Plasmonic Response of Complex Nanoparticle Assemblies.

Optical properties of nanoparticle assemblies reflect distinctive characteristics of their building blocks and spatial organization, giving rise to emergent phenomena. Integrated experimental and computational studies have established design principles connecting the structure to properties for assembled clusters and superlattices. However, conventional electromagnetic simulations are too computationally expensive to treat more complex assemblies. Here we establish a fast, materials agnostic method to simulate the optical response of large nanoparticle assemblies incorporating both structural and compositional complexity. This many-bodied, mutual polarization method resolves limitations of established approaches, achieving rapid, accurate convergence for configurations including thousands of nanoparticles, with some overlapping. We demonstrate these capabilities by reproducing experimental trends and uncovering far- and near-field mechanisms governing the optical response of plasmonic semiconductor nanocrystal assemblies including structurally complex gel networks and compositionally complex mixed binary superlattices. This broadly applicable framework will facilitate the design of complex, hierarchically structured, and dynamic assemblies for desired optical characteristics.

Assembling Inorganic Nanocrystal Gels.

Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network-structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advantages in terms of gel stability, reversibility, or tunability and presents new opportunities for the design of reconfigurable materials and fueled assemblies.

Injectable magnetic montmorillonite colloidal gel for the postoperative treatment of hepatocellular carcinoma.

Bioactive materials have been extensively developed for the adjuvant therapy of cancer. However, few materials can meet the requirements for the postoperative resection of hepatocellular carcinoma (HCC) due to massive bleeding and high recurrence. In particular, combination therapy for HCC has been highly recommended in clinical practice, including surgical resection, interventional therapy, ablation therapy and chemotherapy. Herein, an injectable magnetic colloidal gel (MCG) was developed by controllable electrostatic attraction between clinically available magnetic montmorillonites and amphoteric gelatin nanoparticles. The optimized MCG exhibited an effective magnetic heating effect, remarkable rheological properties, and high gel network stability, realizing the synergistic treatment of postoperative HCC by stimuli-responsive drug delivery, hemostasis and magnetic hyperthermia. Furthermore, a minimal invasive MCG-induced interventional magnetic hyperthermia therapy (MHT) under ultrasound guidance was realized on hepatic tumor rabbits, providing an alternative therapeutics to treat the postoperative recurrence. Overall, MCG is a clinically available injectable formulation for adjuvant therapy after HCC surgical resection.

Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions.

Gelation of colloidal nanocrystals emerged as a strategy to preserve inherent nanoscale properties in multiscale architectures. However, available gelation methods to directly form self-supported nanocrystal networks struggle to reliably control nanoscale optical phenomena such as photoluminescence and localized surface plasmon resonance (LSPR) across nanocrystal systems due to processing variabilities. Here, we report on an alternative gelation method based on physical internanocrystal interactions: short-range depletion attractions balanced by long-range electrostatic repulsions. The latter are established by removing the native organic ligands that passivate tin-doped indium oxide (ITO) nanocrystals while the former are introduced by mixing with small PEG chains. As we incorporate increasing concentrations of PEG, we observe a reentrant phase behavior featuring two favorable gelation windows; the first arises from bridging effects while the second is attributed to depletion attractions according to phase behavior predicted by our unified theoretical model. Our assembled nanocrystals remain discrete within the gel network, based on X-ray scattering and high-resolution transmission electron microscopy. The infrared optical response of the gels is reflective of both the nanocrystal building blocks and the network architecture, being characteristic of ITO nanocrystals' LSPR with coupling interactions between neighboring nanocrystals.

Universal Gelation of Metal Oxide Nanocrystals via Depletion Attractions.

