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    Designing covalent organic framework‐based light‐driven microswimmers toward therapeutic applications
    (2023) Sridhar, Varun; Yildiz, Erdost; Rodríguez‐Camargo, Andrés; Lyu, Xianglong; Yao, Liang; Wrede, Paul; Aghakhani, Amirreza; Akolpoglu, Birgul M.; Podjaski, Filip; Lotsch, Bettina V.; Sitti, Metin
    While micromachines with tailored functionalities enable therapeutic applications in biological environments, their controlled motion and targeted drug delivery in biological media require sophisticated designs for practical applications. Covalent organic frameworks (COFs), a new generation of crystalline and nanoporous polymers, offer new perspectives for light‐driven microswimmers in heterogeneous biological environments including intraocular fluids, thus setting the stage for biomedical applications such as retinal drug delivery. Two different types of COFs, uniformly spherical TABP‐PDA‐COF sub‐micrometer particles and texturally nanoporous, micrometer‐sized TpAzo‐COF particles are described and compared as light‐driven microrobots. They can be used as highly efficient visible‐light‐driven drug carriers in aqueous ionic and cellular media. Their absorption ranging down to red light enables phototaxis even in deeper and viscous biological media, while the organic nature of COFs ensures their biocompatibility. Their inherently porous structures with ≈2.6  and ≈3.4 nm pores, and large surface areas allow for targeted and efficient drug loading even for insoluble drugs, which can be released on demand. Additionally, indocyanine green (ICG) dye loading in the pores enables photoacoustic imaging, optical coherence tomography, and hyperthermia in operando conditions. This real‐time visualization of the drug‐loaded COF microswimmers enables unique insights into the action of photoactive porous drug carriers for therapeutic applications.
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    The role of dimensionality and geometry in quench-induced nonequilibrium forces
    (2021) Nejad, Mehrana Raeisian; Khalilian, Hamidreza; Rohwer, Christian M.; Moghaddam, Ali Ghorbanzadeh
    We present an analytical formalism, supported by numerical simulations, for studying forces that act on curved walls following temperature quenches of the surrounding ideal Brownian fluid. We show that, for curved surfaces, the post-quench forces initially evolve rapidly to an extremal value, whereafter they approach their steady state value algebraically in time. In contrast to the previously-studied case of flat boundaries (lines or planes), the algebraic decay for curved geometries depends on the dimension of the system. Specifically, steady-state values of the force are approached in time as t-d/2 in d-dimensional spherical (curved) geometries. For systems consisting of concentric circles or spheres, the exponent does not change for the force on the outer circle or sphere. However, the force exerted on the inner circles or sphere experiences an overshoot and, as a result, does not evolve to the steady state in a simple algebraic manner. The extremal value of the force also depends on the dimension of the system, and originates from curved boundaries and the fact that particles inside a sphere or circle are locally more confined, and diffuse less freely than particles outside the circle or sphere.
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    Unravelling parameter interactions in calcium alginate/polyacrylamide double network hydrogels using a design of experiments approach for the optimization of mechanical properties
    (2024) Gorke, Oliver; Stuhlmüller, Marc; Tovar, Günter E. M.; Southan, Alexander
    Calcium alginate/polyacrylamide double network hydrogels were reported to be exceptionally tough. However, literature reports so far varied the sample compositions mainly by one parameter at a time approaches, thus only drawing an incomplete picture of achievable material properties. In this contribution, sample compositions are varied according to a face-centered central composite experimental design taking into account the four parameters of alginate concentration cAlg, high/low molar mass alginate mixing ratio RP, acrylamide concentration cAAm, and N,N′-methylenebisacrylamide concentration cMBA. Each sample composition is investigated in triplicate. Thus, 75 samples were investigated by tensile testing, and a detailed analysis of the significant parameters and parameter interactions influencing the mechanical properties is conducted. The data shows that two parameter interactions, involving all four tested parameters, have a large effect on the Young's modulus, the strength, the toughness and the strain at material failure. As a consequence, it becomes evident that the experimental procedure from previous studies did not always result in optimum sample compositions. The results allow optimization of the mechanical properties within the studied parameter space, and a new maximum value of the strength of 710 kPa is reported. The data also give rise to the assumption that other parameters and parameter interactions ignored also in this study may allow further tailoring of mechanical properties.
