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Tannic acid-inspired polymers were synthesized to engineer metal-phenolic network (MPN) capsules with different properties including controlled permeability, high biocompatibility and fluorescence.

Multidentate hydrogen bonds (H-bonds) play a pivotal role in determining the structure, dynamicity, and function of biological macromolecules, motivating many researchers to design artificial H-bon...

Despite high demands from various industries, strong adhesion in a wet environment remains challenging. We investigated the underwater adhesion of gallol-functionalized polymers as a function of molecular weight and gallol content. By optimizing these parameters, the underwater adhesion strength of aluminium substrates exceeded 4 MPa. Therefore, the biomimetic molecular design of phenolic polymers is effective for the development of strong underwater adhesives.

We report on a cost-effective synthesis method for copolymers containing bioinspired phenolic and phosphorylcholine groups in the side chain. Adsorption of the gallol group bearing polymers onto surfaces was compared with reference polymers containing catechol, phenol, phenyl or n-butyl groups. We found that the gallol group was the most effective functional group among those tested to immobilize the low-fouling phospholipid polymer on surfaces. The adlayer exhibited the same degree of low-fouling properties as the commercially available phospholipid polymer (LIPIDURE®-PMB), while exhibiting better solvent resistance, especially in water and alcohol. Thus we expect that the reported method may be advantageous in biomedical applications that often involve an alcohol sterilization process.

This work was partially supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI (Grant No. 20F20373 and 20H02581), the Japan Science and Technology Agency (JST) through the Precursory Research for Embryonic Science and Technology (PRESTO) grant number JPMJPR21N4, and UTokyo-Tsinghua collaborative research fund. JJR acknowledges JSPS for the postdoctoral fellowship for research in Japan (P20373). We acknowledge TokudAw Inc for the silk masks. The development of antimicrobial fabrics and textiles that can sustainably inhibit a broad spectrum of microbes is crucial for protecting against pathogens in various environments. However, engineering antimicrobial textiles is challenging due to issues with discoloration and inhibited breathability, the use of harmful or harsh reagents and synthesis conditions, and complex and/or time-consuming processing. Herein, we develop a facile and rapid approach to deposit antimicrobial coatings using universally adherent plant polyphenols and antimicrobial silver ions. Importantly, the coatings are colorless, thin (

Although the synthesis of thiophenol-pendant polymers was reported in the 1950s, the polymers generally suffered from oxidation and became insoluble in organic solvents, hampering detailed characterization and further applications. Dithiocatechol-pendant polymers, which have one additional ortho-thiol group than thiophenol-pendant polymers, have never been synthesized, despite their promise in various applications due to their analogous molecular structure with catechol-pendant polymers. Herein, we report the first synthesis of dithiocatechol-pendant polymers using a novel protection-deprotection strategy. We carefully examined the synthetic routes and identified the deprotection conditions that do not cause cross-linking of the dithiocatechol moieties. Because the resulting dithiocatechol-pendant polymers were soluble in common organic solvents (e.g., tetrahydrofuran and

Background: Porous micro- and nanoparticles have the capacity to encapsulate a large quantity of therapeutics, making them promising delivery vehicles for a variety of applications. This review aims to highlight the latest development of inorganic and hybrid (inorganic/ organic) particles for drug delivery with an additional emphasis on combatting drug resistant cancer. We go one step further and discuss delivery applications beyond medicinal delivery, as there is generally a translation from medicinal delivery to botanic delivery after a short lag time. Methods: We undertook a search of relevant peer-reviewed publications. The quality of the relevant papers was appraised using standard tools. The characteristics of the papers are described herein, and the relevant material and therapeutic properties are discussed. Results: We discuss 4 classes of porous particles in terms of drug delivery and theranostics. We specifically focus on silica, calcium carbonate, metal-phenolic network, and metalorganic framework particles. Other relevant biomedically relevant applications are discussed and we highlight outstanding therapeutic results in the relevant literature. Conclusion: The findings of this review confirm the importance of studying and utilizing porous particles for therapeutic delivery. Moreover, we show that the properties of porous particles that make them promising for medicinal drug delivery also make them promising candidates for agro-industrial applications.

