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1. Microfluidic Synthesis of Elastomeric Microparticles: A Case Study in Catalysis of Palladium-Mediated Cross-Coupling

   Bennett, Jeffrey A ; Genzer, Jan ; Abolhasani, Milad ( October 2018 , 2018 AIChE Annual Meeting)

   Metal-mediated cross-coupling reactions offer organic chemists a wide array of stereo- and chemically-selective reactions with broad applications in fine chemical and pharmaceutical synthesis.1 Current batch-based synthesis methods are beginning to be replaced with flow chemistry strategies to take advantage of the improved consistency and process control methods offered by continuous flow systems.2,3 Most cross-coupling chemistries still encounter several issues in flow using homogeneous catalysis, including expensive catalyst recovery and air sensitivity due to the chemical nature of the catalyst ligands.1 To mitigate some of these issues, a ligand-free heterogeneous catalysis reaction was developed using palladium (Pd) loaded into a polymeric network of a silicone elastomer, poly(hydromethylsiloxane) (PHMS), that is not air sensitive and can be used with mild reaction solvents (ethanol and water).4 In this work we present a novel method of producing soft catalytic microparticles using a multiphase flow-focusing microreactor and demonstrate their application for continuous Suzuki-Miyaura cross-coupling reactions. The catalytic microparticles are produced in a coaxial glass capillary-based 3D flow-focusing microreactor. The microreactor consists of two precursors, a cross-linking catalyst in toluene and a mixture of the PHMS polymer and a divinyl cross-linker. The dispersed phase containing the polymer, cross-linker, and cross-linking catalyst is continuously mixed and thenmore »formed into microdroplets by the continuous phase of water and surfactant (sodium dodecyl sulfate) introduced in a counter-flow configuration. Elastomeric microdroplets with a diameter ranging between 50 to 300 micron are produced at 25 to 250 Hz with a size polydispersity less than 3% in single stream production. The physicochemical properties of the elastomeric microparticles such as particle swelling/softness can be tuned using the ratio of cross-linker to polymer as well as the ratio of polymer mixture to solvent during the particle formation. Swelling in toluene can be tuned up to 400% of the initial particle volume by reducing the concentration of cross-linker in the mixture and increasing the ratio of polymer to solvent during production.5 After the particles are produced and collected, they are transferred into toluene containing palladium acetate, allowing the particles to incorporate the palladium into the polymer network and then reduce the palladium to Pd0 with the Si-H functionality present on the PHMS backbones. After the reduction, the Pd-loaded particles can be washed and dried for storage or switched into an ethanol/water solution for loading into a micro-packed bed reactor (µ-PBR) for continuous organic synthesis. The in-situ reduction of Pd within the PHMS microparticles was confirmed using energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and focused ion beam-SEM, and TEM techniques. In the next step, we used the developed µ-PBR to conduct continuous organic synthesis of 4-phenyltoluene by Suzuki-Miyaura cross-coupling of 4-iodotoluene and phenylboronic acid using potassium carbonate as the base. Catalyst leaching was determined to only occur at sub ppm concentrations even at high solvent flow rates after 24 h of continuous run using inductively coupled plasma mass spectrometry (ICP-MS). The developed µ-PBR using the elastomeric microparticles is an important initial step towards the development of highly-efficient and green continuous manufacturing technologies in the pharma industry. In addition, the developed elastomeric microparticle synthesis technique can be utilized for the development of a library of other chemically cross-linkable polymer/cross-linker pairs for applications in organic synthesis, targeted drug delivery, cell encapsulation, or biomedical imaging. References 1. Ruiz-Castillo P, Buchwald SL. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions. Chem Rev. 2016;116(19):12564-12649. 2. Adamo A, Beingessner RL, Behnam M, et al. On-demand continuous-flow production of pharmaceuticals in a compact, reconfigurable system. Science. 2016;352(6281):61 LP-67. 3. Jensen KF. Flow Chemistry — Microreaction Technology Comes of Age. 2017;63(3). 4. Stibingerova I, Voltrova S, Kocova S, Lindale M, Srogl J. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity. Org Lett. 2016;18(2):312-315. 5. Bennett JA, Kristof AJ, Vasudevan V, Genzer J, Srogl J, Abolhasani M. Microfluidic synthesis of elastomeric microparticles: A case study in catalysis of palladium-mediated cross-coupling. AIChE J. 2018;0(0):1-10.« less
2. AFREEs: Active Fiber Reinforced Elastomeric Enclosures

   https://doi.org/10.1109/RoboSoft48309.2020.9115988  

   Yoshida, Kyle T. ; Ren, Xinyi ; Blumenschein, Laura H. ; Okamura, Allison M. ; Luo, Ming ( May 2020 , IEEE International Conference on Soft Robotics (RoboSoft))