Nanocrystal gelation provides a powerful framework to translate nanoscale properties into bulk materials and to engineer emergent properties through the assembled microstructure. However, many established gelation strategies rely on chemical reactions and specific interactions, e.g., stabilizing ligands or ions on the nanocrystals' surfaces, and are therefore not easily transferable. Here, we report a general gelation strategy via nonspecific and purely entropic depletion attractions applied to three types of metal oxide nanocrystals. The gelation thresholds of two compositionally distinct spherical nanocrystals agree quantitatively, demonstrating the adaptability of the approach for different chemistries. Consistent with theoretical phase behavior predictions, nanocrystal cubes form gels at a lower polymer concentration than nanocrystal spheres, allowing shape to serve as a handle to control gelation. These results suggest that the fundamental underpinnings of depletion-driven assembly, traditionally associated with larger colloidal particles, are also applicable at the nanoscale.

Size-dependent viscoelasticity in hybrid colloidal gels based on spherical soft nanoparticles and two-dimensional nanosilicates of varying size.

HYPOTHESIS: Hetero-aggregation of oppositely charged colloidal particles with controlled architectural and interactional asymmetry allows modifying gel nanostructure and properties. We hypothesize the relative size ratio between cationic nanospheres and varied-size anionic two-dimensional nanoclays will influence the gel formation mechanisms and resulting rheological performance. EXPERIMENTS: Hybrid colloidal gels formed via hetero-aggregation of cationic gelatin nanospheres (∼400 nm diameter) and five types of nanoclays with similar 1 nm thickness but different lateral sizes ranging from âˆ¼ 30 nm to âˆ¼ 3000 nm. Structure-property relationships were elucidated using a suite of techniques. Microscopy and scattering probed gel nanostructure and particle configuration. Rheology quantified linear and non-linear viscoelastic properties and yielding behavior. Birefringence and polarized imaging assessed size-dependent nanoclay alignment during shear flow. FINDINGS: Nanoclay size ratio relative to nanospheres affected the gelation process, network structure, elasticity, yielding, and shear response. Gels with comparably sized components showed maximum elasticity, while yield stress depended on nanoclay rotational mobility. Shear-induced nanoclay alignment was quantified by birefringence, which is more pronounced for larger nanoclay. Varying nanoclay size and interactions with nanospheres controlled dispersion, aggregation, and nematic ordering. These findings indicate that architectural and interactional asymmetry enables more control over gel properties through controlled assembly of anisotropic building blocks.

Synergistic effect of Hypoxic Conditioning and Cell-Tethering Colloidal Gels enhanced Productivity of MSC Paracrine Factors and Accelerated Vessel Regeneration.

Microporous hydrogels have been widely used for delivering therapeutic cells. However, several critical issues, such as the lack of control over the harsh environment they are subjected to under pathological conditions and rapid egression of cells from the hydrogels, have produced limited therapeutic outcomes. To address these critical challenges, cell-tethering and hypoxic conditioning colloidal hydrogels containing mesenchymal stem cells (MSCs) are introduced to increase the productivity of paracrine factors locally and in a long-term manner. Cell-tethering colloidal hydrogels that are composed of tyramine-conjugated gelatin prevent cells from egressing through on-cell oxidative phenolic crosslinks while providing mechanical stimulation and interconnected microporous networks to allow for host-implant interactions. Oxygenating microparticles encapsulated in tyramine-conjugated colloidal microgels continuously generated oxygen for 2 weeks with rapid diffusion, resulting in maintaining a mild hypoxic condition while MSCs consumed oxygen under severe hypoxia. Synergistically, local retention of MSCs within the mild hypoxic-conditioned and mechanically robust colloidal hydrogels significantly increased the secretion of various angiogenic cytokines and chemokines. The oxygenating colloidal hydrogels induced anti-inflammatory responses, reduced cellular apoptosis, and promoted numerous large blood vessels in vivo. Finally, mice injected with the MSC-tethered oxygenating colloidal hydrogels significantly improved blood flow restoration and muscle regeneration in a hindlimb ischemia (HLI) model.

Silver Nanowire Reinforced Conductive and Injectable Colloidal Gel for Effective Wound Healing via Electrical Stimulation.