Polyphenols are building blocks with many advantages for engineering biomaterials because they are abundant in nature, biocompatible, biodegradable, and capable of assembly through different mechanisms. A variety of biomaterials across different length scales can be made with different physical/chemical properties and unique stimuli responses using modular and straightforward synthesis routes. We review the recent progress of biomaterials engineering based on polyphenols under three broad categories, namely, particles, films, and gels. The size and scale of the biomaterial along with the specific building blocks allow for a variety of biological applications including drug delivery and theranostics. The dynamic interactions, assembly processes, biological functions, and applications of a wide variety of representative polyphenol biomaterials are overviewed.

Extracellular vesicles, including exosomes, shuttle proteins and genetic information between cells and are recently regarded as a promising class of nanoparticles for biomedical applications. Collecting exosomes from patients and amplifying the signal from the exosome cargo could enable new liquid biopsies owing to the exosome’s strong correlation with disease progression. A promising strategy to develop personalized therapeutic carriers is through surface engineering the exosomes and hijacking their inherent messenger system. However, because of the small size and surface complexity, methods to manipulate exosomes are still in their infancy. The purification, preservation, and engineering of exosomes with high scalability and reproducibility is pivotal for practical applications. By regarding exosomes as a bioderived soft nanoparticle, the amassed knowledge and techniques commonly used in materials chemistry and surface science would contribute to exosome development and exploitation. In this perspective...

Metal-phenolic network (MPN) coatings have generated increasing interest owing to their biologically inspired nature, facile fabrication, and near-universal adherence, especially for biomedical applications. However, a key issue in biomedicine is protein fouling, and the adsorption of proteins on tannic acid-based MPNs remains to be comprehensively studied. Herein, we investigate the interaction of specific biomedically relevant proteins in solution (e.g., bovine serum albumin (BSA), immunoglobulin G (IgG), fibrinogen) and complex biological media (serum) using layer-by-layer-assembled tannic acid/FeIII MPN films. When FeIII was the outermost layer, galloyl-modified poly(2-ethyl-2-oxazoline) (P(EtOx)-Gal) could be grafted to the films through coordination bonds. Protein fouling and bacterial adhesion were greatly suppressed after functionalization with P(EtOx)-Gal and the mass of adsorbed protein was reduced by 79%. Interestingly, larger proteins adsorbed more on both the MPNs and P(EtOx)-functionalized MPNs. This study provides fundamental information on the interactions of MPNs with single proteins, mixtures of proteins as encountered in serum, and the noncovalent, coordination-based, functionalization of MPN films.

Growing metal–organic frameworks (MOFs) around biomolecules has recently emerged as a promising method to combine natural and synthetic materials. In parallel, cellulose nanocrystals (CNCs) have fo...

Robust underwater adhesion is challenging because a hydration layer impedes the interaction between substrates and adhesives. Phenolic adhesives inspired by marine creatures such as mussels were extensively studied, but these adhesives have not reached the adhesion strength and substrate diversity of Man-made dry adhesives. Here, we report a class of ultrastrong underwater adhesives with molecular phenolic designs extending beyond what nature has produced. These non-canonical phenolic polymers show versatile adhesion on various materials, with adhesion strengths exceeding 10 MPa on metal. Incorporating even just a small amount (

Single-cell encapsulation using metal-phenolic networks (MPNs) is an emerging technique to protect cells from stressors. Until now, the MPN coatings have been only applied to some bacteria, yeast, and mammalian cells. To further demonstrate their versatility, we herein coat Chlamydomonas reinhardtii with the network consisting of tannic acid and iron(III). The encapsulation served as a mechanical barrier, which delayed proliferation of the coated cells. Furthermore, we investigated the adsorption of tannic acid onto the surface of C. reinhardtii and identified the optimum concentration to achieve partial coverage on the algae's surface. Finally, we explored the effect of MPN coating for flocculation-enhanced algae harvesting. Overall, the results demonstrate that the cell encapsulation technique using metal-phenolic networks is applicable to the C. reinhardtii, which is promising for the surface engineering of the green algae for energy harvesting and biomedical applications.

