Doping of molecular semiconductors through proton-coupled electron transfer.

The chemical doping of molecular semiconductors is based on electron-transfer reactions between the semiconductor and dopant molecules; here, the redox potential of the dopant is key to control the Fermi level of the semiconductor1,2. The tunability and reproducibility of chemical doping are limited by the availability of dopant materials and the effects of impurities such as water. Here we focused on proton-coupled electron-transfer (PCET) reactions, which are widely used in biochemical processes3,4; their redox potentials depend on an easily handled parameter, that is, proton activity. We immersed p-type organic semiconductor thin films in aqueous solutions with PCET-based redox pairs and hydrophobic molecular ions. Synergistic reactions of PCET and ion intercalation resulted in efficient chemical doping of crystalline organic semiconductor thin films under ambient conditions. In accordance with the Nernst equation, the Fermi levels of the semiconductors were controlled reproducibly with a high degree of precision-a thermal energy of about 25 millielectronvolts at room temperature and over a few hundred millielectronvolts around the band edge. A reference-electrode-free, resistive pH sensor based on this method is also proposed. A connection between semiconductor doping and proton activity, a widely used parameter in chemical and biochemical processes, may help create a platform for ambient semiconductor processes and biomolecular electronics.

Interface-Interactive Nanoarchitectonics: Solid and/or Liquid.

The methodology of nanoarchitectonics is to construct functional materials using nanounits such as atoms, molecules, and nanoobjects, just like architecting buildings. Nanoarchitectonics pursues the ultimate concept of materials science through the integration of related fields. In this review paper, under the title of interface-interactive nanoarchitectonics, several examples of structure fabrication and function development at interfaces will be discussed, highlighting the importance of architecting materials with nanoscale considerations. Two sections provide some examples at the solid and liquid surfaces. In solid interfacial environments, molecular structures can be precisely observed and analyzed with theoretical calculations. Solid surfaces are a prime site for nanoarchitectonics at the molecular level. Nanoarchitectonics of solid surfaces has the potential to pave the way for cutting-edge functionality and science based on advanced observation and analysis. Liquid surfaces are more kinetic and dynamic than solid interfaces, and their high fluidity offers many possibilities for structure fabrications by nanoarchitectonics. The latter feature has advantages in terms of freedom of interaction and diversity of components, therefore, liquid surfaces may be more suitable environments for the development of functionalities. The final section then discusses what is needed for the future of material creation in nanoarchitectonics.

The Past and the Future of Langmuir and Langmuir-Blodgett Films.

The Langmuir-Blodgett (LB) technique, through which monolayers are transferred from the air/water interface onto a solid substrate, was the first method to allow for the controlled assembly of organic molecules. With its almost 100 year history, it has been the inspiration for most methods to functionalize surfaces and produce nanocoatings, in addition to serving to explore concepts in molecular electronics and nanoarchitectonics. This paper provides an overview of the history of Langmuir monolayers and LB films, including the potential use in devices and a discussion on why LB films are seldom considered for practical applications today. Emphasis is then given to two areas where these films offer unique opportunities, namely, in mimicking cell membrane models and exploiting nanoarchitectonics concepts to produce sensors, investigate molecular recognitions, and assemble molecular machines. The most promising topics for the short- and long-term prospects of the LB technique are also highlighted.

Molecular machines working at interfaces: physics, chemistry, evolution and nanoarchitectonics.

As a post-nanotechnology concept, nanoarchitectonics combines nanotechnology with advanced materials science. Molecular machines made by assembling molecular units and their organizational bodies are also products of nanoarchitectonics. They can be regarded as the smallest functional materials. Originally, studies on molecular machines analyzed the average properties of objects dispersed in solution by spectroscopic methods. Researchers' playgrounds partially shifted to solid interfaces, because high-resolution observation of molecular machines is usually done on solid interfaces under high vacuum and cryogenic conditions. Additionally, to ensure the practical applicability of molecular machines, operation under ambient conditions is necessary. The latter conditions are met in dynamic interfacial environments such as the surface of water at room temperature. According to these backgrounds, this review summarizes the trends of molecular machines that continue to evolve under the concept of nanoarchitectonics in interfacial environments. Some recent examples of molecular machines in solution are briefly introduced first, which is followed by an overview of studies of molecular machines and similar supramolecular structures in various interfacial environments. The interfacial environments are classified into (i) solid interfaces, (ii) liquid interfaces, and (iii) various material and biological interfaces. Molecular machines are expanding their activities from the static environment of a solid interface to the more dynamic environment of a liquid interface. Molecular machines change their field of activity while maintaining their basic functions and induce the accumulation of individual molecular machines into macroscopic physical properties molecular machines through macroscopic mechanical motions can be employed to control molecular machines. Moreover, research on molecular machines is not limited to solid and liquid interfaces; interfaces with living organisms are also crucial.

