Polymer Films Research Articles

Bioadhesive Polymeric Films Containing Rhamnolipids, An Innovative Antimicrobial Topical Formulation.

Acne affects most of the world's population, causing an impact on the self-esteem of adolescents and young adults. One of the causes is the presence of the bacteria Cutibacterium acnes which are part of the natural microbiota of the skin. Topical treatments consist of anti-inflammatory and antibiotics, which could select resistant strains. Alternatives to the antibiotic are biocomposites that have antimicrobial activity like biosurfactants which are produced by bacteria. An innovative way of applying these compounds is bioadhesive polymeric films that adhere to the skin and release the active principle topically. Rhamnolipids have great potential to be used in the treatment of acne because they present antimicrobial activity against C. acnes in low and safe concentrations (MIC of 15.62µg/mL, CBM of 31.25µg/mL and CC50 of 181.93µg/mL). Four films with different rhamnolipids concentrations (0.0; 0.1; 0.2; and 0.3%, w/w) were obtained as to visual appearance, mass variation, thickness, density, solubility, pH, water vapor transmission, mechanical properties (folding endurance, bioadhesion strength, tensile strength, elongation at break and Young's modulus), scanning electron microscopy and infrared. The results show that these formulations had a homogeneous appearance; elastic mechanical properties; pH similar to human skin and bioadhesive. The polymeric films containing rhamnolipids were effective against C. acnes, in the in vitro test, at the three concentrations tested, the film with the highest concentration (0.3%, w/w) being the most promising for presenting the highest antimicrobial activity. Thus, the polymeric film containing rhamnolipids has the potential to be used in the treatment of acne.

Strengthening the π-conjugation of lignin by constructing its ordered supramolecular structure

The π-conjugation system of lignin makes it one kind of multifunctional biopolymer with many remarkable features such as ultraviolet-shielding properties, photothermal conversion capability, and fluorescence performance. The quest for effective strategies to strengthen the π-conjugation of lignin is significantly important to the design and production of outstanding lignin-based materials. In this work, we strengthen the π-conjugation of lignin by transforming lignin raw materials from disordered aggregates into ordered lignin colloidal spheres (LCSs) through supramolecular self-assembly. Moreover, we explore the relationship between the conjugation of lignin and its supramolecular structure by comparing the LCSs with different sizes, functional group arrangements, and compactness. Results demonstrate that the conjugation is stronger in the LCSs that have more hydrophobic groups inside and higher density. The primary strengthening mechanism of lignin conjugation is that the ordered and compact supramolecular structure results in a shorter average distance between benzene rings and stronger π-π interaction compared with that of disordered and loose supramolecular structure. We further demonstrate the great ultraviolet-shielding property and photothermal conversion capability of LCSs in polymer films, in which LCSs exhibit improved application performances than that of lignin raw materials due to their strengthened conjugation.

Induced polarization imparts piezoelectricity in noncrystalline polymer films

Induced polarization imparts piezoelectricity in noncrystalline polymer films

PYN-based antiferroelectric ceramics with superior energy storage performance within an ultra-wide temperature range

Antiferroelectric (AFE) ceramics are known for their rich field-induced phase transitions, which mainly contribute to their superior energy storage performance. However, the phase transitions instability caused by high temperature often limits its application scenarios. Developing AFE ceramics with high energy storage properties and wide application temperature ranges is challenging. Here, considering the B-site ordering characteristics of Pb(Yb0.5Nb0.5)O3, we propose a simple approach for introducing A-site distortion and adjusting B-site ordering to confront these challenges. In our Fe3+/Sr2+co-doping system, we realized an ultra-wide temperature range of 25–200 °C, within which the recoverable storage density was considerable: 8.48–13.39 J cm−3. In this interval, the discharge energy density could reach 6.15–9.67J cm−3, and the discharge current density and discharge power density were 755.09–1667.36 A cm−2 and 207.65–500.21 MW cm−3, respectively. The obtained high-temperature energy storage performance was superior to that of existing energy storage ceramics or polymer films. The introduction of A-site distortion improves the stability of AFE phase, the decrease in B-site ordering suppresses the remanent polarization and delays change in structural symmetry with temperature. This study forms a basis for further applications of dielectric capacitors and signifies the development of wide-temperature-range energy storage devices.