The use of moisture in self-healing polymeric materials is a very attractive option given the practical environments in which the materials are used. Herein, we incorporated tetrahedral boronate-esters bearing B–N dative bonds as dynamic crosslinks into polymers, which led to moisture-induced self-healing abilities in their bulk states. Owing to the higher rate of ester formation over tetrahedral boronate-ester hydrolysis under wet conditions, these polymers invariably maintain a sufficient number of dynamic crosslinks to facilitate a combination of autonomous healing behavior and mechanical strength, which makes them unique compared to other previously developed water-triggered self-healing polymers. The self-healed materials maintain good mechanical properties, with fracture stresses of ∼2 MPa, and ageing of the cut surfaces does not affect their healing efficiency. Furthermore, the tetrahedral boronate-ester bonds exhibit dual stimuli-responsive dynamic behavior triggered by either moisture or heat, resulting in network polymers with remarkable reprocessabilities.

Man-made glues often fail to stick in wet environments because of hydration-induced softening and dissolution. The wound healing process of a tunicate inspired the synthesis of gallol-functionalized copolymers as underwater adhesive. Copolymers bearing three types of phenolic groups, namely, phenol, catechol, and gallol, were synthesized via the methoxymethyl protection/deprotection route. Surprisingly, the newly synthesized copolymers bearing gallol groups exhibited stronger adhesive performances (typically 7× stronger in water) than the widely used catechol-functionalized copolymers under all tested conditions (in air, water, seawater, or phosphate-buffered saline solution). The higher binding strength was ascribed to the tridentate-related interfacial interaction and chemical cross-linking. Moreover, gallol-functionalized copolymers adhered to all tested surfaces including plastic, glass, metal, and biological material. In seawater, the performance of gallol-functionalized copolymer even exceeds the commercially available isocyanate-based glue. The insights from this study are expected to help in the design of biomimetic materials containing gallol groups that may be utilized as potential bioadhesives and for other applications. The results from such a kind of comparable study among phenol, catechol, and gallol suggests that tridentate structure should be better than bidentate structure for bonding to the surface.

Surface modification is crucial for conferring novel functionalities to objects and interfaces. However, simple yet versatile strategies for the surface modification of multiple classes of nanomaterials, including biointerfaces, are rare, as the chemical interactions between the surface modifiers and the substrates need to be tailored on a case-by-case basis. Recently, metal-phenolic networks (MPNs) have emerged as a versatile surface modifier based on the universal adherent properties of phenolic molecules, namely the constituent gallol and catechol groups. Additionally, the dynamic interactions between metal ions and phenolic molecules confer additional functionalities to the MPNs, such as stimuli-responsiveness. Given the interest in MPNs for nanomaterial and biointerface engineering, this review aims to provide an overview of the assembly process, physicochemical properties and applications of MPN coatings.

Polymers are widely used in marine environments due to their unique thermal/mechanical properties. Imparting self-healing ability to those polymers would be a beneficial strategy for improved durability; e.g. extending the life time and reducing the maintenance cost. However, most of the existing self-healing polymers suffer from swelling-induced mechanical instability and loss of self-healing ability because of a severe water uptake in fully submerged conditions. Thus, a judicious design principle to prevent the swelling-induced deterioration of the self-healing polymers is greatly required for the long-term use in water-related applications. In this study, we report a polymer that is non-swellable (

Adhesion occurs by covalent bonding, as in reactive structural adhesives, or through noncovalent interactions, which are nearly ubiquitous in nature. A classic example of the latter is gecko feet, where hierarchical features enhance friction across the contact area. Biomimicry of such structured adhesion is regularly achieved by top-down lithography, which allows for direction-dependent detachment. However, bottom-up approaches remain elusive given the scarcity of building blocks that yield strong, cohesive, self-assembly across multiple length scales. Herein, an exception is introduced, namely, aqueous dispersions of cellulose nanocrystals (CNCs) that form superstructured, adherent layers between solid surfaces upon confined evaporation-induced self-assembly (C-EISA). The inherently strong CNCs (E