Adsorptive avidity of Prussian blue polypyrrole nanocomposite for elimination of water contaminants: a case study of malachite green and isoniazid.

Persistent water contaminants include a variety of substances that evade natural cleaning processes posing severe risks to ecosystems. Their adsorptive elimination is a key approach to safer attenuation. Herein we present the design and development of Prussian blue incorporated polypyrrole (PPY/PB) hybrid nanocomposite as a high-performance adsorbent for the elimination of malachite green (M.G.), isoniazid (INH) and 4-nitrophenol (4-NP) water contaminants. The nanocomposite synthesis was favored by strong dopant-polymer interactions, leading to a PPY/PB material with enhanced electro-active surface area compared to pristine PPY. The structure-activity response of the nanocomposite for the adsorption of target contaminants was unveiled by evaluating its maximum adsorption capacities under environmentally viable conditions. In-depth analysis and optimization of adsorption influencing factors (pH, temperature, and adsorbent dose) were performed. Using equilibrium studies, kinetic model fitting, aided with FTIR analysis, a multi-step mechanism for the adsorption of target contaminants on the nanocomposite was proposed. Furthermore, the PPY/PB nanocomposite also acts as a catalyst, enabling contaminant elimination following a synergistic scheme that was demonstrated using 4-NP contaminant. The synergetic adsorption and catalytic degradation of 4-NP using PPY/PB as adsorbent and catalyst was demonstrated in the presence of NaBH4 as a reducing agent in absence of light. In summary, this work highlights the targeted design of adsorbent, its optimization for adsorptive avidity, and the synergistic role of adsorption trapping in the catalytic degradation of persistent contaminants.

Bioactive alkaloids from Nepalese Corydalis chaerophylla D.C. acting on the regulation of PCSK9 and LDL-R in vitro.

Four new alkaloids Chaeronepaline-A (1), Chaeronepaline-B (2), Chaeronepaline-C (3), and Chaeronepaline-D (4) were isolated from Corydalis chaerophylla D.C. collected from Nepal and their structures were elucidated by spectroscopic data, 1D, 2D NMR and mass spectrometry. The structures were established as 3,12- Dimethoxy-5,6-dihydroisoquinolino [2,1-b] isoquinolin- 7- ium- 2, 9- diol (1), 7-methyl-5, 6, 7, 8-tetrahydroisoquinoline- 2, 3- methylenedioxy- (8-> 9)- 10, 12- methylenedioxy- benzoic-16-acid (2), 7- methyl-5, 6, 7, 8- tetrahydro- 8H-spiro-9,14-dihydroxy-11,12-methylenedioxy-indane-isoquinoline (3) and 7- methyl-5, 6, 7, 8- tetrahydro- 8H-spiro-9,14-dihydroxy-11,12-methylenedioxy-indane-isoquinoline-N-oxide (4). The new alkaloids were tested in human hepatoma cell line to assess their ability to modulate the expression of low-density lipoprotein receptor (LDL-R), of proprotein convertase subtilisin/kexin 9 (PCSK9) and to affect cellular cholesterol biosynthesis with the aim to evaluate their potential hypocholesterolemic effect. Results indicated that compounds 2 and 3 upregulate the LDLR, and inhibited the cholesterol biosynthesis with compound 2, which also reduced the secretion of PCSK9 by Huh7 cells. These in vitro data indicated a potential hypocholesterolemic effect of compound 2 that requires further in vivo validation.

Cell-derived nanomaterials for biomedical applications.

