Light-Regulated Liquid-Liquid Phase Separation for Spatiotemporal Protein Recruitment and Cell Aggregation.

We have previously shown that the upper critical solution temperature-type thermoresponsive ureido polymers such as polyallylurea and poly(2-ureidoethylmethacrylate) derivatives show liquid-liquid phase separation (LLPS), also known as simple coacervation, under physiological conditions below their phase-separation temperatures (Tp). The addition of the polymer-rich coacervate droplets that result from LLPS to a monolayer cell culture induced aggregation of cells into multicellular spheroids. In this study, we prepared a ureido copolymer, poly(vinylamine-co-vinylurea), with azobenzene substituents (Azo-PVU) and demonstrated light-guided assembly and disassembly of LLPS coacervates. Azo-PVUs with Tp values ranging from 10 to 52 °C were prepared by changing the azobenzene content. Ultraviolet light caused a decrease in the Tp of Azo-PVU because of trans-to-cis photoisomerization of the azobenzene and irradiation with visible light increased the Tp. Thus, LLPS of Azo-PVU was reversibly controlled. The coacervate droplets deposited on a dish surface were immediately dissolved by targeted UV irradiation (owing to a decrease in the Tp). Spatially controlled recruitment of proteins on the dish surface was achieved when protein solution was added to the light-patterned surface. Furthermore, the light-guided deposition of coacervates resulted in the spatiotemporal transformation of monolayer cells to aggregates. This light-controlled LLPS will allow the preparation of novel liquid-based materials for biomolecular and cellular engineering.

One Step e-Beam Radiation Cross-Linking of Quaternary Hydrogels Dressings Based on Chitosan-Poly(Vinyl-Pyrrolidone)-Poly(Ethylene Glycol)-Poly(Acrylic Acid).

We report on the successful preparation of wet dressings hydrogels based on Chitosan-Poly(N-Vinyl-Pyrrolidone)-Poly(ethylene glycol)-Poly(acrylic acid) and Poly(ethylene oxide) by e-beam cross-linking in weakly acidic media, to be used for rapid healing and pain release of infected skin wounds. The structure and compositions of hydrogels investigated according to sol-gel and swelling studies, network parameters, as well as FTIR and XPS analyses showed the efficient interaction of the hydrogel components upon irradiation, maintaining the bonding environment while the cross-linking degree increasing with the irradiation dose and the formation of a structure with the mesh size in the range 11-67 nm. Hydrogels with gel fraction above 85% and the best swelling properties in different pH solutions were obtained for hydrogels produced with 15 kGy. The hydrogels are stable in the simulated physiological condition of an infected wound and show appropriate moisture retention capability and the water vapor transmission rate up to 272.67 g m-2 day-1, to ensure fast healing. The hydrogels proved to have a significant loading capacity of ibuprofen (IBU), being able to incorporate a therapeutic dose for the treatment of severe pains. Simultaneously, IBU was released up to 25% in the first 2h, having a release maximum after 8 h.

Ultrasound-Assisted miR-122-Loaded Polymeric Nanodroplets for Hepatocellular Carcinoma Gene Therapy.

Ultrasound-induced microbubble sonoporation has been shown to effectively improve drug/gene delivery efficiency by enhancing tissue and cell permeability. However, the microscale size and short duration of ultrasound contrast agents limit their accumulation in target areas. Here, a kind of ultrasound-triggered phase-transitioning and size-changing cationic nanodroplet, perfluoropentane/C9F17-PAsp(DET)/miR-122/poly(glutamic acid)-g-MeO-poly(ethylene glycol) (PGA-g-mPEG) ternary nanodroplets (PFP-TNDs/miR-122), was developed to deliver microRNA-122 (miR-122) for hepatocellular carcinoma (HCC) treatment. PFP served as an ultrasound-sensitive core for ultrasound-triggered phase transition and size change from the nanoscale to the microscale. Positively charged C9F17-PAsp(DET) ensured adequate miRNA loading. PGA-g-mPEG, which served as the shell of the nanodroplet, modified the nanodroplets, enhanced their stability in serum, and protected miR-122 from degradation in vivo. The results exhibited that PFP-TNDs/miR-122 has a nanosize diameter (362 ± 15 nm) and remained stable for 24 h. After treatment with PFP-TNDs/miR-122 combined with ultrasound irradiation, the miR-122 expression level was significantly increased by approximately 600-fold in HepG2 cells, 500-fold in SMMC-7721 cells, and 30-fold in human HCC xenografts. Moreover, PFP-TNDs/miR-122 combined with ultrasound radiation effectively suppressed the growth, migration, and invasion of HCC cells, and inhibited tumor proliferation in mice. This study revealed that the biodegradable PFP-TNDs is a promising therapeutic gene carrier with functions of gene protection and effective gene delivery for clinical applications. Furthermore, PFP-TNDs/miR-122 associated with ultrasound irradiation may pave a new way to improve the prognosis of patients with HCC.