The remarkable biocapacity, injectability, and adaptability of colloidal gels have led to their widespread usage in tissue engineering as irregular defect implants. However, multifunctionalities including electroconductivity and antibacterial property are highly required for colloidal gels. In addition, the inherently weak mechanical property of physically crosslinked colloidal gels limits their application. Herein, we present Ag nanowires (Ag NWs)-reinforced colloidal gels composed of biocompatible gelatin nanoparticles and polydopamine-modified Ag NWs through the controlled electrostatic assembly, which are injectable and conductive. One-dimensional Ag NWs can significantly improve the mechanical and electrical properties of the colloidal gel while maintaining its inherent excellent injectability. Owing to the network of Ag NWs, the storage modulus and conductivity of the optimized Ag NW colloidal gel are 7.5 and 13 times higher, respectively, than those of the colloidal gel made up of polydopamine-modified Ag nanoparticles with equivalent Ag concentration. Furthermore, this Ag NW colloidal gel can adapt to sharp wounds on skin, which accelerates the healing of a MRSA-infected wound via electrical stimulation. This article is protected by copyright. All rights reserved.

Mechanomorphological Guidance of Colloidal Gel Regulates Cell Morphogenesis.

Microstructural morphology of the extracellular matrix guides the organization of cells in 3D. However, current biomaterials-based matrices cannot provide distinct spatial cues through their microstructural morphology due to design constraints. To address this, colloidal gels are developed as 3D matrices with distinct microstructure by aggregating ionic polyurethane colloids via electrostatic screening. Due to the defined orientation of interconnected particles, positively charged colloids form extended strands resulting in a dense microstructure whereas negatively charged colloids form compact aggregates with localized large voids. Chondrogenesis of human mesenchymal stem cells (MSCs) and endothelial morphogenesis of human endothelial cells (ECs) are examined in these colloidal gels. MSCs show enhanced chondrogenic response in dense colloidal gel due to their spatial organization achieved by balancing the cell-cell and cell-matrix interactions compared to porous gels where cells are mainly clustered. ECs tend to form relatively elongated cellular networks in dense colloidal gel compared to porous gels. Additionally, the role of matrix stiffness and viscoelasticity in the morphogenesis of MSCs and ECs are analyzed with respect to microstructural morphology. Overall, these results demonstrate that colloidal gels can provide spatial cues through their microstructural morphology and in correlation with matrix mechanics for cell morphogenesis.

Influence of the Preparation Method on the Structural, Morphological and Dielectric Properties of FeNbO4 Ceramics.

In this work, iron niobate (FeNbO4) was prepared via two processes based on the sol-gel method: colloidal gel and polymeric gel. The obtained powders were submitted to heat treatments at different temperatures based on the results obtained via differential thermal analysis. The structures of the prepared samples were characterized via X-ray diffraction and the morphology was characterized via scanning electron microscopy. The dielectric measurements were performed in the radiofrequency region using the impedance spectroscopy technique and in the microwave range using the resonant cavity method. The influence of the preparation method was noticeable in the structural, morphological and dielectric properties of the studied samples. The polymeric gel method promoted the formation of monoclinic and orthorhombic iron niobate at lower temperatures. The differences in the samples' morphology were also remarkable, both in the size and shape of the grains. The dielectric characterization revealed that the dielectric constant and the dielectric losses had the same order of magnitude and similar trends. A relaxation mechanism was identified in all the samples.

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses.

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. The experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard-hard, hard-soft, and soft-soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

Fibrillar biocompatible colloidal gels based on cellulose nanocrystals and poly(N-isopropylacrylamide) for direct ink writing.