The targeted therapy of metastatic melanoma is an important yet challenging goal that has received only limited attention to date. Herein, green tea polyphenols, (–)-epigallocatechin-3-gallate (EGCG), and lanthanide metal ions (Sm3+) are used as building blocks to engineer self-assembled SmIII-EGCG nanocomplexes with synergistically enhanced tumor inhibitory properties. These nanocomplexes have negligible systemic toxic effects on healthy cells but cause a significant reduction in the viability of melanoma cells by efficiently regulating their metabolic pathways. Moreover, the wound-induced migration of melanoma cells can be efficiently inhibited by SmIII-EGCG, which is a key criterion for metastatic melanoma therapy. In a mouse melanoma tumor model, SmIII-EGCG is directly compared with a clinical anticancer drug, 5-fluorouracil and shows remarkable tumor inhibition. Moreover, the targeted therapy of SmIII-EGCG is shown to prevent metastatic lung melanoma from spreading to main organs with no adverse side effects on the body weight or organs. These in vivo results demonstrate significant advantages of SmIII-EGCG over its clinical counterpart. The results suggest that these green tea-based, self-assembled nanocomplexes possess all of the key traits of a clinically promising candidate to address the challenges associated with the treatment of advanced stage metastatic melanoma.

The targeted therapy of metastatic melanoma is a highly challenging therapeutic goal that has received only limited attention to date. In article number 1801688, Junling Guo, Xuepin Liao, and co‐workers report the self‐assembly of therapeutic nanocomplexes composed of green tea polyphenols, epigallocatechin‐3‐gallate (EGCG), and lanthanide metal ions (Sm3+). These nanocomplexes show remarkable targeted therapy against melanoma and prevent aggressive migration to main organs with no adverse side effects.

Methods for depositing thin films are important in generating functional materials for diverse applications in a wide variety of fields. Over the last half-century, the layer-by-layer assembly of nanoscale films has received intense and growing interest. This has been fueled by innovation in the available materials and assembly technologies, as well as the film-characterization techniques. In this Review, we explore, discuss, and detail innovation in layer-by-layer assembly in terms of past and present developments, and we highlight how these might guide future advances. A particular focus is on conventional and early developments that have only recently regained interest in the layer-by-layer assembly field. We then review unconventional assemblies and approaches that have been gaining popularity, which include inorganic/organic hybrid materials, cells and tissues, and the use of stereocomplexation, patterning, and dip-pen lithography, to name a few. A relatively recent development is the use of layer-by-layer assembly materials and techniques to assemble films in a single continuous step. We name this "quasi"-layer-by-layer assembly and discuss the impacts and innovations surrounding this approach. Finally, the application of characterization methods to monitor and evaluate layer-by-layer assembly is discussed, as innovation in this area is often overlooked but is essential for development of the field. While we intend for this Review to be easily accessible and act as a guide to researchers new to layer-by-layer assembly, we also believe it will provide insight to current researchers in the field and help guide future developments and innovation.

Materials assembled by coordination interactions between naturally abundant polyphenols and metals are of interest for a wide range of applications, including crystallization, catalysis, and drug delivery. Such an interest has led to the development of thin films with tunable, dynamic properties, however, creating bulk materials remains a challenge. Reported here is a class of metallogels formed by direct gelation between inexpensive, naturally abundant tannic acid and group(IV) metal ions. The metallogels exhibit diverse properties, including self-healing and transparency, and can be doped with various materials by in situ co-gelation. The robustness and flexibility, combined with the ease, low cost, and scalability of the coordination-driven assembly process make these metallogels potential candidates for chemical, biomedical, and environmental applications.

Polyphenols, which by the Quideau definition are plant-derived chemicals with two or more phenolic groups, have attracted interest because of their antioxidant activity, adsorption on universal substrates, and biocompatibility. Most polyphenols include gallol groups in their chemical structures, which has inspired us to synthesize gallol-functionalized polymers. We report the reversible addition–fragmentation chain transfer polymerization of 3,4,5-trimethoxystyrene using cyanomethyl dodecyl trithiocarbonate as the chain transfer agent. This method produces well-defined polymers with a wide range of molecular weight (from 5.4 to 53.4 kg mol–1) and low polydispersity index (Mw/Mn < 1.3). Subsequent demethylation of poly(3,4,5-trimethoxystyrene) (PTMS) yields poly(3,4,5-trihydroxystyrene) (polyvinylgallol, PVGal). These newly synthesized polymers exhibit greater antioxidant activities than widely used catechol-functionalized polymers based on the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), 2,2′-azinobis(3-...