Noncovalent Spin-Labeling of DNA and RNA Triplexes.

Studying nucleic acids often requires labeling. Many labeling approaches require covalent bonds between the nucleic acid and the label, which complicates experimental procedures. Noncovalent labeling avoids the need for highly specific reagents and reaction conditions, and the effort of purifying bioconjugates. Among the least invasive techniques for studying biomacromolecules are NMR and EPR. Here, we report noncovalent labeling of DNA and RNA triplexes with spin labels that are nucleobase derivatives. Spectroscopic signals indicating strong binding were detected in EPR experiments in the cold, and filtration assays showed micromolar dissociation constants for complexes between a guanine-derived label and triplex motifs containing a single-nucleotide gap in the oligopurine strand. The advantages and challenges of noncovalent labeling via this approach that complements techniques relying on covalent links are discussed.

Stability of the different arms of a DNA tetrahedron and its interaction with a minor groove ligand.

DNA strands can be designed to assemble into stable three-dimensional structures, based on Watson-Crick base pairing rules. The simplest of these is the DNA tetrahedron that is composed of four oligonucleotides. We have re-designed the sequence of a DNA tetrahedron so that it contains a single (AATT) binding site for the minor groove binding ligand Hoechst 33258. We examined the stability of this structure by placing fluorescent groups within each of its edges and have shown that all the edges melt at the same temperature in the absence of the ligand. The minor groove ligand still binds to its recognition sequence within the tetrahedron and increases the melting temperature of the folded complex. This ligand-induced stabilisation is propagated into the adjacent helical arms and the tetrahedron melts as a single entity in a cooperative fashion.

Electron microscopy analysis of the thermal phase transition from hydroxyapatita to ß-TCP observed in human teeth.

Samples of enamel and dentin from human molar teeth were heated in air from room temperature (25°C) up to 1200°C and the phase transition from hydroxyapatite (HAP) to tricalcium phosphate (ß-TCP) was recorded. The changes produced in morphology and chemical composition in the tooth during heating were analysed by light microscopy, scanning electron microscopy (SEM), characteristic x-ray energy dispersion spectroscopy (EDS), x-ray diffraction (XRD), electron diffraction, transmission electron microscopy (TEM) and high-resolution electron microscopy (HRTEM). The results indicated a high correlation relationship among Ca content, P content, O content and Na content, and the existence of the Kirkendall effect during the HAP- ß-TCP phase transition. LAY DESCRIPTION: This work is related with tooth materials. Samples of enamel and dentine from human molar teeth were heated in air from 25°C up to 1200°C and the phase transition from hydroxyapatite (HAP) to tricalcium phosphate (ß-TCP) was recorded. The ß-TCP phase is also known as whitlockite. The changes produced in morphology and chemical composition in the tooth during heating were analysed by electron microscopy and X-ray diffraction. The results indicated a high correlation relationship among Ca, P, O and Na contents, and the existence of the Kirkendall effect, the atomic diffusion producing voids, during the HAP- ß-TCP phase transition.

Light-activated doxorubicin-encapsulated perfluorocarbon nanodroplets for on-demand drug delivery in an in vitro angiogenesis model: Comparison between perfluoropentane and perfluorohexane.