HYPOTHESIS: Hydrogels based on cellulose nanocrystals (CNC) have attracted great interest because of their sustainability, biocompatibility, mechanical strength and fibrillar structure. Gelation of colloidal particles can be induced by the introduction of polymers. Existing examples include gels based on CNC and derivatives of cellulose or poly(vinyl alcohol), however, gel structure and their application for extrusion printing were not shown. Hence, we rationalize formation of colloidal gels based on mixture of poly(N-isopropylacrylamide) (PNIPAM) and CNC and control their structure and mechanical properties by variation of components ratio. EXPERIMENTS: State diagram for colloidal system based on mixture of PNIPAM and CNC were established at 25 and 37 °C. Biocompatibility, fiber diameter and rheological properties of the gels were studied for different PNIPAM/CNC ratio. FINDINGS: We show that depending on the ratio between PNIPAM and CNC, colloidal system could be in sol or gel state at 25 °C and at gel state or phase separated at 37 °C. Physically crosslinked hydrogels were thermosensitive and could reversibly change it transparency from translucent to opaque in biologically relevant temperature range. These colloidal hydrogels were biocompatible, had fibrillar structure and demonstrate shear-thinning behavior, which makes them a promising material for bioapplications related to extrusion printing.

Structural Control of Plasmon Resonance in Molecularly Linked Metal Oxide Nanocrystal Gel Assemblies.

Nanocrystal gels exhibit collective optical phenomena based on interactions among their constituent building blocks. However, their inherently disordered structures have made it challenging to understand, predict, or design properties such as optical absorption spectra that are sensitive to the coupling between the plasmon resonances of the individual nanocrystals. Here, we bring indium tin oxide nanocrystal gels under chemical control and show that their infrared absorption can be predicted and systematically tuned by selecting the nanocrystal sizes and compositions and molecular structures of the link-mediating surface ligands. Thermoreversible assemblies with metal-terpyridine links form reproducible gel architectures, enabling us to derive a plasmon ruler that governs the spectral shifts upon gelation, predicated on the nanocrystal and ligand compositions. This empirical guide is validated using large-scale, many-bodied simulations to compute the optical spectra of gels with varied structural parameters. Based on the derived plasmon ruler, we design and demonstrate a nanocrystal mixture whose spectrum exhibits distinctive line narrowing upon assembly.

Hybrid colloidal gels with tunable elasticity formed by charge-driven assembly between spherical soft nanoparticles and discotic nanosilicates.

Colloidal gels based on electrostatic interparticle attractions hold unexploited potential for tailoring their microstructure and properties. Here, we demonstrate that hetero-aggregation between oppositely charged particles with different geometries is a viable strategy for controlling their properties. Specifically, we studied hybrid colloidal gels prepared by the charge-driven assembly of oppositely charged spherical gelatin nanoparticles and two-dimensional (2D) nanosilicates. We show that the asymmetry between the building blocks and the resulting anisotropic interparticle interactions produces a variety of nanostructures and hybrid colloidal gels that exhibit high elasticity at low colloidal volume fractions. Tuning the competition between different attractive interactions in the system by varying the spatial charge heterogeneity on the 2D nanosheets, composition, and ionic strength was found to alter the mechanism of gel formation and their rheological properties. Remarkably, increasing the mass ratio of 2D nanosheets to spherical nanoparticles at a constant total mass fraction affords hybrid gels that exhibit an inverse relationship between elasticity and volume fraction. However, these hybrid gels are easily fluidized and exhibit rapid structural recovery once the stress is removed. These features allow for the engineering of versatile 3D-printable hybrid colloidal gels, whose structure and viscoelastic response are governed by parameters that have not been explored before.

Cell-derived Extracellular Matrix Proteins in Colloidal Microgel as a Self-Assembly Hydrogel for Regenerative Endodontics.