Phage probe on RAFT polymer surface for rapid enumeration of E. coli K12

This study presents a simple, fast, and sensitive label-free sensing assay for the precise enumeration of modeled pathogenic Escherichia coli K12 (E. coli K12) bacteria for the first time. The method employs the covalent binding bacteriophage technique on the surface of a reversible addition-fragmentation chain transfer (RAFT) polymer film. The Nyquist plots obtained from electrochemical impedance spectroscopy (EIS) identified the charge transfer resistance Rct was calculated from a suitable electrochemical circuit model through an evaluation of the relevant parameter after the immobilization of the bacteriophage and the binding of specific E. coli K12. The impedimetric biosensor reveals specific and reproducible detection with sensitivity in the linear working range of 104.2-107.0 CFU/mL, a limit of detection (LOD) of 101.3 CFU/mL, and a short response time of 15 min. The SERS response validates the surface roughness and interaction of the SERS-tag with E. coli K12-modified electrodes. Furthermore, the covalently immobilized active phage selectivity was proved against various non-targeting bacterial strains in the presence of targeted E.coli K12 with a result of 94 % specificity and 98 % sensitivity. Therefore, the developed phage-based electrode surface can be used as a disposable, label-free impedimetric biosensor for rapid and real-time monitoring of serum samples.

Mechanical Effect Produced by Photo‐Switchable Reactions: Insights from Molecular Simulations

AbstractLight‐responsive shape‐changing polymers are photonastic materials: they can convert light into mechanical energy through macroscopic transformations. Indeed, photochromic molecules embedded in these polymer films present light‐induced structural modifications that can trigger a significant macroscopic deformation. In this theoretical study based on molecular dynamics simulations, analysis tools ranging from atomic to supramolecular scales are developed to investigate this photonastic phenomenon. To this purpose, a model system built upon an azobenzene photochrome embedded in different environments (tetrahydrofuran, cis‐1,4‐polybutadiene and hydroxyl‐terminated polybutadiene) is considered. First, the impact of the environment on the photochrome properties is discussed through the analysis of the structural properties, ultra‐violet visible (UV–vis) absorption spectra and dynamical properties of the photoswitch. Then, the impact of the presence of the photochrome on the polymer is studied. At the atomic scale, the radial distribution functions show some differences between the cis and trans isomers due to geometrical effects. At the molecular scale, the analysis of the size and shape of the polymer chains reveals that the photochrome has no impact on the chain properties. Finally, at the macroscopic scale, the cohesive energy density shows that the polymer is stabilized by the presence of photochrome molecules.

Optical Monitoring of Supramolecular Interactions in Polymers.

Many stimuli-responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self-healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure-property relationships of these materials, direct correlations between molecular-level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen-bonding ureido-4-pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross-linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross-linker content, processing history, and applied stimuli. We demonstrate that the stimuli-induced dissociation of hydrogen-bonding linkages strongly depends on the initial cross-link density, which also dictates whether the force-induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.

Optical Monitoring of Supramolecular Interactions in Polymers

AbstractMany stimuli‐responsive materials harness the reversible association of supramolecular binding motifs to enable advanced functionalities such as self‐healing, switchable adhesion, or mechanical adaptation. Despite extensive research into the structure–property relationships of these materials, direct correlations between molecular‐level changes in supramolecular binding and macroscopic material behaviors have mostly remained elusive. Here, we show that this challenge can be overcome with supramolecular binding motifs featuring integrated binding indicators. We demonstrate this using a novel motif that combines a hydrogen‐bonding ureido‐4‐pyrimidinone (UPy) with two strategically placed pyrene fluorophores. Dimerization of this motif promotes pyrene excimer formation, facilitating the straightforward optical quantification of supramolecular assembly under various conditions. We exploit the new motif as a supramolecular cross‐linker in poly(methyl acrylate)s to probe the extent of (dis)assembly as a function of cross‐linker content, processing history, and applied stimuli. We demonstrate that the stimuli‐induced dissociation of hydrogen‐bonding linkages strongly depends on the initial cross‐link density, which also dictates whether the force‐induced dissociation in polymer films correlates with the applied stress or strain. Thus, beyond introducing a robust tool for the in situ study of dynamic (dis)assembly mechanisms in supramolecular systems, our findings provide new insights into the mechanoresponsive behavior of such materials.