Colloidal lignin particles out of lignocellulosic biorefineries have gained interest due to their improved properties and wide application range compared to standard lignin. In this work, an application as green adhesive was investigated. Solely a suspension of aqueous colloidal lignin particles was used to achieve anisotropic adhesion between two glass slides. The self-assembly of the colloidal lignin particles into macroscopic structures during drying lead to shear strength 8-times higher the tensile strength. Predefined lignin particles are crucial for the adhesion whereas dissolved lignin leads to no practicable adhesion. The high anisotropy of the adhesion and the fact that solely pure lignin is necessary opens new application and research fields and will propagate the application of colloidal lignin particles even more.

Coordination chemistry of natural polyphenols and transition metals allows rapid self-assembly of conformal coatings on diverse substrates. Herein, we report that this coordination-driven self-assembly process applies to simple phenolic molecules with monotopic or ditopic chelating sites (as opposed to macromolecular, multitopic polyphenols), leading to surface-confined amorphous films upon metal coordination. Films fabricated from gallic acid, pyrogallol, and pyrocatechol, which are the major monomeric building blocks of polyphenols, have been studied in detail. Pyrocatechol, with one vicinal diol group (i.e., bidentate), has been observed to be the limiting case for such assembly. This study expands the toolbox of available phenolic ligands for the formation of surface-confined amorphous films, which may find application in catalysis, energy, optoelectronics, and the biomedical sciences.

The creation of hierarchical nanostructures in polymeric materials has been intensively studied due to the great potential to tailor their physicochemical properties. Although much success has been achieved over the past decades in block copolymers, hierarchical structure engineering in polymer blends remains a great challenge. Here, the formation of hierarchical lamellae-in-lamella nanostructures from polymer blends via controlled nonequilibrium freezing is reported. Polymer blends are first dissolved in molten hexamethylbenzene (HMB) to form a homogeneous melt. When cooled to below its melting temperature, the HMB is crystallized and depleted, and the polymers are directionally solidified. This process is rapid enough that phase separation of the polymer blends is kinetically trapped at the nanoscale level. Then, the polymer blend epitaxially crystallizes onto the HMB inside the nanophase, resulting in the hierarchical lamellae-in-lamella structure. This structure is stable under ambient conditions and tunable depending on the annealing temperature and blending ratio.

Periodic lamellar nanostructures have been created in polymer blend thin films composed of poly(L-lactide) (PLLA) and poly(vinyl phenol) (PVPh) via directional solidification and epitaxial crystallization. The obtained morphology was strongly dependent on annealing condition and blending ratio. These processing parameters closely correlate to the strength of the hydrogen bonding between PLLA and PVPh, hence it was highlighted that the noncovalent interaction between polymers affects the pattern formation.

Epitaxial crystallization onto a directionally crystallizable organic solvent, 1,3,5-trichlorobenzene, was applied to polymer blends containing regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT) a...

Stereoselective total synthesis of tabtoxinine-β-lactam has been achieved. The vinylogous Mukaiyama aldol reaction with vinylketene silyl N,O-acetal and α-keto-β-lactam proceeded to afford the adduct possessing a TβL-skeleton with a tert-alcohol in high yield and stereoselectivity. Stereoselective introduction of the amino group has been accomplished by azidation at the α position of the imide followed by hydrogenolysis. A straightforward method to achieve the potent inhibitor of glutamine synthetase, possessing both α-hydroxy-β-lactam and α-amino acid moieties, has been established.

We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules.

Microcapsules are of scientific and technological interest because of their ability to encapsulate cargo inside their hollow interiors, thereby separating and protecting the cargo from the external environment. Both template-free and -mediated strategies have been exploited to prepare microcapsules. For the latter strategy, coating sacrificial particulate templates with robust films is a key step towards obtaining mechanically-stable hollow architectures following template removal. In this review, we focus on phenolic-based film engineering techniques utilizing dopamine (DA) and tannic acid (TA), which have recently emerged as new platforms for template-mediated capsule preparation. The first part of the review describes the self-polymerization of DA, which preferentially occurs at interfaces. The second part of the review describes TA capsules. Particular emphasis is placed on the coordination-triggered rapid deposition of TA on different substrates. These examples highlight the versatility and simplicity of phenolic film engineering strategies for microcapsule preparation. Phenolics are abundant bio-based materials, and thus form an attractive field of research for the future development of microcapsules. This focus review summarizes advances in the recently emerging field of phenolic film engineering for template-mediated microcapsule preparation. By depositing polyphenol films on sacrificial particulate templates and subsequently removing the templates, hollow microcapsules can be readily prepared. Due to the pH-responsive properties, negligible cytotoxicity and the bioactivities of the phenolic building blocks (dopamine and tannic acid), phenolic microcapsules are promising for biomedical applications.

