartz crystal itself reacts to optical stimulation, showing frequency and dissipation shifts known as light induced detuning (LID). This yields an effective measurement artifact and makes data interpretation with respect to dynamic interactions of light responsive materials rather challenging. Here we introduce a simple guideline for correcting the artifacts of the QCM sensor response on irradiation to ensure quantitative analysis for light responsive materials via OCM-D. We also show that the LID depends on the adsorption properties of the sensor and the solvent properties (ionic concentration or viscosity), providing a guideline to minimize impact of the LID.

Making microgels photo-responsive by complexation with a spiropyran surfactant.

We report on triggering of p(NIPAM-AA) microgels' photo-responsiveness by making complexes with a spiropyran (SP) containing surfactant. Being dissolved in water, the SP surfactant in its merocyanine state bears three charges, while irradiation with UV and vis light leads to the partial or complete reversal of the SP state. The complexation of the photo-responsive amphiphile with swollen anionic microgels results in charge compensation within the gel interior and as a consequence its size reduces and the volume phase transition temperature (VPTT) decreases down to 32 °C. Under irradiation the MC form photo-isomerizes to a ring closed SP state generating a more hydrophobic surfactant with one positive charge at the head. The increase in the hydrophobicity of the surfactant and thus of the interior of the gel results in the reversible size change of the microgel. We investigate the photo-responsivity of the microgel as a function of wavelength and irradiation intensity, as well as of surfactant concentration and charge density of the microgel. We show that the change in the size and VPTT of the microgels during irradiation occurs through a combination of two processes: heating of the solution during light absorption by the surfactant (more pronounced in the case of UV irradiation) and the change in the hydrophobicity of the surfactant.

Complexes of photosensitive surfactant and fluorescent dye for light-induced manipulation of colloids.

Light-driven diffusioosmosis is a membrane-free method for manipulating colloidal ensembles at solid-liquid interfaces based on photo-sensitive molecules inducing fluid flows along solid surfaces. In this study, we present our findings on porous colloids settled at a solid wall in an aqueous solution comprising a photo-sensitive azobenzene-containing cationic surfactant and a cyanine-based dye, capable of ionically binding to each other. The surfactant acts as an activation agent for diffusioosmotic flow. When exposed to modulated light, it undergoes photo-isomerization from a hydrophobic trans-state to a more hydrophilic cis-state, creating a concentration gradient near the irradiated area of the wall. The resulting osmotic pressure gradient sets the flow in motion. Porous colloids actively participate in flow generation by readily incorporating the surfactant molecules in the trans-state and releasing them in the cis-state, creating a constant source of diffusioosmotic flow. Under UV illumination, an excess of cis-isomers near the porous colloids elicits long-range repulsive interactions, tenfold the diameter of a particle. The dye acts as a sensor for the surfactant filling or emptying the pores of the colloids. It forms a complex with the trans-isomer and diffuses into the pores, where photoisomerization to cis-state destroys the complex and causes both the dye and the surfactant to leave the pores, altering the luminescence brightness within the colloids. We demonstrated that the presence of the dye affects cis-trans isomer ratios of the surfactant at photo-stationary states, thereby influencing the process of diffusioosmosis. This process enables the manipulation of colloidal particles and remote control of the interaction potential between them, facilitating the formation of well-ordered surface aggregates.

Generation of Local Diffusioosmotic Flow by Light Responsive Microgels.

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.

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental-Theoretical Approach to Photophysical Properties and Self-Assembly.

This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e., upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, the aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form becomes thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol-1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol-1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

A Dual pH- and Light-Responsive Spiropyran-Based Surfactant: Investigations on Its Switching Behavior and Remote Control over Emulsion Stability.

A cationic surfactant containing a spiropyran unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyran (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions.

Light-induced manipulation of passive and active microparticles.

We consider sedimented at a solid wall particles that are immersed in water containing small additives of photosensitive ionic surfactants. It is shown that illumination with an appropriate wavelength, a beam intensity profile, shape and size could lead to a variety of dynamic, both unsteady and steady state, configurations of particles. These dynamic, well-controlled and switchable particle patterns at the wall are due to an emerging diffusio-osmotic flow that takes its origin in the adjacent to the wall electrostatic diffuse layer, where the concentration gradients of surfactant are induced by light. The conventional nonporous particles are passive and can move only with already generated flow. However, porous colloids actively participate themselves in the flow generation mechanism at the wall, which also sets their interactions that can be very long ranged. This light-induced diffusio-osmosis opens novel avenues to manipulate colloidal particles and assemble them to various patterns. We show in particular how to create and split optically the confined regions of particles of tunable size and shape, where well-controlled flow-induced forces on the colloids could result in their crystalline packing, formation of dilute lattices of well-separated particles, and other states.