Interfacial Synthesis of Two‐Dimensional Porphyrin Polymer Films with Large Optical Nonlinearity

Interfacial Synthesis of Two‐Dimensional Porphyrin Polymer Films with Large Optical Nonlinearity

Optimization of fluorinated phenyl azides as universal photocrosslinkers for semiconducting polymers

Fluorinated phenyl azides (FPA) enable photo-structuring of π-conjugated polymer films for electronic device applications. Despite their potential, FPAs have faced limitations regarding their crosslinking efficiency, and more importantly, their impact on critical semiconductor properties, such as charge-carrier mobility. Here, we report that azide photolysis and photocrosslinking can achieve unity quantum efficiencies for specific FPAs. This suggests preferential nitrene insertion into unactivated C‒H bonds over benzazirine and ketenimine reactions, which we attribute to rapid interconversion between the initially formed hot states. Furthermore, we establish a structure‒activity relationship for carrier mobility quenching. The binding affinity of FPA crosslinker to polymer π-stacks governs its propensity for mobility quenching in both PM6 and PBDB-T used as model conjugated polymers. This binding affinity can be suppressed by FPA ring substitution, but varies in a non-trivial way with π-stack order. Utilizing the optimal FPA, photocrosslinking enables the fabrication of morphology-stabilized, acceptor-infiltrated donor polymer networks (that is, PBDB-T: ITIC and PM6: Y6) for solar cells. Our findings demonstrate the exceptional potential of the FPA photochemistry and offer a promising approach to address the challenges of modelling realistic molecular interactions in complex polymer morphologies, moving beyond the limitations of Flory‒Huggins mean field theory.

Extremely Stable, Multidirectional, All‐in‐One Piezoelectric Bending Sensor with Cycle up to Million Level

AbstractFlexible bending sensors are crucial components of flexible/wearable electronics. However, their broad application is restricted by their difficulty in sensing different bending directions and, more importantly, their significant output attenuation after long cycles. Herein, a new design of an All‐in‐One piezoelectric bending sensor is proposed, in which double‐deck, cross‐over 3D interdigital microelectrodes (silver nanowires (Ag NWs)) are embedded in a piezoelectric polymer film (poly(vinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE))). The piezoelectric film with the embedded 3D microelectrodes exhibits a high anisotropy coefficient ( > 1) based on dual piezoelectric modes (d31 and d33), which renders it more sensitive to different bending directions. More importantly, the homogeneous interconnected interface and heterogeneous microinterlocked interface formed inside the sensor significantly enhance its interface mechanical properties, with at least a tensile strength of 51 MPa, a shear strength of 28 MPa, and an interfacial toughness of 300 J m−2, which are nearly two orders of magnitude greater than those of conventional sandwich architectures. The prepared All‐in‐One sensor shows an extremely stable piezoelectric output over as many as 16 00 000 bending cycles, which represents a remarkable breakthrough. Furthermore, a single sensor can be used to remotely control the multidirectional motion of a smart car, demonstrating enormous potential in practical applications.

Hydrogel-based hybrid membrane enhances in vitro ophthalmic drug evaluation in the OphthalMimic device

Envisaging to improve the evaluation of ophthalmic drug products while minimizing the need for animal testing, our group developed the OphthalMimic device, a 3D-printed device that incorporates an artificial lacrimal flow, a cul-de-sac area, a moving eyelid, and a surface that interacts effectively with ophthalmic formulations, thereby providing a close representation of human ocular conditions. An important application of such a device would be its use as a platform for dissolution/release tests that closely mimic in vivo conditions. However, the surface that artificially simulates the cornea should have a higher resistance (10 min) than the previously described polymeric films (5 min). For this key assay upgrade, we describe the process of obtaining and thoroughly characterizing a hydrogel-based hybrid membrane to be used as a platform base to simulate the cornea artificially. Also, the OphthalMimic device suffered design improvements to fit the new membrane and incorporate the moving eyelid. The results confirmed the successful synthesis of the hydrogel components. The membrane’s water content (86.25 ± 0.35 %) closely mirrored the human cornea (72 to 85 %). Furthermore, morphological analysis supported the membrane’s comparability to the natural cornea. Finally, the performance of different formulations was analysed, demonstrating that the device could differentiate their drainage profile through the viscosity of PLX 14 (79 ± 5 %), PLX 16 (72 ± 4 %), and PLX 20 (57 ± 14 %), and mucoadhesion of PLXCS0.5 (69 ± 1 %), PLX16CS1.0 (65 ± 3 %), PLX16CS1.25 (67 ± 3 %), and the solution (97 ± 8 %). In conclusion, using the hydrogel-based hybrid membrane in the OphthalMimic device represents a significant advancement in the field of ophthalmic drug evaluation, providing a valuable platform for dissolution/release tests. Such a platform aligns with the ethical mandate to reduce animal testing and promises to accelerate the development of safer and more effective ophthalmic drugs.

