Suppression of the Coffee Ring Effect in a Single Solvent-Based Silicon Nanoparticle Ink.

Silicon (Si) is made printable by dispersing Si nanoparticles in a single organic solvent. Viscoelastic properties of the prepared inks as well as the uniformity of inkjet-printed thin films are investigated in dependence on the Si volume fraction. It has been demonstrated that no ink additives are needed to completely suppress the occurrence of the coffee ring effect. This is obtained by increasing the ink's volume fraction to induce gelation in order to generate elasticity. The printability of our inks is investigated in terms of Weber, Reynolds, and Ohnesorge numbers and found to be maintained even at high particle loads due to shear-thinning viscosity behavior. When printed onto tungsten (W) substrates, Si inks with ϕ(Si) = 0.4% and ϕ(Si) = 2.1% leave a ring stain after drying, whereas coffee rings are absent for inks with ϕ(Si) = 3.0% and above. The reason for this is a significant ink elasticity achieved by the buildup of a gel network for higher particle loads, which leads to thixotropy-like properties. These are low viscosity for printability and elevated elasticity during ink drying, made possible by a breakup of the gel network during drop formation in conjunction with a rapid network reformation after deposition.

Aptamer Clicked Poly(ferrocenylsilanes) at Au Nanoparticles as Platforms with Multiple Function[†].

Aptamers are widely used in biosensing due to their specific sensitivity toward many targets. Thus, gold nanoparticle (AuNP) aptasensors are subject to intense research due to the complementary properties of aptamers as sensing elements and AuNPs as transducers. We present herein a novel method for the functional coupling of thrombin-specific aptamers to AuNPs via an anionic, redox-active poly(ferrocenylsilane) (PFS) polyelectroyte. The polymer acts as a co-reductant and stabilizer for the AuNPs, provides grafting sites for the aptamer, and can be used as a redox sensing element, making the aptamer-PFS-AuNP composite (aptamer-AuNP) a promising model system for future multifunctional sensors. The aptamer-AuNPs exhibit excellent colloidal stability in high ionic strength environments owing to the combined electrosteric stabilizing effects of the aptamer and the PFS. The synthesis of each assembly element is described, and the colloidal stability and redox responsiveness are studied. As an example to illustrate applications, we present results for thrombin sensitivity and specificity using the specific aptamer.

Dual functionality of ferrocene-based metallopolymers as radical scavengers and nanoparticle stabilizing agents.

The beneficial redox properties of ferrocene-based polymers have been utilized during in situ preparation of metallic nanoparticles, while such redox features also indicate a great promise in applications as free radical scavengers. Here, colloidal dispersions of an antioxidant nanozyme composed of amidine-functionalized polystyrene latex (AL) nanoparticles, negatively charged poly(ferrocenylsilane) (PFS(-)) organometallic polyions, and ascorbic acid (AA) were formulated. The AL was first functionalized with PFS(-). Increasing the polymer dose resulted in charge neutralization and subsequent charge reversal of the particles. The strength of repulsive interparticle forces of electrostatic nature was significant at low and high doses leading to stable colloids, while attractive forces dominated near the charge neutralization point giving rise to unstable dispersions. The saturated PFS(-) layer adsorbed on the surface of the AL (p-AL nanozyme) enhanced the colloidal stability against salt-induced aggregation without affecting the pH-dependent charge and size of the particles. The joint effect of PFS(-) and the AA in radical decomposition was observed indicating the antioxidant potential of the system. The immobilization of PFS(-) deteriorated its scavenging activity, yet the combination with AA improved this feature. The results indicate that p-AL-AA is a promising radical scavenger since the high colloidal stability of the particles allows application in heterogeneous systems, such as in industrial manufacturing processes, where antioxidants are required to maintain acceptable product quality.

Engineering of Adhesion at Metal-Poly(lactic acid) Interfaces by Poly(dopamine): The Effect of the Annealing Temperature.