The ever-growing use of nature-derived materials creates exciting opportunities for novel development in various therapeutic biomedical applications. Living cells, serving as the foundation of nanoarchitectonics, exhibit remarkable capabilities that enable the development of bioinspired and biomimetic systems, which will be explored in this review. To understand the foundation of this development, we first revisited the anatomy of cells to explore the characteristics of the building blocks of life that is relevant. Interestingly, animal cells have amazing capabilities due to the inherent functionalities in each specialized cell type. Notably, the versatility of cell membranes allows red blood cells and neutrophils' membranes to cloak inorganic nanoparticles that would naturally be eliminated by the immune system. This underscores how cell membranes facilitate interactions with the surroundings through recognition, targeting, signalling, exchange, and cargo attachment. The functionality of cell membrane-coated nanoparticles can be tailored and improved by strategically engineering the membrane, selecting from a variety of cell membranes with known distinct inherent properties. On the other hand, plant cells exhibit remarkable capabilities for synthesizing various nanoparticles. They play a role in the synthesis of metal, carbon-based, and polymer nanoparticles, used for applications such as antimicrobials or antioxidants. One of the versatile components in plant cells is found in the photosynthetic system, particularly the thylakoid, and the pigment chlorophyll. While there are challenges in consistently synthesizing these remarkable nanoparticles derived from nature, this exploration begins to unveil the endless possibilities in nanoarchitectonics research.

We have highlighted the Cell-derived Nanomaterials for Biomedical Applications through the lenses of our team who have experiences with working on cell membrane, thylakoids, and studying the impact of nanoparticles on biological phenomenon such as nanomaterialsinduced endothelial leakiness (NanoEL). In this review, we have discussed the progress and the wide potential of nanoarchitectonics in plant systems, animal cells and microorganisms. Due to our unique backgrounds, our take on this topic may be the novelty of the review.

Interaction of vascular endothelial cells with hydrophilic fullerene nanoarchitectured structures in 2D and 3D environments.

The interaction between diverse nanoarchitectured fullerenes and cells is crucial for biomedical applications. Here, we detailed the preparation of hydrophilic self-assembled fullerenes by the liquid-liquid interfacial precipitation (LLIP) method and hydrophilic coating of the materials as a possible vascularization strategy. The interactions of vascular endothelial cells (ECs) with hydrophilic fullerene nanotubes (FNT-P) and hydrophilic fullerene nanowhiskers (FNW-P) were investigated. The average length and diameter of FNT-P were 16 ± 2 µm and 3.4 ± 0.4 µm (i.e. aspect ratios of 4.6), respectively. The average length and diameter of FNW-P were 65 ± 8 µm and 1.2 ± 0.2 µm (i.e. aspect ratios of 53.9), respectively. For two-dimensional (2D) culture after 7 days, the ECs remained viable and proliferated up to ~ 420% and ~ 400% with FNT-P and FNW-P of 50 µg/mL, respectively. Furthermore, an optimized chitosan-based self-healing hydrogel with a modulus of ~400 Pa was developed and used to incorporate self-assembled fullerenes as in vitro three-dimensional (3D) platforms to investigate the impact of FNT-P and FNW-P on ECs within a 3D environment. The addition of FNW-P or FNT-P (50 µg/mL) in the hydrogel system led to proliferation rates of ECs up to ~323% and ~280%, respectively, after 7 days of culture. The ECs in FNW-P hydrogel displayed an elongated shape with aligned morphology, while those in FNT-P hydrogel exhibited a rounded and clustered distribution. Vascular-related gene expressions of ECs were significantly upregulated through interactions with these fullerenes. Thus, the combined use of different nanoarchitectured self-assembled fullerenes and self-healing hydrogels may offer environmental cues influencing EC development in a 3D biomimetic microenvironment, holding promise for advancing vascularization strategy in tissue engineering.

Self-assembled fullerenes with large aspect ratios modulate the morphology and gene expression of endothelial cells within a soft biomimetic 3D microenvironment, representing a promising new vascularization strategy in tissue engineering.

Mild selective photochemical oxidation of an organic sulfide using OxP-polyimide porous polymers as singlet oxygen generators.

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g-1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Oxoporphyrinogen (OxP) is a unique chromophore compound in that it is intrinsically de-aggregated allowing large quantum yields of singlet oxygen generation. Due to its structure, OxP is also an ideal building block for porous systems. In this work, we describe the first incorporation of OxP in highly stable microporous polymers strongly enhanced singlet oxygen generation for selective oxidation of organic sulfides to sulfoxides (as a model reaction) under heterogeneous conditions. The novelty of this work lies in the high stability and easy recovery of the materials, the synergetic enhancement of singlet oxygen generation in the polymers over the starting OxP, and the excellent selectivity for the oxidation reaction.

Liquid-Liquid and Liquid-Solid Interfacial Nanoarchitectonics.