Adjustable optoelectronic properties of triphenylamine-ethylenedioxythiophene based hybrid electrochromic polymer with different electron-donating substituents

Due to the good optoelectronic properties of triphenylamine (TPA) and its derivatives-based organic conjugated polymers, they have been widely used in various organic electronic devices. They are easy to lose electrons to form stable cationic free radicals with color change under electrochemical oxidation conditions. Therefore, TPA derivatives-based electrochromism materials have attracted the widely attentions of researchers. In this work, a series of TPA derivatives were successfully obtained by Stille coupling reactions, and their basic optical and electrical properties were investigated in detail. Their corresponding polymer films (P(TPA-EDOT), P(PhTPA-EDOT), and P(OCH3TPA-EDOT)) were also prepared on transparent ITO glass by electrodeposition method and their electrochromic properties were further studied. Due to the relatively strong electron donating ability of OCH3– group on the TPA unit, the intramolecular charge transfer peak of OCH3TPA-EDOT is obvious red-shifted and its initial oxidation potential is relatively low, which is beneficial for it to get high-quality electrochromic polymers. Electrochemical analysis shows that all these three polymer films show reversible redox reaction with excellent redox stability. Spectroelectrochemistry shows that all of them have good electrochromic properties and show multi-electrochromic behavior with strong color change. The dynamic study show that all these three polymers have relatively fast switching time (as low as 0.8 s), high coloration efficiency (up to 206.2 C−1 cm2) and obvious optical contrast change. Especially in the near infrared region, the optical contrast is relatively high (P(TPA-EDOT) is 45.3 % at 1100 nm, P(PPhTPA-EDOT) is 53.1 % at 1100 nm, and P(OCH3TPA-EDOT) is 57.2 % at 1100 nm). All these results show that the different substituents on the TPA unit have a certain influence on the resultant monomers’ optoelectronic performances, and they also can adjust the optical band gap of the corresponding polymers with different electrochromic properties.

Linear stability analysis of micropolar nanofluid flow across the accelerated surface with inclined magnetic field

PurposeThe purpose of this paper is to study the two-dimensional micropolar fluid flow with conjugate heat transfer and mass transpiration. The considered nanofluid has graphene nanoparticles.Design/methodology/approachGoverning nonlinear partial differential equations are converted to nonlinear ordinary differential equations by similarity transformation. Then, to analyze the flow, the authors derive the dual solutions to the flow problem. Biot number and radiation effect are included in the energy equation. The momentum equation was solved by using boundary conditions, and the temperature equation solved by using hypergeometric series solutions. Nusselt numbers and skin friction coefficients are calculated as functions of the Reynolds number. Further, the problem is governed by other parameters, namely, the magnetic parameter, radiation parameter, Prandtl number and mass transpiration. Graphene nanofluids have shown promising thermal conductivity enhancements due to the high thermal conductivity of graphene and have a wide range of applications affecting the thermal boundary layer and serve as coolants and thermal management systems in electronics or as heat transfer fluids in various industrial processes.FindingsResults show that increasing the magnetic field decreases the momentum and increases thermal radiation. The heat source/sink parameter increases the thermal boundary layer. Increasing the volume fraction decreases the velocity profile and increases the temperature. Increasing the Eringen parameter increases the momentum of the fluid flow. Applications are found in the extrusion of polymer sheets, films and sheets, the manufacturing of plastic wires, the fabrication of fibers and the growth of crystals, among others. Heat sources/sinks are commonly used in electronic devices to transfer the heat generated by high-power semiconductor devices such as power transistors and optoelectronics such as lasers and light-emitting diodes to a fluid medium, thermal radiation on the fluid flow used in spectroscopy to study the properties of materials and also used in thermal imaging to capture and display the infrared radiation emitted by objects.Originality/valueMicropolar fluid flow across stretching/shrinking surfaces is examined. Biot number and radiation effects are included in the energy equation. An increase in the volume fraction decreases the momentum boundary layer thickness. Nusselt numbers and skin friction coefficients are presented versus Reynolds numbers. A dual solution is obtained for a shrinking surface.