Control over adhesion at interfaces from strong bonding to release between thermoplastic polymers (TPs) and metal oxides is highly significant for polymer composites. In this work, we showcase a simple and inexpensive method to tune adhesion between a TP of growing interest, poly(lactic acid) (PLA), and two commercial metal alloys, based on titanium and stainless steel. This is realized by coating titanium and stainless steel wires with polydopamine (PDA), thermally treating them under vacuum at temperatures ranging from 25 to 250 °C, and then comolding them with PLA to form pullout specimens for adhesion tests. Pullout results indicate that PDA coatings treated at low temperatures up to a given threshold significantly improve adhesion between PLA and the metals. Conversely, at higher PDA annealing temperatures beyond the threshold, interfacial bonding gradually declines. The excellent control over interfacial adhesion is attributed to the thermally induced transformation of PDA. In this work, we show using thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared, and 13C solid-state NMR that the extent of the thermal transformation is dependent on the annealing temperature. By selecting the annealing temperature, we vary the concentration of primary amine and hydroxyl groups in PDA, which influences adhesion at the metal/PLA interface. We believe that these findings contribute to optimizing and broadening the applications of PDA in composite materials.

Targeted Positioning of Quantum Dots Inside 3D Silicon Photonic Crystals Revealed by Synchrotron X-ray Fluorescence Tomography.

It is a major outstanding goal in nanotechnology to precisely position functional nanoparticles, such as quantum dots, inside a three-dimensional (3D) nanostructure in order to realize innovative functions. Once the 3D positioning is performed, the challenge arises how to nondestructively verify where the nanoparticles reside in the 3D nanostructure. Here, we study 3D photonic band gap crystals made of Si that are infiltrated with PbS nanocrystal quantum dots. The nanocrystals are covalently bonded to polymer brush layers that are grafted to the Si-air interfaces inside the 3D nanostructure using surface-initiated atom transfer radical polymerization (SI-ATRP). The functionalized 3D nanostructures are probed by synchrotron X-ray fluorescence (SXRF) tomography that is performed at 17 keV photon energy to obtain large penetration depths and efficient excitation of the elements of interest. Spatial projection maps were obtained followed by tomographic reconstruction to obtain the 3D atom density distribution with 50 nm voxel size for all chemical elements probed: Cl, Cr, Cu, Ga, Br, and Pb. The quantum dots are found to be positioned inside the 3D nanostructure, and their positions correlate with the positions of elements characteristic of the polymer brush layer and the ATRP initiator. We conclude that X-ray fluorescence tomography is very well suited to nondestructively characterize 3D nanomaterials with photonic and other functionalities.

Adhesion Engineering in Polymer-Metal Comolded Joints with Biomimetic Polydopamine.

Joints that connect thermoplastic polymer matrices (TPMs) and metals, which are obtained by comolding, are of growing importance in numerous applications. The overall performance of these constructs is strongly impacted by the TPM-metal interfacial strength, which can be tuned by tailoring the surface chemistry of the metal prior to the comolding process. In the present work, a model TPM-metal system consisting of poly(methyl methacrylate) (PMMA) and titanium is used to prepare comolded joints. The interfacial adhesion is quantified by wire pullout experiments. Pullout tests prior to and following surface modification are performed and analyzed. Unmodified wires show poor interfacial strength, with a work of adhesion (Ga) value of 3.8 J m-2. To enhance interfacial adhesion, a biomimetic polydopamine (PDA) layer is first deposited on titanium followed by a second layer of a poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) copolymer prior to comolding. During processing, the MAA moieties of the copolymer thermally react with PDA, forming amide bonds, while MMA promotes the formation of secondary bonds and molecular interdigitation with the PMMA matrix. Control testing reveals that neither PDA nor the copolymer provides a substantial increase in adhesion. However, when used in combination, a significant increase in adhesion is detected. This observation indicates a pronounced synergistic effect between the two layers that strengthens the PMMA-titanium bonding. Enhanced adhesion is optimized by tuning the MMA-to-MAA ratio of the copolymer, which shows a maximum at a 24% MAA content and a greatly increased Ga value of 155 J m-2; this value corresponds to a 40-fold increase. Further growth in the Ga values at higher MAA contents is hindered by the thermal cross-linking of MAA; MAA contents above 24% restrict the formation of secondary bonds and molecular interdigitation with the PMMA chains. Our results provide new design principles to produce thermoplastic-metal comolded joints with strong interfaces.

Designer Core-Shell Nanoparticles as Polymer Foam Cell Nucleating Agents: The Impact of Molecularly Engineered Interfaces.