Phase-transition perfluorocarbon (PFC) nanodroplets have been developed for on-demand drug delivery carriers with external triggers such as ultrasound or laser irradiation techniques. Although various perfluorocarbons, including perfluoropentane (C5F12) and perfluorohexane (C6F14), have been investigated for their theranostic use, comparison of the phase-transition efficiency, the drug delivery efficacy by light activation, and physical properties of the PFC nanodroplets have not been reported. We have synthesized gold nanorod-coated doxorubicin-encapsulated perfluorocarbon nanodroplets using perfluoropentane and perfluorohexane as light-activated on-demand drug delivery carriers, called PF5 and PF6, respectively. When gold nanorods on the perfluorocarbon nanodroplets resonate with a laser wavelength, plasmonic heat generated on the gold nanorods vaporizes the nanodroplets to gas bubbles (phase-transition), and releases the encapsulated drug from the nanodroplet core. Overall, the nanodroplet size, drug encapsulation efficiency, number density, and cytotoxicity were similar between PF5 and PF6. However, the long-term stability against passive phase-transition or coalescence in physiological conditions and the phase-transition efficiency were different from each other. PF6 was better in long-term stability but showed lower phase-transition than PF5. The lower phase-transition of PF6 might have led to lower drug delivery efficiency compared to PF5. This is probably because PF6 has higher temperature thresholds required for phase-transition due to its higher boiling point. The study demonstrated feasibility of the light-activated nanodroplets for on-demand targeted nanotherapy, which suppresses the development of angiogenesis.

Off-on switching of enzyme activity by near-infrared light-induced photothermal phase transition of nanohybrids.

The off-on manipulation of enzyme activity is a challenging task. We report a new strategy for reversible off-on control of enzyme activity by near-infrared light. Enzymes acting on macromolecular substrates are embedded with an ultrasmall platinum nanoparticle and decorated with thermoresponsive copolymers, which exhibit upper critical solution temperature (UCST) behavior. The polymer-enzyme nanohybrids form microscale aggregates in solution below the UCST to prevent macromolecular substrates from approaching the enzymes and thus inhibit the enzyme activity, and they disassemble above the UCST to reactivate the enzyme. Upon near-infrared irradiation, platinum nanoparticles inside the enzymes generate heat through a photothermal effect to cause phase transition of the copolymers. Therefore, we can reversibly switch off and on the activities of three enzymes acting on polysaccharide, protein, and plasmid. The enzyme activities are increased by up to 61-fold after laser irradiation. This study provides a facile and efficient method for off-on control of enzyme activity.

Excellent Temperature-Control Based on Reversible Thermochromic Materials for Light-Driven Phase Change Materials System.

Light-driven phase change materials (PCMs) have received significant attention due to their capacity to convert visible light into thermal energy, storing it as latent heat. However, continuous photo-thermal conversion can cause the PCMs to reach high thermal equilibrium temperatures after phase transition. In our study, a novel light-driven phase change material system with temperature-control properties was constructed using a thermochromic compound. Thermochromic phase change materials (TC-PCMs) were prepared by introducing 2-anilino-6-dibutylamino-3-methylfluoran (ODB-2) and bisphenol A (BPA) into 1-hexadecanol (1-HD) in various proportions. Photo-thermal conversion performance was investigated with solar radiation (low power of 0.09 W/cm2) and a xenon lamp (at a high power of 0.14 W/cm2). The TC-PCMs showed a low equilibrium temperature due to variations in absorbance. Specifically, the temperature of TC-PCM180 (ODB-2, bisphenol A and 1-HD ratio 1:2:180) could stabilize at 54 °C approximately. TC-PCMs exhibited reversibility and repeatability after 20 irradiation and cooling cycles.

Effect of radiant exposure and UV accelerated aging on physico-chemical and mechanical properties of composite resins.