INTRODUCTION: This study investigated a colloidal microgel for angiogenic and odontogenic differentiation of cells in the presence of cell-derived extracellular matrix (ECM) proteins using a 3-dimensional culture model. METHODS: Viscoelastic properties of human dental pulp were determined to understand the native ECM environment. ECM proteins were extracted from dental pulp stem cell (DPSC) cultures, and MaxGel (Millipore Sigma, Burlington, MA) was used as a commercially available ECM protein. DPSCs were incubated in colloidal microgels in the presence of ECM proteins or gelatin methacryloyl (GelMA) as a bulk hydrogel (n = 9/group). The viability and odontogenic differentiation of DPSCs within hydrogels was determined using viability assays, mineralization staining, calcium and alkaline phosphatase assays, and quantitative polymerase chain reaction for odontogenic gene expression. Angiogenic properties of endothelial cells were determined using tubule formation assays and quantitative polymerase chain reaction to detect angiogenic gene expression. RESULTS: Dental pulp had a higher elastic modulus than the viscous modulus, showing a solidlike response similar to hydrogels. DPSC-derived ECM showed higher collagen and GAG than MaxGel (P < .05). The viability of DPSCs was similar in colloidal microgels, whereas higher cell viability, calcium deposition, and alkaline phosphatase activity were observed in GelMA (P < .05). Colloidal microgels allowed tubule-like structures by endothelial cells, whereas no tubular formation was observed in GelMA. DPSC-derived ECM in colloidal microgel up-regulated odontogenic gene expression, whereas MaxGel up-regulated angiogenic gene expression (P < .05). CONCLUSIONS: Colloidal microgels allowed cellular organization that can improve penetration and nutritional supply in a full-length root canal system. The bioactivity of cell-derived ECM proteins can be modified depending on the external stimulus.

Gelatin-Based Colloidal Versus Monolithic Gels to Regulate Macrophage-Mediated Inflammatory Response.

Unlike conventional monolithic hydrogels with covalent cross-linkage that are typically elastic, colloidal gels assembled by reversibly assembled particles as building blocks have shown fascinating viscoelastic properties. They follow a gel-sol transition upon yielding and recover to the initial state upon the release of the shear force (so-called shear-thinning and self-healing behavior); this makes them an ideal candidate as injectable and moldable biomaterials for tissue regeneration. The immune response provoked by the implantation of the colloidal gels with special viscoelastic and structural features is critical for the successful integration of the implants with the host tissues, which, however, remains little explored. Since macrophages are known as the primary immune cells in determining the inflammatory response against the implants, we herein investigated in vitro macrophage polarization and in vivo inflammatory response induced by gelatin-based colloidal gels as compared to monolithic gels. Specifically, self-healing colloidal gels composed of pure gelatin nanoparticles, or methacrylate gelatin (GelMA) nanoparticles to allow secondary covalent cross-linkage were compared with GelMA bulk hydrogels. We demonstrated that hydrogel's elasticity plays a more dominant role rather than the structural feature in determining in vitro macrophage polarization evidenced by the stiffer gels inducing pro-inflammation M2 macrophage phenotype as compared to soft gels. However, subcutaneous implantation revealed a significantly alleviated immune response characterized by less fibrous capsule formation for the colloidal gels as compared to bulk gels of similar matrix elasticity. We speculated this can be related to the improved permeability of the colloidal gels for cell penetration, thereby leading to less fibrosis. In general, this study provided in-depth insight into the biophysical regulator of hydrogel materials on macrophage behavior and related inflammatory response, which can further direct future implant design and predict biomaterial-host interactions for immunotherapy and regenerative medicine. Impact statement Macrophages response to implanted biomaterials is a highly regulated process that influences device functionality and clinical outcome. Nowadays, the viscoelastic properties of colloidal versus monolithic hydrogels on macrophage phenotype in vitro and the host inflammatory response are not known. Our study found that colloidal hydrogels composed of nanoparticles of gelatin and methacrylate gelatin (GelMA) led to more anti-inflammatory polarization especially on soft colloidal gel (5.9 KPa) compared to bulk GelMA hydrogels. It suggested that macrophage response can be mechanically regulated by the viscoelastic signals of the hydrogels, which could be a promising strategy for the future design and application of novel biomaterials.

Rheology of protein-stabilised emulsion gels envisioned as composite networks. 2 - Framework for the study of emulsion gels.

