Advances in Nanoarchitectonics: A Review of "Static" and "Dynamic" Particle Assembly Methods.

Particle assembly is a promising technique to create functional materials and devices from nanoscale building blocks. However, the control of particle arrangement and orientation is challenging and requires careful design of the assembly methods and conditions. In this study, the static and dynamic methods of particle assembly are reviewed, focusing on their applications in biomaterial sciences. Static methods rely on the equilibrium interactions between particles and substrates, such as electrostatic, magnetic, or capillary forces. Dynamic methods can be associated with the application of external stimuli, such as electric fields, magnetic fields, light, or sound, to manipulate the particles in a non-equilibrium state. This study discusses the advantages and limitations of such methods as well as nanoarchitectonic principles that guide the formation of desired structures and functions. It also highlights some examples of biomaterials and devices that have been fabricated by particle assembly, such as biosensors, drug delivery systems, tissue engineering scaffolds, and artificial organs. It concludes by outlining the future challenges and opportunities of particle assembly for biomaterial sciences. This review stands as a crucial guide for scholars and professionals in the field, fostering further investigation and innovation. It also highlights the necessity for continuous research to refine these methodologies and devise more efficient techniques for nanomaterial synthesis. The potential ramifications on healthcare and technology are substantial, with implications for drug delivery systems, diagnostic tools, disease treatments, energy storage, environmental science, and electronics.

Nanodeformations of microcapsules: comparing the effects of cross-linking and nanoparticles.

The mechanical properties of proteinaceous and composite microcapsules loaded with oil were measured by SFM and evaluated using the Reissner model. Comparison of the obtained results reveals significantly higher Young's moduli of protein capsules due to intermolecular crosslinking. In contrast, conformational restrictions in composite microcapsules inhibit protein crosslinking leading to the reduction of their elasticity.

Synthesis of nanostructured protein-mineral-microcapsules by sonication.

We propose a simple and eco-friendly method for the formation of composite protein-mineral-microcapsules induced by ultrasound treatment. Protein- and nanoparticle-stabilized oil-in-water (O/W) emulsions loaded with different oils are prepared using high-intensity ultrasound. The formation of thin composite mineral proteinaceous shells is realized with various types of nanoparticles, which are pre-modified with Bovine Serum Albumin (BSA) and subsequently characterized by EDX, TGA, zeta potential measurements and Raman spectroscopy. Cryo-SEM and EDX mapping visualizations show the homogeneous distribution of the densely packed nanoparticles in the capsule shell. In contrast to the results reported in our previous paper,1 the shell of those nanostructured composite microcapsules is not cross-linked by the intermolecular disulfide bonds between BSA molecules. Instead, a Pickering-Emulsion formation takes place because of the amphiphilicity-driven spontaneous attachment of the BSA-modified nanoparticles at the oil/water interface. Using colloidal particles for the formation of the shell of the microcapsules, in our case silica, hydroxyapatite and calcium carbonate nanoparticles, is promising for the creation of new functional materials. The nanoparticulate building blocks of the composite shell with different chemical, physical or morphological properties can contribute to additional, sometimes even multiple, features of the resulting capsules. Microcapsules with shells of densely packed nanoparticles could find interesting applications in pharmaceutical science, cosmetics or in food technology.

A Dual pH- and Light-Responsive Spiropyran-Based Surfactant: Investigations on Its Switching Behavior and Remote Control over Emulsion Stability.

A cationic surfactant containing a spiropyran unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyran (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions.

New way for cell differentiation: Reaction, diffusion and chaotic waves.

In this paper, we consider reaction-diffusion systems, which describe the propagation of waves with chaotic and time periodic fronts. Using this property, we show that there exist reaction-diffusion models with a few of reagents, which, by a variation of initial data, is capable to generate all possible one-dimensional cell patterns. We describe algorithms, which allow to obtain any prescribed target cell patterns by chaotic waves. Our model can be considered as a reaction-diffusion analogue of universal Turing machine. So, we propose a new robust mechanism of positional information transfer, which, in contrast to Wolpert' gradients, can work at long distances. Universality of our model helps to explain why genes, responsible for morphogenesis, are highly conservative within long evolution periods.

Wear patterns and dental functioning in an Early Cretaceous stegosaur from Yakutia, Eastern Russia.