Currently, there is no consensus in terms of defining the minimum radiant exposure values necessary for achieving adequate properties of composite resin. In addition, the long-term influence that radiant exposure has on the properties of composite resins is still questionable. OBJECTIVE: The objective of this study was to evaluate the effect of radiant exposure and UV accelerated aging on the physico-chemical and mechanical properties of micro-hybrid and nanofilled composite resins. MATERIAL AND METHODS: A nanofilled (Filtek Supreme; 3M ESPE) and a micro-hybrid composite resin (Filtek Z250; 3M ESPE) were investigated under different radiant exposures (3.75, 9, and 24 J/cm2) and UV accelerated aging protocols (0, 500, 1000, and 1500 aging hours). The degree of conversion (DC), flexural strength (FS), modulus (M), water sorption (WS), and solubility (WL) were evaluated. The results obtained were analyzed using two-way ANOVA and Tukey's test. Comparisons were performed using a significance level of α=0.05. RESULTS: The DC, FS, and M were found to be significantly influenced by both radiant exposure and accelerated aging time. The DC and EM increased with radiant exposure in the no-aging group (0-hour aging) for both micro-hybrid and nanofilled composites, whereas no correlation was found after accelerated aging protocols. WS and WL of micro-hybrid and nanofilled composite resins were scarcely affected by radiant exposure (p>0.05), whereas they were significantly reduced by accelerated aging (p<0.001). CONCLUSIONS: Although increasing radiant exposure affected the degree of conversion and mechanical properties of micro-hybrid and nanofilled composites, no influence on the hydrolytic degradation of the material was observed. In contrast, UV accelerated aging affected both the physico-chemical and mechanical properties of the composites.

Photomodulated Morphologies in Halogen Bond-Driven Assembly during Gel-Sol Transition.

Photoresponsive supramolecular gels with various applications are being constantly pursued; however, achieving well-defined morphology changes of gels via light irradiation remains a formidable challenge. In this study, a gel is prepared through halogen bond between azopyridine-containing Azopy-C10 and 1,4-tetrafluorodiiodobenzene. The gel exhibits gel-sol transition due to trans-cis isomerization of the azopyridine moiety upon UV irradiation. During this transition, the morphologies vary from flake to fluffy bobble-like and finally to peony-like with increasing exposure time, which is difficult to achieve in traditional assembly systems. The microstructure change is attributed to the variations of cis-isomer content and halogen-bonding strength. The supramolecular gel provides a novel method to achieve photomodulated morphologies and broadens the applications of such kind of materials, ranging from information storage to high-tech anticounterfeit.

Effect of radiant exposure and UV accelerated aging on physico-chemical and mechanical properties of composite resins

Abstract Currently, there is no consensus in terms of defining the minimum radiant exposure values necessary for achieving adequate properties of composite resin. In addition, the long-term influence that radiant exposure has on the properties of composite resins is still questionable. Objective: The objective of this study was to evaluate the effect of radiant exposure and UV accelerated aging on the physico-chemical and mechanical properties of micro-hybrid and nanofilled composite resins. Material and Methods: A nanofilled (Filtek Supreme; 3M ESPE) and a micro-hybrid composite resin (Filtek Z250; 3M ESPE) were investigated under different radiant exposures (3.75, 9, and 24 J/cm2) and UV accelerated aging protocols (0, 500, 1000, and 1500 aging hours). The degree of conversion (DC), flexural strength (FS), modulus (M), water sorption (WS), and solubility (WL) were evaluated. The results obtained were analyzed using two-way ANOVA and Tukey's test. Comparisons were performed using a significance level of α=0.05. Results: The DC, FS, and M were found to be significantly influenced by both radiant exposure and accelerated aging time. The DC and EM increased with radiant exposure in the no-aging group (0-hour aging) for both micro-hybrid and nanofilled composites, whereas no correlation was found after accelerated aging protocols. WS and WL of micro-hybrid and nanofilled composite resins were scarcely affected by radiant exposure (p>0.05), whereas they were significantly reduced by accelerated aging (p<0.001). Conclusions: Although increasing radiant exposure affected the degree of conversion and mechanical properties of micro-hybrid and nanofilled composites, no influence on the hydrolytic degradation of the material was observed. In contrast, UV accelerated aging affected both the physico-chemical and mechanical properties of the composites.