   Soft continuum manipulators provide a safe alternative to traditional rigid manipulators, because their bodies can absorb and distribute contact forces. Soft manipulators have near infinite potential degrees of freedom, but a limited number of control inputs. This underactuation means soft continuum manipulators often lack either the controllability or the dexterity to achieve desired tasks. In this work, we present an extension of McKibben actuators, which have well-known models, that increases the controllable degrees of freedom using active reconfiguration of the constraining fibers. These Active Fiber Reinforced Elastomeric Enclosures (AFREEs) preform some combination of length change and twisting, depending on the fiber configuration. Experimental results shows that by changing the fiber angles within a range of -30 to 30 degrees and actuating the resulting configuration between 10.3 kPa and 24.1 kPa, we can achieve twists between ± 60 degrees and displacements between -2 and 4 mm. By additionally controlling the fiber lengths and pressure, we can modify the AFREE kinematics further, creating dynamic behaviors and trajectories of actuation. The presented actuator creates the possibility to reconFigure actuator kinematics to meet desired soft robot motions.
3. The elastic Rayleigh drop

   https://doi.org/10.1039/C9SM01753D  

   Tamim, S. I. ; Bostwick, J. B. ( November 2019 , Soft Matter)

   Bioprinting technologies rely on the formation of soft gel drops for printing tissue scaffolds and the dynamics of these drops can affect the process. A model is developed to describe the oscillations of a spherical gel drop with finite shear modulus, whose interface is held by surface tension. The governing elastodynamic equations are derived and a solution is constructed using displacement potentials decomposed into a spherical harmonic basis. The resulting nonlinear characteristic equation depends upon two dimensionless numbers, elastocapillary and compressibility, and admits two types of solutions, (i) spheroidal (or shape change) modes and (ii) torsional (rotational) modes. The torsional modes are unaffected by capillarity, whereas the frequency of shape oscillations depend upon both the elastocapillary and compressibility numbers. Two asymptotic dispersion relationships are derived and the limiting cases of the inviscid Rayleigh drop and elastic globe are recovered. For a fixed polar wavenumber, there exists an infinity of radial modes that each transition from an elasticity wave to a capillary wave upon increasing the elastocapillary number. At the transition, there is a qualitative change in the deformation field and a set of recirculation vortices develop at the free surface. Two special modes that concern volume oscillations and translational motionmore »are characterized. A new instability is documented that reflects the balance between surface tension and compressibility effects due to the elasticity of the drop.« less
4. Plant Movements as Concept Generators for the Development of Biomimetic Compliant Mechanisms

   https://doi.org/10.1093/icb/icaa028  

   Poppinga, Simon ; Correa, David ; Bruchmann, Bernd ; Menges, Achim ; Speck, Thomas ( May 2020 , Integrative and Comparative Biology)

   Synopsis Plant movements are of increasing interest for biomimetic approaches where hinge-free compliant mechanisms (flexible structures) for applications, for example, in architecture, soft robotics, and medicine are developed. In this article, we first concisely summarize the knowledge on plant movement principles and show how the different modes of actuation, that is, the driving forces of motion, can be used in biomimetic approaches for the development of motile technical systems. We then emphasize on current developments and breakthroughs in the field, that is, the technical implementation of plant movement principles through additive manufacturing, the development of structures capable of tracking movements (tropisms), and the development of structures that can perform multiple movement steps. Regarding the additive manufacturing section, we present original results on the successful transfer of several plant movement principles into 3D printed hygroscopic shape-changing structures (“4D printing”). The resulting systems include edge growth-driven actuation (as known from the petals of the lily flower), bending scale-like structures with functional bilayer setups (inspired from pinecones), modular aperture architectures (as can be similarly seen in moss peristomes), snap-through elastic instability actuation (as known from Venus flytrap snap-traps), and origami-like curved-folding kinematic amplification (inspired by the carnivorous waterwheel plant). Our novel biomimetic compliantmore »mechanisms highlight the feasibility of modern printing techniques for designing and developing versatile tailored motion responses for technical applications. We then focus on persisting challenges in the field, that is, how to speed-boost intrinsically slow hydraulically actuated structures and how to achieve functional resilience and robustness, before we propose the establishment of a motion design catalog in the conclusion.« less
5. 3D Structuring of Magnetoelastomers for Anisotropic Actuation Properties

   Atescan, Yagmur ; Yamamoto, Namiko. ( January 2020 , AIAA paper)

   Smart structures with actuation function are desired for aerospace applications, including morphing airfoils, deployable structures and more. While shape memory alloys and piezoelectric ceramics and polymers are currently a popular smart material options for such applications, magnetoelastomers (MEs) can be uniquely actuated with application of non-contact magnetic field. Magnetoelastomers (MEs), composite materials made of magnetic particles and soft, non-magnetic matrix, can potentially contribute to such smart structures as a light-weight, smart material option with large strain change, fast response time (milliseconds) and anisotropic actuation properties. Other than aerospace applications, MEs, as soft actuators, have been investigated for flexible electronics, soft robotics, and biomedical applications. Anisotropic actuation properties of MEs can be controlled with particle organization within the elastomer. To provide this control, parametric studies on fabrication of MEs need to be performed. This study presents experimental work on nanoparticle organization within MEs using uniaxial, biaxial and triaxial magnetic fields and on the structure-property relationships of MEs. Iron oxide nanoparticles were used as a model nanofillers, and their surfaces were treated with silane coupling agent to improve dispersion and suspension within a polydimethylsiloxane (PDMS) elastomer. The fabricated MEs were inspected using microCT, and their anisotropic susceptibilities are being measured.