Motile metal−organic frameworks (MOFs) are potential candidates to serve as small‐scale robotic platforms for applications in environmental remediation, targeted drug delivery, or nanosurgery. Here, magnetic helical microstructures coated with a kind of zinc‐based MOF, zeolitic imidazole framework‐8 (ZIF‐8), with biocompatibility characteristics and pH‐responsive features, are successfully fabricated. Moreover, it is shown that this highly integrated multifunctional device can swim along predesigned tracks under the control of weak rotational magnetic fields. The proposed systems can achieve single‐cell targeting in a cell culture media and a controlled delivery of cargo payloads inside a complex microfluidic channel network. This new approach toward the fabrication of integrated multifunctional systems will open new avenues in soft microrobotics beyond current applications.
Neurodegenerative diseases generally result in irreversible neuronal damage and neuronal death. Cell therapy shows promise as a potential treatment for these diseases. However, the therapeutic targeted delivery of these cells and the in situ provision of a suitable microenvironment for their differentiation into functional neuronal networks remain challenging. A highly integrated multifunctional soft helical microswimmer featuring targeted neuronal cell delivery, on-demand localized wireless neuronal electrostimulation, and post-delivery enzymatic degradation is introduced. The helical soft body of the microswimmer is fabricated by two-photon lithography of the photocurable gelatin-methacryloyl (GelMA)-based hydrogel. The helical body is then impregnated with composite multiferroic nanoparticles displaying magnetoelectric features (MENPs). While the soft GelMA hydrogel chassis supports the cell growth, and is degraded by enzymes secreted by cells, the MENPs allow for the magnetic transportation of the bioactive chassis, and act as magnetically mediated electrostimulators of neuron-like cells. The unique combination of the materials makes these microswimmers highly integrated devices that fulfill several requirements for their future translation to clinical applications, such as cargo delivery, cell stimulation, and biodegradability. The authors envision that these devices will inspire new avenues for targeted cell therapies for traumatic injuries and diseases in the central nervous system.
Metal-organic frameworks (MOFs) are a class of crystalline materials constructed from organic linkers and inorganic nodes. MOFs typically possess ultra-high surface areas and pore volumes; thus, they are ideal candidates for biomedical applications. Zinc Imidazolate Framework 8 (ZIF-8) has been widely established in the literature as a potential candidate for on-demand drug delivery applications due to its remarkable loading capacity, stability in physiological environments, and pH triggered controlled drug release. Using ZIF-8 for in vivo applications requires a clear understanding of the interaction of ZIF-8 with biological tissue. In this work, we investigated the biocompatibility of ZIF-8 towards six different cell lines representing various body parts (kidney, skin, breast, blood, bones, and connective tissue). Our results suggested that ZIF-8 has no significant cytotoxicity up to a threshold value of 30 µg/mL. Above 30 µg/mL the cytotoxicity is shown to result from the effect of released Zinc ions (Zn 2+) on the mitochondrial ROS production, causing cell cycle arrest in the G2/M phase due to irreversible DNA damage, and ultimately initiating cellular apoptosis pathways. Due to this insight, we then encapsulated the hormone insulin into ZIF-8 and compared its drug delivery capabilities to the aforementioned cytotoxicity values. Our results suggest that ZIF-8 is suitable for therapeutic applications and furthermore, establish a clear understanding of the interaction of ZIF-8 and its constituents with various cell lines including, and highlight the important biocompatibility factors that must be considered for future in vivo testing.
The controlled preparation of chiral structures is a contemporary challenge for supramolecular science because of the interesting properties that can arise from the resulting materials, and here we show that a synthetic nonamphiphilic C(3) compound containing π-functional tetrathiafulvalene units can form this kind of object. We describe the synthesis, characterization, and self-assembly properties in solution and in the solid state of the enantiopure materials. Circular dichroism (CD) measurements show optical activity resulting from the presence of twisted stacks of preferential helicity and also reveal the critical importance of fiber nucleation in their formation. Molecular mechanics (MM) and molecular dynamics (MD) simulations combined with CD theoretical calculations demonstrate that the (S) enantiomer provides the (M) helix, which is more stable than the (P) helix for this enantiomer. This relationship is for the first time established in this family of C(3) symmetric compounds. In addition, we show that introduction of the "wrong" enantiomer in a stack decreases the helical reversal barrier in a nonlinear manner, which very probably accounts for the absence of a "majority rules" effect. Mesoscopic chiral fibers, which show inverted helicity, i.e. (P) for the (S) enantiomer and (M) for the (R) one, have been obtained upon reprecipitation from dioxane and analyzed by optical and electronic microscopy. The fibers obtained with the racemic mixture present, as a remarkable feature, opposite homochiral domains within the same fiber, separated by points of helical reversal. Their formation can be explained through an "oscillating" crystallization mechanism. Although C(3) symmetric disk-shaped molecules containing a central benzene core substituted in the 1,3,5 positions with 3,3'-diamido-2,2'-bipyridine based wedges have shown peculiar self-assembly properties for amphiphilic derivatives, the present result shows the benefits of reducing the nonfunctional part of the molecule, in our case with short chiral isopentyl chains. The research reported herein represents an important step toward the preparation of functional mesostructures with controlled helical architectures.
Functional high-density micro-arrays for mass spectrometry enable rapid picolitre-volume aliquoting and ultrasensitive analysis of microscale samples, for example, single cells.
Doped and wired: The organization of the π functional units in amide‐functionalized tetrathiafulvalene in a gel by hydrogen‐bonding interactions has given rise to nanofibers. Doping with iodine generates a conducting material, which upon annealing gives rise to nanowires with metal‐like conductivity (see current‐sensing AFM image).
Electrical stimulation has shown great promise in biomedical applications, such as regenerative medicine, neuromodulation, and cancer treatment. Yet, the use of electrical end effectors such as electrodes requires connectors and batteries, which dramatically hamper the translation of electrical stimulation technologies in several scenarios. Piezoelectric nanomaterials can overcome the limitations of current electrical stimulation procedures as they can be wirelessly activated by external energy sources such as ultrasound. Wireless electrical stimulation mediated by piezoelectric nanoarchitectures constitutes an innovative paradigm enabling the induction of electrical cues within the body in a localized, wireless, and minimally invasive fashion. In this review, we highlight the fundamental mechanisms of acoustically mediated piezoelectric stimulation and its applications in the biomedical area. Yet, the adoption of this technology in a clinical practice is in its infancy, as several open issues, such as piezoelectric properties measurement, control of the ultrasound dose in vitro , modeling and measurement of the piezo effects, knowledge on the triggered bioeffects, therapy targeting, biocompatibility studies, and control of the ultrasound dose delivered in vivo , must be addressed. This article explores the current open challenges in piezoelectric stimulation and proposes strategies that may guide future research efforts in this field toward the translation of this technology to the clinical scene.
Microfluidics enables selection of different pathways in self-assembly processes, while allowing for an exquisite control over the processing of self-assembled materials.
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