The interface between nucleating agents and polymers plays a pivotal role in heterogeneous cell nucleation in polymer foaming. We describe how interfacial engineering of nucleating particles by polymer shells impacts cell nucleation efficiency in CO2 blown polymer foams. Core-shell nanoparticles (NPs) with a 80 nm silica core and various polymer shells including polystyrene (PS), poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and poly(acrylonitrile) (PAN) are prepared and used as heterogeneous nucleation agents to obtain CO2 blown PMMA and PS micro- and nanocellular foams. Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy are employed to confirm the successful synthesis of core-shell NPs. The cell size and cell density are determined by scanning electron microscopy. Silica NPs grafted with a thin PDMS shell layer exhibit the highest nucleation efficiency values, followed by PAN. The nucleation efficiency of PS- and PMMA-grafted NPs are comparable with the untreated particles and are significantly lower when compared to PDMS and PAN shells. Molecular dynamics simulations (MDS) are employed to better understand CO2 absorption and nucleation, in particular to study the impact of interfacial properties and CO2-philicity. The MDS results show that the incompatibility between particle shell layers and the polymer matrix results in immiscibility at the interface area, which leads to a local accumulation of CO2 at the interfaces. Elevated CO2 concentrations at the interfaces combined with the high interfacial tension (caused by the immiscibility) induce an energetically favorable cell nucleation process. These findings emphasize the importance of interfacial effects on cell nucleation and provide guidance for designing new, highly efficient nucleation agents in nanocellular polymer foaming.

Sponges with Janus Character from Nanocellulose: Preparation and Applications in the Treatment of Hemorrhagic Wounds.

The development of a rapid and effective hemostatic dressing is highly desired in the treatment of hemorrhagic wounds. In this study, sponges with Janus character are developed using cellulose nanofibers (CNFs) that exhibit materials facets of different wettability characteristics using heterogeneous mixing and freeze-drying. The bonding of the interface between the hydrophilic and hydrophobic facets is achieved by using interpenetrating chemical cross-linking between CNFs and organosilanes. The hydrophilic layer absorbs water from blood and works synergistically with the inherent hemostatic chitosan-rich complementary layer to accelerate blood clotting, displaying both active and passive hemostatic mechanisms. The hydrophobic layer prevents blood penetration into the construct and exerts proper pressure on the wound. Compared with the hydrophilic control samples and commercial gauzes, the Janus sponges can achieve effective bleeding control with nearly 50% less blood loss in a femoral artery injury model and prolong the survival time in a carotid artery injury model. Compared with the only hydrophilic layer, the time to hemostasis of Janus sponge are reduced from 165 ± 20 to 131 ± 26 s in femoral artery injury model and from 102 ± 21 to 83 ± 15 s in liver femoral artery injury model.

Bubble Seeding Nanocavities: Multiple Polymer Foam Cell Nucleation by Polydimethylsiloxane-Grafted Designer Silica Nanoparticles.

We describe a successful strategy to substantially enhance cell nucleation efficiency in polymer foams by using designer nanoparticles as nucleating agents. Bare and poly(dimethylsilane) (PDMS)-grafted raspberry-like silica nanoparticles with diameters ranging from ∼80 nm to ∼200 nm were synthesized and utilized as highly efficient cell nucleators in CO2-blown nanocellular polymethyl methacrylate (PMMA) foams. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller measurements, and transmission electron microscopy. The cell size and cell density of the obtained PMMA micro- and nanocellular foams were determined by scanning electron microscopy. The results show that increased surface roughness enhances the nucleation efficiency of the designer silica particles. This effect is ascribed to a decreased nucleation free energy for foam cell nucleation in the nanocavities at the melt-nucleator interface. For PDMS grafted raspberry-like silica nanoparticles with diameters of 155 and 200 nm, multiple cell nucleation events were observed. These hybrid particles had nucleation efficiencies of 3.7 and 6.2, respectively. The surprising increase in nucleation efficiency to above unity is ascribed to the significant increase in CO2 absorption and capillary condensation in the corresponding PMMA during saturation. This increase results in the presence of large amounts of the physical blowing agent close to energetically favorable nucleation points. Additionally, it is shown that as a consequence of cell coalescence, the increased number of foam cells is rapidly reduced during the first seconds of foaming. Hence, the design of highly efficient nucleating particles, as well as careful selection of foam matrix materials, seems to be of pivotal importance for obtaining polymer cellular materials with cell dimensions at the nanoscale. These findings contribute to the fabrication of polymer foams with high thermal insulation capacity and have relevance in general to the area of cellular materials.

Printing "Smart" Inks of Redox-Responsive Organometallic Polymers on Microelectrode Arrays for Molecular Sensing.