Minimization of polymerization shrinkage effects on composite resins by the control of irradiance during the photoactivation process.

INTRODUCTION: High levels of shrinkage stress caused by volumetric variations during the activation process are one of the main problems in the practical application of composite resins. OBJECTIVE: The aim of this study is to reduce the shrinkage stress and minimize the effects caused by composite resin volumetric variation due to the photopolymerization. In this way, this work proposes a systematic study to determine the optimal dimming function to be applied to light curing processes. MATERIAL AND METHODS: The study was performed by applying mathematical techniques to the optimization of nonlinear objective functions. The effectiveness of the dimming function was evaluated by monitoring the polymerization shrinkage stress during the curing process of five brands/models of composites. This monitoring was performed on a universal testing machine using two steel bases coupled in the arms of the machine where the resin was inserted and polymerized. The quality of the composites cured by the proposed method was analyzed and compared with the conventional photoactivation method by experiments to determine their degree of conversion (DC). Absorbance measurements were performed using Fourier-transform infrared spectroscopy (FT-IR). A T-test was performed on DC results to compare the photoactivation techniques. We also used scanning electron microscopy (SEM) to analyze in-vitro the adhesion interface of the resin in human teeth. RESULTS: Our results showed that the use of the optimal dimming function, named as exponential, resulted in the significant reduction of the shrinkage stress (~36.88% ±6.56 when compared with the conventional method) without affecting the DC (t=0.86, p-value=0.44). The SEM analyses show that the proposed process can minimize or even eliminate adhesion failures between the tooth and the resin in dental restorations. CONCLUSION: The results from this study can promote the improvement of the composite resin light curing process by the minimization of polymerization shrinkage effects, given an operational standardization of the photoactivation process.

Minimization of polymerization shrinkage effects on composite resins by the control of irradiance during the photoactivation process

Abstract High levels of shrinkage stress caused by volumetric variations during the activation process are one of the main problems in the practical application of composite resins. Objective The aim of this study is to reduce the shrinkage stress and minimize the effects caused by composite resin volumetric variation due to the photopolymerization. In this way, this work proposes a systematic study to determine the optimal dimming function to be applied to light curing processes. Material and Methods The study was performed by applying mathematical techniques to the optimization of nonlinear objective functions. The effectiveness of the dimming function was evaluated by monitoring the polymerization shrinkage stress during the curing process of five brands/models of composites. This monitoring was performed on a universal testing machine using two steel bases coupled in the arms of the machine where the resin was inserted and polymerized. The quality of the composites cured by the proposed method was analyzed and compared with the conventional photoactivation method by experiments to determine their degree of conversion (DC). Absorbance measurements were performed using Fourier-transform infrared spectroscopy (FT-IR). A T-test was performed on DC results to compare the photoactivation techniques. We also used scanning electron microscopy (SEM) to analyze in-vitro the adhesion interface of the resin in human teeth. Results Our results showed that the use of the optimal dimming function, named as exponential, resulted in the significant reduction of the shrinkage stress (~36.88% ±6.56 when compared with the conventional method) without affecting the DC (t=0.86, p-value=0.44). The SEM analyses show that the proposed process can minimize or even eliminate adhesion failures between the tooth and the resin in dental restorations. Conclusion The results from this study can promote the improvement of the composite resin light curing process by the minimization of polymerization shrinkage effects, given an operational standardization of the photoactivation process.

Does laser diode irradiation improve the degree of conversion of simplified dentin bonding systems?