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    Investigation of oxide layer development of X6CrNiNb18-10 stainless steel exposed to high-temperature water
    (2024) Veile, Georg; Hirpara, Radhika; Lackmann, Simon; Weihe, Stefan
    The oxide layer development of X6CrNiNb18-10 (AISI 347) during exposure to high-temperature water has been investigated. Stainless steels are known to form a dual oxide layer in corrosive environments. The secondary Fe-rich oxide layer has no significant protective effect. In contrast, the primary Cr-rich oxide layer is known to reach a stabilized state, protecting the base metal from further oxidation. This study’s purpose was to determine the development of oxide layer dimensions over exposure time using SEM, TEM and EDX line scans. While a parabolic development of Cr in the protective primary layer and Fe in the secondary layer was observed, the dimensions of the Ni layer remained constant. Ni required the presence of a pronounced Fe-rich secondary layer before being able to reside on the outer secondary layer. With increasing immersion time, the Ni element fraction surpassed the Cr element fraction in the secondary layer. Oxide growth on the secondary layer could be observed. After 480 h, nearly the entire surface was covered by the outer oxide layer. In the metal matrix, no depletion of Cr or Ni could be observed over time; however, an increased presence of Cr and Ni in the primary layer was found at the expense of Fe content. The Nb-stabilized stainless steel was subject to the formation of Niobium pentoxide (Nb2O5), with the quantity and magnitude of element fraction increasing over exposure time.
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    Cohesive properties of bcc and fcc rubidium from ab initio pseudopotentials
    (1985) Maysenhölder, Waldemar; Louie, Steven G.; Cohen, Marvin L.
    Total-energy calculations have been performed for Rb at zero temperature using a self-consistent ab initio pseudopotential approach within a local-density-functional scheme. The energy difference between fcc and bcc Rb, and the energy barrier between these structures, are found to be extremely small near the equilibrium volume. Agreement of the calculated cohesive properties of bcc Rb with experimental values is good in view of the softness of the material. A transition from bcc to fcc has been calculated to occur at a pressure of about 52 kbar for T=0 K, which compares favorably with the observed value of 70 kbar for this transition at room temperature.
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    PFG-NMR studies of ATP diffusion in PEG-DA hydrogels and aqueous solutions of PEG-DA polymers
    (2018) Majer, Günter; Southan, Alexander
    Adenosine triphosphate (ATP) is the major carrier of chemical energy in cells. The diffusion of ATP in hydrogels, which have a structural resemblance to the natural extracellular matrix, is therefore of great importance to understand many biological processes. In continuation of our recent studies of ATP diffusion in poly(ethylene glycol) diacrylate (PEG-DA) hydrogels by pulsed field gradient nuclear magnetic resonance (PFG-NMR), we present precise diffusion measurements of ATP in aqueous solutions of PEG-DA polymers, which are not cross-linked to a three-dimensional network. The dependence of the ATP diffusion on the polymer volume fraction in the hydrogels, φ, was found to be consistent with the predictions of a modified obstruction model or the free volume theory in combination with the sieving behavior of the polymer chains. The present measurements of ATP diffusion in aqueous solutions of the polymers revealed that the diffusion coefficient is determined by φ only, regardless of whether the polymers are cross-linked or not. These results seem to be inconsistent with the free volume model, according to which voids are formed by a statistical redistribution of surrounding molecules, which is expected to occur more frequently in the case of not cross-linked polymers. The present results indicate that ATP diffusion takes place only in the aqueous regions of the systems, with the volume fraction of the polymers, including a solvating water layer, being blocked for the ATP molecules. The solvating water layer increases the effective volume of the polymers by 66%. This modified obstruction model is most appropriate to correctly describe the ATP diffusion in PEG-DA hydrogels.
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    Dynamic ultrasound projector controlled by light
    (2022) Ma, Zhichao; Joh, Hyungmok; Fan, Donglei Emma; Fischer, Peer
    Dynamic acoustic wavefront control is essential for many acoustic applications, including biomedical imaging and particle manipulation. Conventional methods are either static or in the case of phased transducer arrays are limited to a few elements and hence limited control. Here, a dynamic acoustic wavefront control method based on light patterns that locally trigger the generation of microbubbles is introduced. As a small gas bubble can effectively stop ultrasound transmission in a liquid, the optical images are used to drive a short electrolysis and form microbubble patterns. The generation of microbubbles is controlled by structured light projection at a low intensity of 65 mW cm-2 and only requires about 100 ms. The bubble pattern is thus able to modify the wavefront of acoustic waves from a single transducer. The method is employed to realize an acoustic projector that can generate various acoustic images and patterns, including multiple foci and acoustic phase gradients. Hydrophone scans show that the acoustic field after the modulation by the microbubble pattern forms according to the prediction. It is believed that combining a versatile optical projector to realize an ultrasound projector is a general scheme, which can benefit a multitude of applications based on dynamic acoustic fields.