Printing arrays of responsive spots for multiplexed sensing with electrochemical readout requires new molecules and precise, high-throughput deposition of active compounds on microelectrodes with spatial control. We have designed and developed new redox-responsive polymers, featuring a poly(ferrocenylsilane) (PFS) backbone and side groups with disulfide units, which allow an efficient and stable bonding to Au substrates, using sulfur-gold coupling chemistry in a "grafting-to" approach. The polymer molecules can be employed for area selective molecular sensing following their deposition by high-precision inkjet printing. The new PFS derivatives, which serve as "molecular inks", were characterized by 1H NMR, 13C NMR, and FTIR spectroscopies and by gel permeation chromatography. The viscosity and surface tension of the inks were assessed by rheology and pendant drop contact angle measurements, respectively. Commercial microelectrode arrays were modified with the new PFS ink by using inkjet printing in the "drop-on-demand" mode. FTIR spectroscopy, AFM, and EDX-SEM confirmed a successful, spatially localized PFS modification of the individual electrodes within the sensing cells of the microelectrode arrays. The potential application of these devices to act as an electrochemical sensor array was demonstrated with a model analyte, ascorbic acid, by using cyclic voltammetry and amperometric measurements.

Brush Swelling and Attachment Strength of Barnacle Adhesion Protein on Zwitterionic Polymer Films as a Function of Macromolecular Structure.

The exceptional hydration of sulfobetaine polymer brushes and their resistance toward nonspecific protein absorption allows for the construction of thin films with excellent antibiofouling properties. In this work, swollen sulfobetaine brushes, prepared by surface-initiated atom transfer radical polymerization of two monomers, differentiated by the nature of the polymerizable group, are studied and compared by a liquid-cell atomic force microscopy technique and spectroscopic ellipsometry. Colloidal AFM-based force spectroscopy is employed to estimate brush grafting density and characterize nanomechanical properties in salt water. When the ionic strength-induced swelling behaviors of the two systems are compared, the differences observed on the antipolyelectrolyte response can be correlated with the stiffness variation on brush compression, likely to be promoted by solvation differences. The higher solvation of amide groups is proposed to be responsible for the lower adhesion force of the barnacle cyprid's temporary adhesive proteins. The adhesion results provide further insights into the antibiofouling activity against barnacle cyprid settlement attributed to polysulfobetaine brushes.

Fluorescent Patterns by Selective Grafting of a Telechelic Polymer.

The preparation of patterned ultrathin films (sub-10 nm) composed of end-anchored fluorescently labeled poly(methyl methacrylate) (PMMA) is presented. Telechelic PMMA was synthesized utilizing activator regenerated by electron transfer atom transfer radical polymerization and consecutively end-functionalized with alkynylated fluorescein by Cu-catalyzed azide-alkyne cycloaddition (CuAAC) "click" chemistry. The polymers were grafted via the α-carboxyl groups to silica or glass substrates pretreated with (3-aminopropyl)triethoxysilane (APTES). Patterned surfaces were prepared by inkjet printing of APTES onto glass substrates and selectively grafted with fluorescently end-labeled PMMA to obtain emissive arrays on the surface.

Silica-Assisted Nucleation of Polymer Foam Cells with Nanoscopic Dimensions: Impact of Particle Size, Line Tension, and Surface Functionality.

Core-shell nanoparticles consisting of silica as core and surface-grafted poly(dimethylsiloxane) (PDMS) as shell with different diameters were prepared and used as heterogeneous nucleation agents to obtain CO2-blown poly(methyl methacrylate) (PMMA) nanocomposite foams. PDMS was selected as the shell material as it possesses a low surface energy and high CO2-philicity. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The cell size and cell density of the PMMA micro- and nanocellular materials were determined by scanning electron microscopy. The cell nucleation efficiency using core-shell nanoparticles was significantly enhanced when compared to that of unmodified silica. The highest nucleation efficiency observed had a value of ∼0.5 for nanoparticles with a core diameter of 80 nm. The particle size dependence of cell nucleation efficiency is discussed taking into account line tension effects. Complete engulfment by the polymer matrix of particles with a core diameter below 40 nm at the cell wall interface was observed corresponding to line tension values of approximately 0.42 nN. This line tension significantly increases the energy barrier of heterogeneous nucleation and thus reduces the nucleation efficiency. The increase of the CO2 saturation pressure to 300 bar prior to batch foaming resulted in an increased line tension length. We observed a decrease of the heterogeneous nucleation efficiency for foaming after saturation with CO2 at 300 bar, which we attribute to homogenous nucleation becoming more favorable at the expense of heterogeneous nucleation in this case. Overall, it is shown that the contribution of line tension to the free energy barrier of heterogeneous foam cell nucleation must be considered to understand foaming of viscoelastic materials. This finding emphasizes the need for new strategies including the use of designer nucleating particles to enhance the foam cell nucleation efficiency.