We report the assembly of metal-polyphenol complex (MPC) films and capsules through the sequential deposition of iron(III) ions (Fe(III)) and a natural polyphenol, tannic acid (TA), driven by metal–ligand coordination. Stable Fe(III)/TA films and capsules were formed, indicating lateral and longitudinal cross-linking of TA by Fe(III) in the film structure. Quartz crystal microbalance, ultraviolet–visible (UV-vis) spectrophotometry, and X-ray photoelectron spectroscopy were carried out to quantitatively analyze the film growth. A comparison of the MPC capsules prepared through multistep assembly with those obtained through one-step deposition, as reported previously [Ejima et al., Science 2013, 341, 154–156], reveals substantial differences in the nature of complexation and in their physicochemical properties, including permeability, stiffness, and degradability. This study highlights the importance of engineering MPC films with different properties through implementing different assembly methods.

We report a versatile approach for the design of substrate-independent low-fouling surfaces via mussel-inspired immobilisation of zwitterionic peptides. Using mussel-inspired polydopamine (PDA) coatings, zwitterionic glutamic acid- and lysine-based peptides were immobilised on various substrates, including noble metals, metal oxides, polymers, and semiconductors. The variation of surface chemistry and surface wettability upon surface treatment was monitored with X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Following peptide immobilisation, the surfaces became more hydrophilic due to the strong surface hydration compared with PDA-coated surfaces. The peptide-functionalised surfaces showed resistance to human blood serum adsorption and also effectively prevented the adhesion of gram-negative and gram-positive bacteria (i.e., Escherichia coli and Staphylococcus epidermidis) and mammalian cells (i.e., NIH 3T3 mouse embryonic fibroblast cells). The versatility of mussel-inspired chemistry combined with the unique biological nature and tunability of peptides allows for the design of low-fouling surfaces, making this a promising coating technique for various applications.

A novel class of nanoparticles is developed for the co-delivery of a short cell penetrating peptide and a chemotherapeutic drug to achieve enhanced cytotoxicity. Tunable cytotoxicity is achieved through non-toxic peptide-facilitated gating. The strategy relies on a one-step blending process from polymer building blocks to form monodisperse, PEGylated particles that are sensitive to cellular pH variations. By varying the amount of peptide loading, the chemotherapeutic effects can be enhanced by up to 30-fold.

geometries, largely due to the challenge of fiappropriate template materials. Herein, we exploit metal-organic framework (MOF) crystals as templates to prepare monodisperse rhombic dodecahedral microcapsules. The MOF crystals can be completely removed under mild aqueous conditions, thus providing an advantageous class of template material for microcapsule preparation. The obtained faceted microcapsules are stiffer than spherical counterparts of the same size and shell thickness, refl ecting the near-incompressibility of the facet edges. During observation of up to one month, there is no tendency for these hollow polyhedra to revert toward a lower-energy spherical geometry. These results suggest that faceting can be used as a powerful strategy for tuning the mechanical properties of polymer microcapsules. Faceted geometries are widely found in naturally occurring particles (e.g., viruses), and play a pivotal role in material properties such as elasticity and stiffness. [ 4 ] Polymer microcapsules with a spherical shape have often been prepared via the layer-by-layer (LbL) method [ 5 ] for potential applications in drug/gene delivery, catalysis, biosensing, and microreactors. [ 1 ] Recently, control over the shape of LbL capsules has emerged as an exciting research area, as anisotropic colloids exhibit geometrically dependent interactions with biological interfaces, [ 6 ] such as in cellular processing. [ 7 ] To date, spherical