Nanoscale science is becoming increasingly important and prominent, and further development will necessitate integration with other material chemistries. In other words, it involves the construction of a methodology to build up materials based on nanoscale knowledge. This is also the beginning of the concept of post-nanotechnology. This role belongs to nanoarchitectonics, which has been rapidly developing in recent years. However, the scope of application of nanoarchitectonics is wide, and it is somewhat difficult to compile everything. Therefore, this review article will introduce the concepts of liquid and interface, which are the keywords for the organization of functional material systems in biological systems. The target interfaces are liquid-liquid interface, liquid-solid interface, and so on. Recent examples are summarized under the categories of molecular assembly, metal-organic framework and covalent organic framework, and living cell. In addition, the latest research on the liquid interfacial nanoarchitectonics of organic semiconductor film is also discussed. The final conclusive section summarizes these features and discusses the necessary components for the development of liquid interfacial nanoarchitectonics.

Liquid-Liquid Interfacial Nanoarchitectonics.

Science in the small world has become a crucial key that has the potential to revolutionize materials technology. This trend is embodied in the postnanotechnology concept of nanoarchitectonics. The goal of nanoarchitectonics is to create bio-like functional structures, in which self-organized and hierarchical structures are working efficiently. Liquid-liquid interface like environments such as cell membrane surface are indispensable for the expression of biological functions through the accumulation and organization of functional materials. From this viewpoint, it is necessary to reconsider the liquid-liquid interface as a medium where nanoarchitectonics can play an active role. In this review, liquid-liquid interfacial nanoarchitectonics is classified by component materials such as organic, inorganic, carbon, and bio, and recent research examples are discussed. Examples discussed in this paper include molecular aggregates, supramolecular polymers, conductive polymers film, crystal-like capsules, block copolymer assemblies, covalent organic framework (COF) films, complex crystals, inorganic nanosheets, colloidosomes, fullerene assemblies, all-carbon π-conjugated graphite nanosheets, carbon nanoskins and fullerphene thin films at liquid-liquid interfaces. Furthermore, at the liquid-liquid interface using perfluorocarbons and aqueous phases, cell differentiation controls are discussed with the self-assembled structure of biomaterials. The significance of liquid-liquid interfacial nanoarchitectonics in the future development of materials will then be discussed.

Two-Dimensional Nanoarchitectonics for Two-Dimensional Materials: Interfacial Engineering of Transition-Metal Dichalcogenides.

Transition-metal dichalcogenides (TMDs) have attracted increasing attention in fundamental studies and technological applications owing to their atomically thin thickness, expanded interlayer distance, motif band gap, and phase-transition ability. Even though TMDs have a wide variety of material assets from semiconductor to semimetallic to metallic, the materials with fixed features may not show excellence for precise application. As a result of exclusive crystalline polymorphs, physical and chemical assets of TMDs can be efficiently modified via various approaches of interface nanoarchitectonics, including heteroatom doping, heterostructure, phase engineering, reducing size, alloying, and hybridization. With modified properties, TMDs become interesting materials in diverse fields, including catalysis, energy, electronics, transistors, and optoelectronics.

Field-effect transistors engineered via solution-based layer-by-layer nanoarchitectonics.

The layer-by-layer (LbL) technique has been proven to be one of the most versatile approaches in order to fabricate functional nanofilms. The use of simple and inexpensive procedures as well as the possibility to incorporate a very wide range of materials through different interactions have driven its application in a wide range of fields. On the other hand, field-effect transistors (FETs) are certainly among the most important elements in electronics. The ability to modulate the flowing current between a source and a drain electrode via the voltage applied to the gate electrode endow these devices to switch or amplify electronic signals, being vital in all of our everyday electronic devices. In this topical review, we highlight different research efforts to engineer field-effect transistors using the LbL assembly approach. We firstly discuss on the engineering of the channel material of transistors via the LbL technique. Next, the deposition of dielectric materials through this approach is reviewed, allowing the development of high-performance electronic components. Finally, the application of the LbL approach to fabricate FETs-based biosensing devices is also discussed, as well as the improvement of the transistor's interfacial sensitivity by the engineering of the semiconductor with polyelectrolyte multilayers.

Chemical Characterization of Corydalis chaerophylla D.C. Extracts and Preliminary Evaluation of Their in Vitro and in Vivo Biological Properties.