OBJECTIVE: This study aimed to investigate the effect of laser diode irradiation on the degree of conversion (DC), water sorption (WS), and water solubility (WSB) of these bonding systems in an attempt to improve their physico-mechanical resistance. MATERIAL AND METHODS: Two bonding agents were tested: a two-step total-etch system [Adper™ Single Bond 2, 3M ESPE (SB)] and a universal system [Adper™ Single Bond Universal, 3M ESPE (SU)]. Square-shaped specimens were prepared and assigned into 4 groups (n=5): SB and SU (control groups - no laser irradiation) and SB-L and SU-L [SB and SU laser (L) - irradiated groups]. DC was assessed using Fourier transform infrared spectroscopy with attenuated total reflectance. Additional uncured resin samples (≈3.0 µL, n=5) of each adhesive were also scanned for final DC calculation. For WS/WSB tests, similar specimens (n=10) were prepared and measured by monitoring the mass changes after dehydration/water storage cycles. For both tests, adhesive fluids were dropped into standardized Teflon molds (6.0×6.0×1.0 mm), irradiated with a 970-nm laser diode, and then polymerized with an LED-curing unit (1 W/cm2). RESULTS: Laser irradiation immediately before photopolymerization increased the DC (%) of the tested adhesives: SB-L>SB>SU-L>SU. For WS/WSB (µg/mm3), only the dentin bonding system (DBS) was a significant factor (p<0.05): SB>SU. CONCLUSION: Irradiation with a laser diode improved the degree of conversion of all tested simplified dentin bonding systems, with no impact on water sorption and solubility.

Does laser diode irradiation improve the degree of conversion of simplified dentin bonding systems?

Abstract Simplified dentin-bonding systems are clinically employed for most adhesive procedures, and they are prone to hydrolytic degradation. Objective This study aimed to investigate the effect of laser diode irradiation on the degree of conversion (DC), water sorption (WS), and water solubility (WSB) of these bonding systems in an attempt to improve their physico-mechanical resistance. Material and Methods Two bonding agents were tested: a two-step total-etch system [Adper™ Single Bond 2, 3M ESPE (SB)] and a universal system [Adper™ Single Bond Universal, 3M ESPE (SU)]. Square-shaped specimens were prepared and assigned into 4 groups (n=5): SB and SU (control groups - no laser irradiation) and SB-L and SU-L [SB and SU laser (L) - irradiated groups]. DC was assessed using Fourier transform infrared spectroscopy with attenuated total reflectance. Additional uncured resin samples (≈3.0 µL, n=5) of each adhesive were also scanned for final DC calculation. For WS/WSB tests, similar specimens (n=10) were prepared and measured by monitoring the mass changes after dehydration/water storage cycles. For both tests, adhesive fluids were dropped into standardized Teflon molds (6.0×6.0×1.0 mm), irradiated with a 970-nm laser diode, and then polymerized with an LED-curing unit (1 W/cm2). Results Laser irradiation immediately before photopolymerization increased the DC (%) of the tested adhesives: SB-L>SB>SU-L>SU. For WS/WSB (μg/mm3), only the dentin bonding system (DBS) was a significant factor (p<0.05): SB>SU. Conclusion Irradiation with a laser diode improved the degree of conversion of all tested simplified dentin bonding systems, with no impact on water sorption and solubility.

Exploring the impact of the side-chain length on peptide/RNA binding events.

The impact of the amino-acid side-chain length on peptide-RNA binding events has been investigated using HIV-1 Tat derived peptides as ligands and the HIV-1 TAR RNA element as an RNA model. Our studies demonstrate that increasing the length of all peptide side-chains improves unexpectedly the binding affinity (KD) but reduces the degree of compactness of the peptide-RNA complex. Overall, the side-chain length appears to modulate in an unpredictable way the ability of the peptide to compete with the cognate TAR RNA partner. Beyond the establishment of non-intuitive fundamental relationships, our results open up new perspectives in the design of effective RNA ligand competitors, since a large number of them have already been identified but few studies report on the modulation of the biological activity by modifying in the same way the length of all chains connecting RNA recognition motives to the central scaffold of a ligand.

Impact of light transmittance mode on polymerisation kinetics in bulk-fill resin-based composites.