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    Endowing a NAO robot with practical social-touch perception
    (2022) Burns, Rachael Bevill; Lee, Hyosang; Seifi, Hasti; Faulkner, Robert; Kuchenbecker, Katherine J.
    Social touch is essential to everyday interactions, but current socially assistive robots have limited touch-perception capabilities. Rather than build entirely new robotic systems, we propose to augment existing rigid-bodied robots with an external touch-perception system. This practical approach can enable researchers and caregivers to continue to use robotic technology they have already purchased and learned about, but with a myriad of new social-touch interactions possible. This paper presents a low-cost, easy-to-build, soft tactile-perception system that we created for the NAO robot, as well as participants’ feedback on touching this system. We installed four of our fabric-and-foam-based resistive sensors on the curved surfaces of a NAO’s left arm, including its hand, lower arm, upper arm, and shoulder. Fifteen adults then performed five types of affective touch-communication gestures (hitting, poking, squeezing, stroking, and tickling) at two force intensities (gentle and energetic) on the four sensor locations; we share this dataset of four time-varying resistances, our sensor patterns, and a characterization of the sensors’ physical performance. After training, a gesture-classification algorithm based on a random forest identified the correct combined touch gesture and force intensity on windows of held-out test data with an average accuracy of 74.1%, which is more than eight times better than chance. Participants rated the sensor-equipped arm as pleasant to touch and liked the robot’s presence significantly more after touch interactions. Our promising results show that this type of tactile-perception system can detect necessary social-touch communication cues from users, can be tailored to a variety of robot body parts, and can provide HRI researchers with the tools needed to implement social touch in their own systems.
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    Soft urinary bladder phantom for endoscopic training
    (2021) Choi, Eunjin; Waldbillig, Frank; Jeong, Moonkwang; Li, Dandan; Goyal, Rahul; Weber, Patricia; Miernik, Arkadiusz; Grüne, Britta; Hein, Simon; Suarez-Ibarrola, Rodrigo; Kriegmair, Maximilian Christian; Qiu, Tian
    Bladder cancer (BC) is the main disease in the urinary tract with a high recurrence rate and it is diagnosed by cystoscopy (CY). To train the CY procedures, a realistic bladder phantom with correct anatomy and physiological properties is highly required. Here, we report a soft bladder phantom (FlexBlad) that mimics many important features of a human bladder. Under filling, it shows a large volume expansion of more than 300% with a tunable compliance in the range of 12.2 ± 2.8 - 32.7 ± 5.4 mL cmH2O-1 by engineering the thickness of the bladder wall. By 3D printing and multi-step molding, detailed anatomical structures are represented on the inner bladder wall, including sub-millimeter blood vessels and reconfigurable bladder tumors. Endoscopic inspection and tumor biopsy were successfully performed. A multi-center study was carried out, where two groups of urologists with different experience levels executed consecutive CYs in the phantom and filled in questionnaires. The learning curves reveal that the FlexBlad has a positive effect in the endourological training across different skill levels. The statistical results validate the usability of the phantom as a valuable educational tool, and the dynamic feature expands its use as a versatile endoscopic training platform.
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    Magnetic putty as a reconfigurable, recyclable, and accessible soft robotic material
    (2023) Li, Meng; Pal, Aniket; Byun, Junghwan; Gardi, Gaurav; Sitti, Metin
    Magnetically hard materials are widely used to build soft magnetic robots, providing large magnetic force/torque and macrodomain programmability. However, their high magnetic coercivity often presents practical challenges when attempting to reconfigure magnetization patterns, requiring a large magnetic field or heating. In this study, magnetic putty is introduced as a magnetically hard and soft material with large remanence and low coercivity. It is shown that the magnetization of magnetic putty can be easily reoriented with maximum magnitude using an external field that is only one‐tenth of its coercivity. Additionally, magnetic putty is a malleable, autonomous self‐healing material that can be recycled and repurposed. The authors anticipate magnetic putty could provide a versatile and accessible tool for various magnetic robotics applications for fast prototyping and explorations for research and educational purposes.