Isolated stegosaurian teeth from the Early Cretaceous high-latitude (palaeolatitude estimate of N 62°- 66.5°) Teete locality in Yakutia (Eastern Siberia, Russia) are characterized by a labiolingually compressed, slightly asymmetrical and mesiodistally denticulated (9-14 denticles) crown, a pronounced ring-like cingulum, as well as a "complex network of secondary ridges". The 63 teeth (found during on-site excavation in 2012, 2017-2019 and screen-washing in 2017-2019) most likely belong to one species of a derived (stegosaurine) stegosaur. Most of the teeth exhibit a high degree of wear and up to three wear facets has been observed on a single tooth. The prevalence of worn teeth with up to three wear facets and the presence of different types of facets (including steeply inclined and groove-like) indicate the tooth-tooth contact and precise dental occlusion in the Teete stegosaur. The microwear pattern (mesiodistally or slightly obliquely oriented scratches; differently oriented straight and curved scratches on some wear facets) suggest a complex jaw mechanism with palinal jaw motion. Histological analysis revealed that the Teete stegosaur is characterized by relatively short tooth formation time (95 days) and the presence of a "wavy enamel pattern". Discoveries of a "wavy enamel pattern" in the Teete stegosaur, in a Middle Jurassic stegosaur from Western Siberia, and in the basal ceratopsian Psittacosaurus, suggest that this histological feature is common for different ornithischian clades, including ornithopods, marginocephalians, and thyreophorans. A juvenile tooth in the Teete sample indicates that stegosaurs were year-round residents and reproduced in high latitudes. The combination of high degree of tooth wear with formation of multiple wear facets, complex jaw motions, relatively short tooth formation time and possibly high tooth replacement rates is interpreted as a special adaptation for a life in high-latitude conditions or, alternatively, as a common stegosaurian adaptation making stegosaurs a successful group of herbivorous dinosaurs in the Middle Jurassic-Early Cretaceous and enabeling them to live in both low- and high-latitude ecosystems.

About the mechanism of ultrasonically induced protein capsule formation.

In this paper, we propose a consistent mechanism of protein microcapsule formation upon ultrasound treatment. Aqueous suspensions of bovine serum albumin (BSA) microcapsules filled with toluene are prepared by use of high-intensity ultrasound following a reported method. Stabilization of the oil-in-water emulsion by the adsorption of the protein molecules at the interface of the emulsion droplets is accompanied by the creation of the cross-linked capsule shell due to formation of intermolecular disulfide bonds caused by highly reactive species like superoxide radicals generated sonochemically. The evidence for this mechanism, which until now remained elusive and was not proven properly, is presented based on experimental data from SDS-PAGE, Raman spectroscopy and dynamic light scattering.

Recent advances and remaining barriers to producing novel formulations of fungicides for safe and sustainable agriculture.

BACKGROUND: Fungi have evolved for 1 billion years and due to their adaptability and resilience can be found in multiple habitats around the globe. Among numerous species of fungi, some are pathogenic, and humans have battled since the dawn of organized agriculture to reduce production losses. With the arrival of fungicides many gains have been made in this struggle. However, though fungicides have greatly contributed to substantial increase in agricultural productivity, their over usage has led to both health and environmental repercussions. They remain cornerstone of the agriculture industry, however, development of safer formulations to champion sustainable and eco-friendly agriculture is of great importance, especially in face of a growing global population, climate change and increasing fungal resistance to existing compounds. SCOPE AND APPROACH: The aim of this review is to present the state of the art in fungicides formulations developed for agrochemistry, also describing recent improvements in their safety, with special focus on fungicides used most against the ten most important fungal pathogens. KEY FINDINGS AND CONCLUSIONS: The major focus in the field remains to be the improvement of the overall performance of the fungicide formulations. The research trends are also moving towards developing more eco-friendly formulations. However, there are still very few studies assessing nanoformulations toxicity and environmental impact. For example, there is still a limited body of research on the holistic assessment of nanoformulation shells' fate in soil and in the environment after release, as well as redistribution within plants after absorption, with no studies on human or environmental exposure.

Self-Assembly Behavior of Oppositely Charged Inverse Bipatchy Microcolloids.

A directed attractive interaction between predefined "patchy" sites on the surfaces of anisotropic microcolloids can provide them with the ability to self-assemble in a controlled manner to build target structures of increased complexity. An important step toward the controlled formation of a desired superstructure is to identify reversible electrostatic interactions between patches which allow them to align with one another. The formation of bipatchy particles with two oppositely charged patches fabricated using sandwich microcontact printing is reported. These particles spontaneously self-aggregate in solution, where a diversity of short and long chains of bipatchy particles with different shapes, such as branched, bent, and linear, are formed. Calculations show that chain formation is driven by a combination of attractive electrostatic interactions between oppositely charged patches and the charge-induced polarization of interacting particles.

Mono-patchy zwitterionic microcolloids as building blocks for pH-controlled self-assembly.