Adsorption of Photoresponsive Surfactants at Solid-Liquid Interfaces.

We report on the adsorption kinetics of azobenzene-containing surfactants on solid surfaces of different hydrophobicity. The understanding of this processes is of great importance for many interfacial phenomena that can be actuated and triggered by light, since the surfactant molecules contain a photoresponsive azobenzene group in their hydrophobic tail. Three surfactant types are studied, differing in the spacer connecting the headgroup and the azobenzene unit by between 6 and 10 CH2 groups. Under irradiation with light of a suitable wavelength, the azobenzene undergoes reversible photoisomerization between two states, a nonpolar trans-state and a highly polar cis-state. Consequently, the surfactant molecule changes its hydrophobicity and thus affinity to a surface depending on the photoisomerization state of the azobenzene. The adsorption behavior on hydrophilic (glass) and hydrophobic (TeflonAF) surfaces is analyzed using quartz crystal microbalance with dissipation (QCM-D) and ζ-potential measurements. At equilibrium, the adsorbed surfactant amount is almost twice as large on glass compared to TeflonAF for both isomers. The adsorption rate for the trans-isomers on both surfaces is similar, but the desorption rate of the trans-isomers is faster at the glass-water interface than at the Teflon-water interface. This result demonstrates that the trans-isomers have higher affinity for the glass surface, so the trans-to-cis ratios on glass and TeflonAF are 80/1 and 2/1, respectively, with similar trends for all three surfactant types.

Extremely Long-Range Light-Driven Repulsion of Porous Microparticles.

The repulsive surface forces, such as electrostatic or steric, acting between particles explain why they remain well separated in aqueous electrolyte solutions and are responsible for the stability of colloidal dispersions. However, the effective range of these interactions is always well below hundreds of nanometers and typically can be controlled by advanced manipulations such as tuning the electrolyte concentration or modifying the particle surface or, in some more specific cases, via subjecting the suspension to an external electric or magnetic field. Here we employ solutions with small additives of a photosensitive ionic surfactant to investigate if a repulsive interaction of microsized particles sedimented at the solid surface can be remotely controlled simply by illuminating it with an appropriate wavelength. We show that interactions of conventional impermeable particles remain practically unaffected by light, but, in contrast, for porous particles, we observe a long-range repulsion, several orders of magnitude longer than any conceivable equilibrium surface force. This repulsion emerges due to the diffusio-osmotic flow generated near the porous particles that in this scenario are playing a role of micropumps. The diffusio-osmotic repulsion of porous particles can be used for a remote control of their two-dimensional assemblies at the solid wall, and in particular, we demonstrate that by simply using two different illumination wavelengths it is possible to reversibly switch the state of porous particle dispersion from densely packed surface aggregates to a periodic lattice of particles separated by distances on the order of tens of micrometers.

Light driven guided and self-organized motion of mesoporous colloidal particles.

We report on guided and self-organized motion of ensembles of mesoporous colloidal particles that can undergo dynamic aggregation or separation upon exposure to light. The forces on particles involve the phenomenon of light-driven diffusioosmosis (LDDO) and are hydrodynamic in nature. They can be made to act passively on the ensemble as a whole but also used to establish a mutual interaction between particles. The latter scenario requires a porous colloid morphology such that the particle can act as a source or sink of a photosensitive surfactant, which drives the LDDO process. The interplay between the two modes of operation leads to fascinating possibilities of dynamical organization and manipulation of colloidal ensembles adsorbed at solid-liquid interfaces. While the passive mode can be thought of to allow for a coarse structuring of a cloud of colloids, the inter-particle mode may be used to impose a fine structure on a 2D particle grid. Local flow is used to impose and tailor interparticle interactions allowing for much larger interaction distances that can be achieved with, e.g., DLVO type of forces, and is much more versatile.

Light driven diffusioosmotic repulsion and attraction of colloidal particles.