Hydrogels with a Memory: Dual-Responsive, Organometallic Poly(ionic liquid)s with Hysteretic Volume-Phase Transition.

We report on the synthesis and structure-property relations of a novel, dual-responsive organometallic poly(ionic liquid) (PIL), consisting of a poly(ferrocenylsilane) backbone of alternating redox-active, silane-bridged ferrocene units and tetraalkylphosphonium sulfonate moieties in the side groups. This PIL is redox responsive due to the presence of ferrocene in the backbone and also exhibits a lower critical solution temperature (LCST)-type thermal responsive behavior. The LCST phase transition originates from the interaction between water molecules and the ionic substituents and shows a concentration-dependent, tunable transition temperature in aqueous solution. The PIL's LCST-type transition temperature can also be influenced by varying the redox state of ferrocene in the polymer main chain. As the polymer can be readily cross-linked and is easily converted into hydrogels, it represents a new dual-responsive materials platform. Interestingly, the as-formed hydrogels display an unusual, strongly hysteretic volume-phase transition indicating useful thermal memory properties. By employing the dispersing abilities of this cationic PIL, CNT-hydrogel composites were successfully prepared. These hybrid conductive composite hydrogels showed bi-stable states and tunable resistance in heating-cooling cycles.

Effect of Variations in Micropatterns and Surface Modulus on Marine Fouling of Engineering Polymers.

We report on the marine fouling and fouling release effects caused by variations of surface mechanical properties and microtopography of engineering polymers. Polymeric materials were covered with hierarchical micromolded topographical patterns inspired by the shell of the marine decapod crab Myomenippe hardwickii. These micropatterned surfaces were deployed in field static immersion tests. PDMS, polyurethane, and PMMA surfaces with higher elastic modulus and hardness were found to accumulate more fouling and exhibited poor fouling release properties. The results indicate interplay between surface mechanical properties and microtopography on antifouling performance.

Thermoresponsive Semi-IPN Hydrogel Microfibers from Continuous Fluidic Processing with High Elasticity and Fast Actuation.

Hydrogels with rapid and strong response to external stimuli and possessing high elasticity and strength have been considered as platform materials for numerous applications, e.g., in biomaterials engineering. Thermoresponsive hydrogels based on semi-interpenetrating polymer networks (semi-IPN) featuring N-isopropylacrylamide with copolymers of poly(N-isopropylacrylamide-co-hydroxyethyl methacrylate) p(NIPAM-HEMA) chains are prepared and described. The copolymer was characterized by FTIR, NMR, and GPC. The semi-IPN structured hydrogel and its responsive properties were evaluated by dynamic mechanical measurements, SEM, DSC, equilibrium swelling ratio, and dynamic deswelling tests. The results illustrate that the semi-IPN structured hydrogels possess rapid response and high elasticity compared to conventional pNIPAM hydrogels. By using a microfluidic device with double coaxial laminar flow, we succeeded in fabricating temperature responsive ("smart") hydrogel microfibers with core-shell structures that exhibit typical diameters on the order of 100 µm. The diameter of the fibers can be tuned by changing the flow conditions. Such hydrogel fibers can be used to fabricate "smart" devices, and the core layer can be potentially loaded with cargos to incorporate biological function in the constructs. The platforms obtained by this approach hold promise as artificial "muscles", and also "smart" hydrogel carriers providing a unique biophysical and bioactive environment for regenerative medicine and tissue engineering.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature.

Measuring protein isoelectric points by AFM-based force spectroscopy using trace amounts of sample.

Protein charge at various pH and isoelectric point (pI) values is important in understanding protein function. However, often only trace amounts of unknown proteins are available and pI measurements cannot be obtained using conventional methods. Here, we show a method based on the atomic force microscope (AFM) to determine pI using minute quantities of proteins. The protein of interest is immobilized on AFM colloidal probes and the adhesion force of the protein is measured against a positively and a negatively charged substrate made by layer-by-layer deposition of polyelectrolytes. From the AFM force-distance curves, pI values with an estimated accuracy of ±0.25 were obtained for bovine serum albumin, myoglobin, fibrinogen and ribonuclease A over a range of 4.7-9.8. Using this method, we show that the pI of the 'footprint' of the temporary adhesive proteins secreted by the barnacle cyprid larvae of Amphibalanus amphitrite is in the range 9.6-9.7.