A directional molecular interaction between microcolloids can be achieved through pre-defined sites on their surface, "patches", which might make them follow each other in a controlled way and assemble into target structures of more complexity. In this article, we report the successful generation and characterization of mono-patchy melamine-formaldehyde microparticles with oppositely charged patches made of poly(methyl vinyl ether-alt-maleic acid) or polyethyleneimine via microcontact printing. The study of their self-aggregation behavior in solution shows that by change of pH, particle dimers are formed via attractive electrostatic force between the patchy and non-patchy surface of the particles, which reaches its optimum at a specific pH.

From 2D to 3D patches on multifunctional particles: how microcontact printing creates a new dimension of functionality.

A straightforward approach for the precise multifunctional surface modification of particles with three-dimensional patches using microcontact printing is presented. By comparison to previous works it was possible to not only control the diameter, but also to finely tune the thickness of the deposited layer, opening up the way for three-dimensional structures and orthogonal multifunctionality. The use of PEI as polymeric ink, PDMS stamps for microcontact printing on silica particles and the influence of different solvents during particle release on the creation of functional particles with three-dimensional patches are described. Finally, by introducing fluorescent properties by incorporation of quantum dots into patches and by particle self-assembly via avidin-biotin coupling, the versatility of this novel modification method is demonstrated.

Characteristics of microcontact printing with polyelectrolyte ink for the precise preparation of patches on silica particles.

This publication demonstrates the abilities of a precise and straightforward microcontact printing approach for the preparation of patchy silica particles. In a broad particle size range, it is possible to finely tune the number and parameters of three-dimensional patches like diameter and thickness using only polyethyleneimine ink, poly(dimethoxysilane) as stamp material and a suitable release solvent.

Modified Mesoporous Silica Nanoparticles with a Dual Synergetic Antibacterial Effect.

Application of mesoporous silica nanoparticles (MSNs) as antifouling/antibacterial carriers is limited and specifically with a dual synergetic effect. In the present work, MSNs modified with quaternary ammonium salts (QASs) and loaded with the biocide Parmetol S15 were synthesized as functional fillers for antifouling/antibacterial coatings. From the family of the MSNs, MCM-48 was selected as a carrier because of its cubic pore structure, high surface area, and high specific pore volume. The QASs used for the surface modification of MCM-48 were dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and dimethyltetradecyl[3-(triethoxysilyl)propyl]ammonium chloride. The QAS-modified MCM-48 reveals strong covalent bonds between the QAS and the surface of the nanoparticles. The surface functionalization was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and ζ-potential measurements. Additional loading of the QAS-modified MCM-48 with a commercially available biocide (Parmetol S15) resulted in a synergetic dual antibacterial/antifouling effect. Either loaded or unloaded QAS-modified MSNs exhibited high antibacterial performance confirming their dual activity. The QAS-modified MCM-48 loaded with the biocide Parmetol S15 killed all exposed bacteria after 3 h of incubation and presented 100% reduction at the antibacterial tests against Gram-negative and Gram-positive bacteria. Furthermore, the QAS-modified MCM-48 without Parmetol S15 presented 77-89% reduction against the exposed Gram-negative bacteria and 78-94% reduction against the exposed Gram-positive bacteria. In addition, the modified MCM-48 was mixed with coating formulations, and its antifouling performance was assessed in a field test trial in northern Red Sea. All synthesized paints presented significant antifouling properties after 5 months of exposure in real seawater conditions, and the dual antifouling effect of the nanoparticles was confirmed.

Nonuniform Growth of Composite Layer-by-Layer Assembled Coatings via Three-Dimensional Expansion of Hydrophobic Magnetite Nanoparticles.

Nanocomposite coatings are promising for a range of practical applications, and layer-by-layer assembly (LbL) is a versatile tool for nanocomposite formation. However, conventional LbL is a quite laborious procedure taking a lot of time to reach a sufficient thickness of the coatings required for practical applications. Herein, we proposed a novel variant of the LbL approach based on the deposition of hydrophilic polyelectrolyte molecules from a polar solvent and hydrophobic magnetite nanoparticles (NPs) from a nonpolar dispersion medium with an intermediate washing in the same polar solvent. The composite multilayers formed in this way exhibit exponential growth of the thickness and mass. On the basis of quartz crystal microbalance (QCM), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), and surface profile measurements, we propose a model describing the driving force of multilayer formation and the factors leading to nonlinear growth of their mass and thickness. The results allow one to expand the understanding of the mechanism of the LbL assembly in order to form multifunctional nanocomposites in a more efficient way.

Preparation of multifunctional polysaccharide microcontainers for lipophilic bioactive agents.