In this paper, we introduce the phenomenon of light driven diffusioosmotic long-range attraction and repulsion of porous particles under irradiation with UV light. The change in the inter-particle interaction potential is governed by flow patterns generated around single colloids and results in reversible aggregation or separation of the mesoporous silica particles that are trapped at a solid surface. The range of the interaction potential extends to several times the diameter of the particle and can be adjusted by varying the light intensity. The "fuel" of the process is a photosensitive surfactant undergoing photo-isomerization from a more hydrophobic trans-state to a rather hydrophilic cis-state. The surfactant has different adsorption affinities to the particles depending on the isomerization state. The trans-isomer, for example, tends to accumulate in the negatively charged pores of the particles, while the cis-isomer prefers to remain in the solution. This implies that when under UV irradiation cis-isomers are being formed within the pores, they tend to diffuse out readily and generate an excess concentration near the colloid's outer surface, ultimately resulting in the initiation of diffusioosmotic flow. The direction of the flow depends strongly on the dynamic redistribution of the fraction of trans- and cis-isomers near the colloids due to different kinetics of photo-isomerization within the pores as compared to the bulk. The unique feature of the mechanism discussed in the paper is that the long-range mutual repulsion but also the attraction can be tuned by convenient external optical stimuli such as intensity so that a broad variety of experimental situations for manipulation of a particle ensemble can be realized.

Kinetics of photo-isomerization of azobenzene containing surfactants.

We report on photoisomerization kinetics of azobenzene containing surfactants in aqueous solution. The surfactant molecule consists of a positively charged trimethylammonium bromide head group, a hydrophobic spacer connecting via 6 to 10 CH2 groups to the azobenzene unit, and the hydrophobic tail of 1 and 3CH2 groups. Under exposure to light, the azobenzene photoisomerizes from more stable trans- to metastable cis-state, which can be switched back either thermally in dark or by illumination with light of a longer wavelength. The surfactant isomerization is described by a kinetic model of a pseudo first order reaction approaching equilibrium, where the intensity controls the rate of isomerization until the equilibrated state. The rate constants of the trans-cis and cis-trans photoisomerization are calculated as a function of several parameters such as wavelength and intensity of light, the surfactant concentration, and the length of the hydrophobic tail. The thermal relaxation rate from cis- to trans-state is studied as well. The surfactant isomerization shows a different kinetic below and above the critical micellar concentration of the trans isomer due to steric hindrance within the densely packed micelle but does not depend on the spacer length.

Photo-Isomerization Kinetics of Azobenzene Containing Surfactant Conjugated with Polyelectrolyte.

Ionic complexation of azobenzene-containing surfactants with any type of oppositely charged soft objects allows for making them photo-responsive in terms of their size, shape and surface energy. Investigation of the photo-isomerization kinetic and isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged objects is a necessary prerequisite for understanding the structural response of photo-sensitive complexes. Here, we report on photo-isomerization kinetics of a photo-sensitive surfactant in the presence of poly(acrylic acid, sodium salt). We show that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in aqueous solution. In a photo-stationary state, the ratio between the trans and cis isomers is shifted to a higher trans-isomer concentration for all irradiation wavelengths. This is explained by the formation of surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration and inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates.

DNA Interaction with Head-to-Tail Associates of Cationic Surfactants Prevents Formation of Compact Particles.

Cationic azobenzene-containing surfactants are capable of condensing DNA in solution with formation of nanosized particles that can be employed in gene delivery. The ratio of surfactant/DNA concentration and solution ionic strength determines the result of DNA-surfactant interaction: Complexes with a micelle-like surfactant associates on DNA, which induces DNA shrinkage, DNA precipitation or DNA condensation with the emergence of nanosized particles. UV and fluorescence spectroscopy, low gradient viscometry and flow birefringence methods were employed to investigate DNA-surfactant and surfactant-surfactant interaction at different NaCl concentrations, [NaCl]. It was observed that [NaCl] (or the Debye screening radius) determines the surfactant-surfactant interaction in solutions without DNA. Monomers, micelles and non-micellar associates of azobenzene-containing surfactants with head-to-tail orientation of molecules were distinguished due to the features of their absorption spectra. The novel data enabled us to conclude that exactly the type of associates (together with the concentration of components) determines the result of DNA-surfactant interaction. Predomination of head-to-tail associates at 0.01 M < [NaCl] < 0.5 M induces DNA aggregation and in some cases DNA precipitation. High NaCl concentration (higher than 0.8 M) prevents electrostatic attraction of surfactants to DNA phosphates for complex formation. DAPI dye luminescence in solutions with DNA-surfactant complexes shows that surfactant tails overlap the DNA minor groove. The addition of di- and trivalent metal ions before and after the surfactant binding to DNA indicate that the bound surfactant molecules are located on DNA in islets.

Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties.

We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). It was found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of the work function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions.

Communication: Light driven remote control of microgels' size in the presence of photosensitive surfactant: Complete phase diagram.

Here we report on a light triggered remote control of microgel size in the presence of photosensitive surfactant. The hydrophobic tail of the cationic surfactant contains azobenzene group that undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. We have investigated light assisted behaviour and the complex formation of the microgels with azobenzene containing surfactant over the broad concentrational range starting far below and exceeding several times of the critical micelle concentration (CMC). At small surfactant concentration in solution (far below CMC), the surfactant in the trans-state accommodates within the microgel causing its compaction, while the cis-isomer desorbs out of microgel resulting in its swelling. The process of the microgel size change can be described as swelling on UV irradiation (trans-cis isomerization) and shrinking on irradiation with blue light (cis-trans isomerization). However, at the surfactant concentrations larger than CMC, the opposite behaviour is observed: the microgel swells on blue irradiation and shrinks during exposure to UV light. We explain this behaviour theoretically taking into account isomer dependent micellization of surfactant within the microgels.

Photosensitive Peptidomimetic for Light-Controlled, Reversible DNA Compaction.

Light-induced DNA compaction as part of nonviral gene delivery was investigated intensively in the past years, although the bridging between the artificial light switchable compacting agents and biocompatible light insensitive compacting agents was not achieved until now. In this paper, we report on light-induced compaction and decompaction of DNA molecules in the presence of a new type of agent, a multivalent cationic peptidomimetic molecule containing a photosensitive Azo-group as a branch (Azo-PM). Azo-PM is synthesized using a solid-phase procedure during which an azobenzene unit is attached as a side chain to an oligo(amidoamine) backbone. We show that within a certain range of concentrations and under illumination with light of appropriate wavelengths, these cationic molecules induce reversible DNA compaction/decompaction by photoisomerization of the incorporated azobenzene unit between a hydrophobic trans- and a hydrophilic cis-conformation, as characterized by dynamic light scattering and AFM measurements. In contrast to other molecular species used for invasive DNA compaction, such as widely used azobenzene containing cationic surfactant (Azo-TAB, C4-Azo-OCX-TMAB), the presented peptidomimetic agent appears to lead to different complexation/compaction mechanisms. An investigation of Azo-PM in close proximity to a DNA segment by means of a molecular dynamics simulation sustains a picture in which Azo-PM acts as a multivalent counterion, with its rather large cationic oligo(amidoamine) backbone dominating the interaction with the double helix, fine-tuned or assisted by the presence and isomerization state of the Azo-moiety. However, due to its peptidomimetic backbone, Azo-PM should be far less toxic than photosensitive surfactants and might represent a starting point for a conscious design of photoswitchable, biocompatible vectors for gene delivery.

A comparative study of photoinduced deformation in azobenzene containing polymer films.

In this paper two groups supporting different views on the mechanism of light induced polymer deformation argue about the respective underlying theoretical conceptions, in order to bring this interesting debate to the attention of the scientific community. The group of Prof. Nicolae Hurduc supports the model claiming that the cyclic isomerization of azobenzenes may cause an athermal transition of the glassy azobenzene containing polymer into a fluid state, the so-called photo-fluidization concept. This concept is quite convenient for an intuitive understanding of the deformation process as an anisotropic flow of the polymer material. The group of Prof. Svetlana Santer supports the re-orientational model where the mass-transport of the polymer material accomplished during polymer deformation is stated to be generated by the light-induced re-orientation of the azobenzene side chains and as a consequence of the polymer backbone that in turn results in local mechanical stress, which is enough to irreversibly deform an azobenzene containing material even in the glassy state. For the debate we chose three polymers differing in the glass transition temperature, 32 °C, 87 °C and 95 °C, representing extreme cases of flexible and rigid materials. Polymer film deformation occurring during irradiation with different interference patterns is recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. We also demonstrated the unique behaviour of azobenzene containing polymeric films to switch the topography in situ and reversibly by changing the irradiation conditions. We discuss the results of reversible deformation of three polymers induced by irradiation with intensity (IIP) and polarization (PIP) interference patterns, and the light of homogeneous intensity in terms of two approaches: the re-orientational and the photo-fluidization concepts. Both agree in that the formation of opto-mechanically induced stresses is a necessary prerequisite for the process of deformation. Using this argument, the deformation process can be characterized either as a flow or mass transport.