HYPOTHESIS: The aggregation of protein-stabilised emulsions leads to the formation of emulsion gels. These soft solids may be envisioned as droplet-filled matrices. Here however, it is assumed that protein-coated sub-micron droplets contribute to the network formation in a similar way to proteins. Emulsion gels are thus envisioned as composite networks made of proteins and droplets. EXPERIMENTS: Emulsion gels with a wide range of composition are prepared and their viscoelasticity and frequency dependence are measured. Their rheological behaviours are then analysed and compared with the properties of pure gels presented in the first part of this study. FINDINGS: When the concentrations of droplets and protein are expressed as an effective volume fraction, the rheological behaviour of emulsion gels is shown to depend mostly on the total volume fraction, while the composition of the gel indicates its level of similarity with either pure droplet gels or pure protein gels. These results help to form an emerging picture of protein-stabilised emulsion gel as intermediate between droplet and protein gels. This justifies a posteriori the hypothesis of composite networks, and opens the road for the formulation of emulsion gels with fine-tuned rheology.

Elastic and Stretchable Double Network Hydrogel as Printable Ink for High-Resolution Fabrication of Ionic Skin.

A hydrogel that combines both printability and adaptability, high elasticity, and stretchability can provide ideal mechanical properties, and also render complex and accurate construction for ionic skin. However, it is extremely challenging. Here, we propose a colloidal-based double-network (DN) hydrogel as printable inks for high-precision fabrication of ionic skins. Particularly, polyacrylamide (PAAm), as the covalent network that can maintain the long-term material integrity, was combined with gelatin colloidal network to improve the injectability and printability of the resulting DN hydrogels. The DN design cooperatively provides the hydrogels with higher toughness values and deformability than what single colloidal or PAAm network can achieve. Further design of ionic skin based on capacitor microarray was demonstrated to serve as a sensitive and stable capacitor that can respond to external stimuli, thereby allowing to sense the body movements such as finger bending, laugh, and wrist pulse by translating mechanical changes into electric signals. Therefore, this study provides a novel strategy for the design and preparation of high-resolution ionic skins as the wearable sensor.

A new fractal structural-mechanical theory of particle-filled colloidal networks with heterogeneous stress translation.

This work addresses the role of rigid inclusions in determining the elastic modulus of particle-filled colloidal networks by modifying an established fractal scaling model. The approach acknowledges the heterogeneous nature of stress distribution at length scales beyond the colloidal aggregates, while maintaining structural information at the level of individual clusters. This was achieved by introducing a scaling factor to account for system heterogeneity which contains intrinsic information about the network's capacity to form load-bearing links. Rigid fillers bound to the network induce stress concentration, but additionally serve as junction zones which introduce additional load-bearing pathways. This gives rise to the observed increase in the modulus with filler volume fraction. The proposed relationship between the load-bearing network connectivity and scaling behavior may have additional implications on the fractal dimension determined by rheological methods. Further, this model accommodates an experimentally observed correlation between the scaling behavior of the modulus associated with the addition of fillers and that arising from increasing structurant concentration. The modified fractal model thus provides an alternative view of how fillers contribute to the small- and large-deformation mechanical behavior of filled colloidal gels in a manner consistent with experimental observations.

Conceptual Progress for Explaining and Predicting Self-Organization on Anodized Aluminum Surfaces.

Over the past few years, researchers have made numerous breakthroughs in the field of aluminum anodizing and faced the problem of the lack of adequate theoretical models for the interpretation of some new experimental findings. For instance, spontaneously formed anodic alumina nanofibers and petal-like patterns, flower-like structures observed under AC anodizing conditions, and hierarchical pores whose diameters range from several nanometers to sub-millimeters could be explained neither by the classical field-assisted dissolution theory nor by the plastic flow model. In addition, difficulties arose in explaining the basic indicators of porous film growth, such as the nonlinear current-voltage characteristics of electrochemical cells or the evolution of hexagonal pore patterns at the early stages of anodizing experiments. Such a conceptual crisis resulted in new multidisciplinary investigations and the development of novel theoretical models, whose evolution is discussed at length in this review work. The particular focus of this paper is on the recently developed electroconvection-based theories that allowed making truly remarkable advances in understanding the porous anodic alumina formation process in the last 15 years. Some explanation of the synergy between electrode reactions and transport processes leading to self-organization is provided. Finally, future prospects for the synthesis of novel anodic architectures are discussed.