Enhanced modified poly-tyrosine voltammetric sensor for the quantification detection of salivary pepsin

Pepsin as an aspartic acid protease member and one of the three foremost proteolytic enzymes in the digestive system is essential to be detected. An electrochemically polymerized tyrosine film on carbon paste electrode (pTyr/CPE) has been synthesized by electro-polymerization donating an affordable electrochemical sensor to sense salivary pepsin as a diagnostic technique for gastroesophageal reflux disease (GRD) due to saliva collection is non-invasive and relatively comfortable. The pTyr/CPE was applied for Voltammetric sensing of pepsin and its quantification in phosphate buffer solution of pH 2.0 (PBS). Scanning electron microscopy (SEM) was conducted to learn the surface morphology. Cyclic voltammetry (CV), differential pulse voltammetry (DPVs), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) were developed to realize the electrocatalytic activity of the sensor. The pTyr/CPE proceeded as a sensitive detector to pepsin with two linear ranges from 1 to 20 & 20 to 100 ng/mL donating two limits of detection as 0.5 & 0.09 ng/mL, respectively, and high selectivity toward pepsin, as well as stability and fast response of 1.5 s. Consequently, it is guessed that the pTyr/CPE sensor could be supportive for the initial diagnosis of GRD through the detection of pepsin in saliva. Finally, we quantified the pepsin levels in saliva samples of LPR patients (n = 2), showing that the results were agreeable with those from the electrochemical sensor.

Experimental investigation on Nano-Al2O3 and hydroxypropyl methyl cellulose (HPMC) modified cement-based coatings for corrosion resistance

In this work, cementitious coatings doped with nano-Al2O3 (NA) and hydroxypropyl methyl cellulose (HPMC) were prepared in order to enhance corrosion resistance of steel bar. The electro-chemical behaviors and corrosion inhibition properties of coated steel bar and tensioned coated steel bars (subjected to 10 %, 30 % and 50 % yield load) were analyzed in 3.5 wt% NaCl solution for 840 h (35 days). At the end of electrochemical test, coating overall performance was evaluated by visual inspection. In addition, scanning electron microscopy (SEM), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS) were used to examine microstructure and elemental composition of coatings. To comprehend the anti-corrosion mechanism of the coatings, X-ray diffraction (XRD) and infrared spectroscopy (FTIR) analysis to characterize products composition and chemical groups. Test results obtained by linear polarization resistance and electrochemical impedance spectroscopy indicated that both tensile and non-tensile coatings resistance show an increasing trend followed by a decrease with increasing NA content. Cementitious coatings incorporating 1 % NA and 0.12 % HPMC by weight of cement exhibited the best corrosion protection. The LPR fluctuates around 3700 Ω cm2, which is about twice as much as a single doped NA coating. Whether subjected to tensile loads or not, OCP values for all coated steel bar were below −0.273 V/SCE, indicating has a 90 % probability of being in active-corrosion. The corrosion resistance of tensioned coated bars decreased as time and increased load level. According to SEM and TEM image, HPMC forms a thin and continuous film on the substrate surface, which acts as a barrier to the penetration of moisture and corrosive agents. Coatings doped with 1 % NA and 0.12 % HPMC formed denser integrated polymer films at the microscopic. FTIR and XRD results showed that coating incorporated NA consumed the cement hydration product Ca(OH)2 to generate more nanofibers filling pores and microcracks. Coatings incorporating HPMC show better resistance to carbonization.

Self-assembly TiO2@Silane@SiO2 core-shell as s-scheme heterojunction photocatalyst against methylene blue degradation: synthesis and mechanism insights

Pollutants are the most critical threats to the health of water resources. On this basis, fabricating a core-shell as an S-scheme heterojunction photocatalyst for the treatment of wastewater from methylene blue (MB) dye was aimed in this research. In this study, TiO2-doped silanized silica dielectric nanocomposites were synthesized as self-assembly TiO2@Silane@SiO2 heterojunction through sol-gel and solvothermal methods using tetrabutyl orthotitanate (TBOT) as precursor followed by calcination at 650 °C for 3 h. Silanization of silica nanoparticles was done at two different concentrations. The results showed that layer-by-layer synthesis (i.e. self-assembly of APTES on SiO2, precipitation of TiO2 layer on it by sol-gel technique and then calcination) was the optimum preparation method. The structural and morphological features were investigated by XRD, FTIR, BET, TGA-DTG, FE-SEM, EIS and ESR techniques. It was found that the band gap energy of nanocomposite particles reduced from 3.14 eV for the sample prepared by the solvothermal method (i.e. without APTES) to 2.91 eV (i.e. shifting the light absorption from UV to the visible region) for the sample prepared by the sol-gel layer-by-layer method. The prepared samples were used against the photo-degradation of MB. TiO2@Silane@SiO2 core-shell nanoparticles exhibited efficient photocatalytic degradation against MB with a photodegradation efficiency of 85 % under UV and 60 % under visible irradiation. Finally, the prepared nanocomposite particles were incorporated to an emulsion acrylic resin to prepare photocatalytic polymer film. The prepared films were evaluated for photocatalytic degradation of MB stain and mechanical performances. It was found that the TiO2@Silane@SiO2 nanocomposite particles that prepared by layer-by-layer method caused about 56 % improvement in hydrophobicity, 276.7 % increment in the tensile strength, 109.6 times enhancement in the modulus, 381.4 times enhancement in the toughness and 57.6 times improvement in the elongation at break of the acrylic film compared to the pure TiO2-containing acrylic film, respectively.