Chitosan/xanthan gum microcontainers with a core-shell structure formed due to chemical interactions between polysaccharide chains induced by ultrasonication are presented. Containers were prepared by sonication of water-immiscible (oil-like) liquids in the solution of polysaccharides. One-step fabrication of the container permanent shell is possible, because of the contribution of ultrasonically caused formation of hydrogen bonds and amide linkages. We synthesized containers in a wide size range from 350 nm to 7500 nm, varying in oil/water ratio. The microcontainers were modified with oppositely charged polyelectrolytes and microparticles, which could be used to impart the specified properties to the system. The biocide 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one (DCOIT) was loaded into the proposed containers by utilizing its solution as an oil phase. The following incorporation of the DCOIT containers into the polymer coating demonstrated more sustained antimicrobial activity (∼30%) of the biocide in the encapsulated state, compared to its non-encapsulated form.

Development of nanoparticle stabilized polymer nanocontainers with high content of the encapsulated active agent and their application in water-borne anticorrosive coatings.

A novel method for the encapsulation of organic active agents in nanoparticle-armored polymer composite nanocontainers (analog of Pickering emulsions) is introduced. The multifunctionality of the constituents allows a fabrication path that does not require auxiliary materials. Embedding the composite nanocontainers into a water-based alkyd resin and subsequent film formation yields a homogeneous polymer film doped with highly disperse composite nanocontainers. The resistance and self-healing of such a film on aluminium is enhanced.

Cytotoxic effects of chemotherapeutic drugs and heterocyclic compounds at application on the cells of primary culture of neuroepithelium tumors.

Neuroepithelial tumor cells were cultured in vitro. The biopsy material was taken from 93 children at removal of the brain tumors during neurosurgical operations. The individual features of the cells sensitivity of primary cultures in respect to protocol-approved chemotherapy drugs and changes in the Interleukin-6 (Il-6) level in the culture medium after the application of chemotherapy were established. The initial level of Il-6 exceeded 600.0 pg/ml in the cultural medium with histologically verified pilomyxoid astrocytoma cells, and ranged from 100.0 to 200.0 pg/ml in the medium at cultivation of ganglioneuroblastoma and pilocytic astrocytoma. A decrease in the Il-6 level in the medium culture of primary tumors cells was observed after the application of chemotherapeutic agents on the cells of pilomyxoid astrocytoma, astrocytomas, and pilocytic desmoplastic/nodular medulloblastoma. The production of Il-6 increased after application of cytostatic drugs on the cells of oligoastrocytomas. A decrease in Il-6 level after application of Cisplatin and Methotrexate and a 5-10 fold increase in the level of Il-6 after application of Etoposide, Carboplatin, Cytarabine, and Gemcitabine were registered in the medium with ganglioneuroblastoma. To improve the cytotoxic action of chemotherapeutic agents, the combined application of cytostatics with heterocyclic compounds was carried out. A computer modeling of ligand-protein complexes of carbamide using the Dock 6.4 and USF Chimera program packages was performed with molecular mechanics method. Special attention was drawn to the ability of several isoxazole heterocycles and isothiazolyl to inhibit the tyrosine kinase. It was proved in vitro that the joint application of chemotherapeutic agents and heterocyclic compounds could reduce the concentration of the cytostatic factor by 10 or more times, having maintained the maximum cytotoxic effect. It was assumed that the target amplification of cytotoxic action of chemotherapeutic agents had prospects for reducing toxic side effects of chemotherapy in vivo, which would be carried out only after the preclinical studies.

Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions.

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.

Interfacial assembly of partially hydrophobic silica nanoparticles induced by ultrasonic treatment.

A sonochemical approach has effectively been applied to prepare aqueous dispersions of air-filled nanostructured quartz silica shells from surface-engineered amorphous silica nanoparticles. The non-equilibrium nature of the cavitation process and high temperature and pressure in the cavitation microbubble can lead to partial crystallization of the amorphous silica nanoparticles producing the quartz phase and a high degree of interconnection between the silica nanoparticles in the microsphere shells. The very high stability of the silica shells against collapse and aggregation is determined by the hydrophobic nature of the silica nanoparticles. Because of the shell thickness and its high density caused by sintering of the silica nanoparticles, the gas (liquid) permeability through the shell is limited thus prolonging the life time of the air-filled nanostructured silica shells.

Mixed monolayers of alkylated azacrown ethers and palmitic acid at the air-water surface.

The Langmuir films of two alkylated azacrown ethers at the air-water surface were characterized using surface pressure-area isotherms, ellipsometry, Brewster angle microscopy, and constant-area surface pressure relaxation. The azacrown ether molecules aggregate in the monolayer, which significantly stabilizes the film against dissolution. Mixed azacrown ether-palmitic acid monolayers were also characterized; results suggest that at high compression the two molecules interact repulsively. The influence of Cu(II) ions present in the aqueous subphase on the single components and mixed monolayer characteristics was also studied.