OBJECTIVES: to determine the mode of light transmission and its impact on the polymerisation kinetic in modern bulk-fill resin-based composites (B-RBC). MATERIALS AND METHODS: Four low-viscosity methacrylate-based and one high-viscosity ormocer-based B-RBCs were considered. One material was available in three different shades that were all analyzed. Polymerization kinetic and light transmittance were assessed in 2 and 4mm specimen depths. Incident and transmitted irradiance and radiant exposure were measured in real-time on a laboratory-grade spectrometer. RESULTS: A progressive enhanced light transmittance during polymerisation was identified in all materials except for TetricEvoFlow BulkFill, which became progressively opaque in all shades. One-way ANOVA and multivariate analysis (α=0.05) were performed. The parameter material has a significant (p<0.001) effect on DC (ηP2=0.856) and light transmittance parameters (irradiance, ηP2=0.965; radiant exposure, ηP2=0.956); specimen depth influences only transmittance (ηP2=0.978; 0.980). DC variation in time was best described by an exponential sum function (R2>0.95), differentiating between the gel- and the glass-phase and revealing a faster initiation of polymerization and a slower transition into the glass-phase by lowering the filler volume. Depth retarded the transition into the glass-phase, but did not alter DC measured 300s post-irradiation. Moderate inverse correlation was identified among DC and filler volume% (-0.646) or filler weight% (-0.403), while no correlation among DC and light transmittance (p=0.141; 0.125). The maximal rate of carbon-carbon double bond conversion varied within the analyzed materials but was independent from specimen's depths. CONCLUSIONS: Light transmission changes during polymerization do not alter polymerization kinetics in modern B-RBCs. DC 300s post-irradiation was maintained with depth, while light was attenuated, the faster the more translucent the material was. DC and quality of curing cannot be related to light transmittance in B-RBCs.

Continuous Isotropic-Nematic Transition in Amyloid Fibril Suspensions Driven by Thermophoresis.

The isotropic and nematic (I + N) coexistence for rod-like colloids is a signature of the first-order thermodynamics nature of this phase transition. However, in the case of amyloid fibrils, the biphasic region is too small to be experimentally detected, due to their extremely high aspect ratio. Herein, we study the thermophoretic behaviour of fluorescently labelled ß-lactoglobulin amyloid fibrils by inducing a temperature gradient across a microfluidic channel. We discover that fibrils accumulate towards the hot side of the channel at the temperature range studied, thus presenting a negative Soret coefficient. By exploiting this thermophoretic behaviour, we show that it becomes possible to induce a continuous I-N transition with the I and N phases at the extremities of the channel, starting from an initially single N phase, by generating an appropriate concentration gradient along the width of the microchannel. Accordingly, we introduce a new methodology to control liquid crystal phase transitions in anisotropic colloidal suspensions. Because the induced order-order transitions are achieved under stationary conditions, this may have important implications in both applied colloidal science, such as in separation and fractionation of colloids, as well as in fundamental soft condensed matter, by widening the accessibility of target regions in the phase diagrams.

Phase-transitional Fe3O4/perfluorohexane Microspheres for Magnetic Droplet Vaporization.

Activating droplets vaporization has become an attractive strategy for ultrasound imaging and physical therapy due to the significant increase in ultrasound backscatter signals and its ability to physically damage the tumor cells. However, the current two types of transitional droplets named after their activation methods have their respective limitations. To circumvent the limitations of these activation methods, here we report the concept of magnetic droplet vaporization (MDV) for stimuli-responsive cancer theranostics by a magnetic-responsive phase-transitional agent. This magnetic-sensitive phase-transitional agent-perfluorohexane (PFH)-loaded porous magnetic microspheres (PFH-PMMs), with high magnetic-thermal energy-transfer capability, could quickly respond to external alternating current (AC) magnetic fields to produce thermal energy and trigger the vaporization of the liquid PFH. We systematically demonstrated MDV both in vitro and in vivo. This novel trigger method with deep penetration can penetrate the air-filled viscera and trigger the vaporization of the phase-transitional agent without the need of pre-focusing lesion. This unique MDV strategy is expected to substantially broaden the biomedical applications of nanotechnology and promote the clinical treatment of tumors that are not responsive to chemical therapies.