Phase Behaviors and Photoresponsive Thin Films of Syndiotactic Side-Chain Liquid Crystalline Polymers with High Densely Substituted Azobenzene Mesogens.

Azobenzene-containing polymers (azopolymers) are a kind of fascinating stimuli-responsive materials with broad and versatile applications. In this work, a series of syndiotactic C1 type azopolymers of Pm-Azo-Cn with side-chain azobenzene mesogens of varied length alkoxy tails (n=1, 4, 8, 10) and different length alkyl spacers (m=6, 10) have been prepared via Rh-catalyzed carbene polymerization. The thermal properties and ordered assembly structures of thus synthesized side chain liquid crystalline polymers (SCLCPs) have been systematically investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM) and variable-temperature small/wide-angle X-ray scattering (SAXS/WAXS) analyses. P10-Azo-C1 and P10-Azo-C4 with shorter alkoxy tails exhibited hierarchical structures SmB/Colob and transformed into SmA/Colob at a higher temperature, while P10-Azo-C8 and P10-Azo-C10 with longer alkoxy tails only displayed side group dominated layered SmB phase and transformed into SmA phase at higher temperatures. For P6-Azo-C4 with a shorter spacer only showed a less ordered SmA phase owing to interference by partly coupling between the side chain azobenzene mesogens and the helical backbone. More importantly, the series high densely substituted syndiotactic C1 azopolymer thin films, exhibited evidently and smoothly reversible photoresponsive properties, which demonstrated promising photoresponsive device applications.

Drug polymer conjugates: Average release time from thin films

The reaction–diffusion problem describing the release of drugs conjugated through labile bonds to polymeric thin films has a known analytical solution, when the reaction kinetics is of first order. Using this solution, an exact formula is derived for the average release time of the system. This simple expression provides the characteristic time of release tav as the sum of the corresponding average diffusion time plus the inverse reaction rate constant: tav=(1/12)⋅(L2/D)+(1/k), where L is the slab thickness, D the diffusion coefficient, and k the reaction rate constant. The former term dominates in a diffusion-controlled release, while the latter one in a reaction-controlled delivery. The crossover regime is exactly described by their sum. The obtained result for the average release time is verified by direct numerical integration through the drug release profiles of the analytical solution. The value of fractional drug release at the characteristic average time is between 60–64%. These results can be used for the design of polymer-drug conjugates with a desired delivery time scale, as well as for the experimental determination of the values of microscopic parameters D and k in a conjugated system of interest.

Non-close-packed plasmonic Bravais lattices through a fluid interface-assisted colloidal assembly and transfer process

AbstractThe assembly of colloids at fluid interfaces followed by their transfer to solid substrates represents a robust bottom-up strategy for creating colloidal monolayers over large, macroscopic areas. In this study, we showcase how subtle adjustments in the transfer process, such as varying the contact angle of the substrate and controlling deposition speed and direction, enable the realization of all five two-dimensional Bravais lattices. Leveraging plasmonic core–shell microgels as the building blocks, we successfully engineered non-close-packed plasmonic lattices exhibiting hexagonal, square, rectangular, centered rectangular, and oblique symmetries. Beyond characterizing the monolayer structures and their long-range order, we employed extinction spectroscopy alongside finite difference time domain simulations to comprehensively investigate and interpret the plasmonic response of these monolayers. Additionally, we probed the influence of the refractive index environment on the plasmonic properties by two methods: first, by plasma treatment to remove the microgel shells, and second, by overcoating the resulting gold nanoparticle lattices with a homogeneous refractive index polymer film. Graphical Abstract