Genus Corydalis is a rich source of isoquinoline alkaloids reported to having potential bioactivities. Corydalis chaerophylla collected from Nepal at an altitude of 2400-4800 m was extracted using hexane, methanol and chloroform as solvents. The resulting hexane, methanol and chloroform extracts were subjected to LC-DAD-MSn analysis to yield fifteen different alkaloids. To assess any potential pharmacological properties, antimicrobial activity against two Gram-positive, two Gram-negative bacterial strains and one fungal strain was assessed, revealing significant inhibitive action of the methanol and chloroform extracts. Of the extracts obtained using chloroform contained the highest content of phenolic compounds at 113 mg GAE/g, while the highest total flavonoid content was found for the hexane extract with a value of 46.45 mg QE/g. The chloroform extract also exhibited a considerable antioxidant activity at IC50 value, 261.5±3 µg/mL, for the DPPH assay. Conversely, the methanol extract exhibited the highest LC50 value for Brine Shrimp cytotoxicity at 196±3 µg/mL being least potential for the test. The methanol extract was found to be the most active against α-amylase inhibition with an IC50 of 51.52±2 µg/mL. In an in vivo acute oral toxicity study against mice, methanol and chloroform extracts presented harmful effects with 1000.36 mg/kg BW and 515 mg/kg BW for LD50 , respectively. By analyzing all the results of the solvents used, the chloroform extract was found to be the most active, a feature that will be used in future isolation procedures and other pharmacological tests.

Materials Space-Tectonics: Atomic-level Compositional and Spatial Control Methodologies for Synthesis of Future Materials.

Reactions occurring at surfaces and interfaces necessitate the creation of well-designed surface and interfacial structures. To achieve a combination of bulk material (i.e., framework) and void spaces, a meticulous process of "nano-architecting" of the available space is necessary. Conventional porous materials such as mesoporous silica, zeolites, and metal-organic frameworks lack advanced cooperative functionalities owing to their largely monotonous pore geometries and limited conductivities. To overcome these limitations and develop functional structures with surface-specific functions, the novel materials space-tectonics methodology has been proposed for future materials synthesis. This review summarizes recent examples of materials synthesis based on designing building blocks (i.e., tectons) and their hybridization, along with practical guidelines for implementing materials syntheses and state-of-the-art examples of practical applications. Lastly, the potential integration of materials space-tectonics with emerging technologies, such as materials informatics, is discussed.

Photosensitizer Encryption with Aggregation Enhanced Singlet Oxygen Production.

Chromophores that generate singlet oxygen (1O2) in water are essential to developing noninvasive disease treatments using photodynamic therapy (PDT). A facile approach for formation of stable colloidal nanoparticles of 1O2 photosensitizers, which exhibit aggregation enhanced 1O2 generation in water toward applications as PDT agents, is reported. Chromophore encryption within a fuchsonarene macrocyclic scaffold insulates the photosensitizer from aggregation induced deactivation pathways, enabling a higher chromophore density than typical 1O2 generating nanoparticles. Aggregation enhanced 1O2 generation in water is observed, and variation in molecular structure allows for regulation of the physical properties of the nanoparticles which ultimately affects the 1O2 generation. In vitro activity and the ability of the particles to pass through the cell membrane into the cytoplasm is demonstrated using confocal fluorescence microscopy with HeLa cells. Photosensitizer encryption in rigid macrocycles, such as fuchsonarenes, offers new prospects for the production of biocompatible nanoarchitectures for applications involving 1O2 generation.

Mechanical Tuning of Aggregated States for Conformation Control of Cyclized Binaphthyl at the Air-Water Interface.

An air-water interface enables molecular assemblies and conformations to be controlled according to their intrinsic interactions and anisotropic stimuli. The chirality and conformation of binaphthyl derivatives have been controlled by tuning molecular aggregated states in solution. In this study, we have tuned molecular aggregated states of monobinaphthyldurene (MBD) by applying different mechanical stimuli to control the conformation at the air-water interface. Density functional theory calculations indicate that MBD exists essentially in two conformations, namely, 1-MBD (most stable) and 2-MBD (less stable). MBD was mechanically dissolved in appropriate lipid matrices using the Langmuir-Blodgett (LB) method, while pure MBD was self-assembled at the dynamic air-water interface in the absence of or by applying vortex motions (vortex LB method). In MBD mixed monolayer, surface pressure-molecular area measurements and atomic force microscopy observations suggest that separate lipids and MBD phases transform to mixed phases induced by the dissolution of MBD into the lipid matrices during mechanical compression at the air-water interface. Circular dichroism measurements indicate that molecular conformation changes from 1-MBD to 2-MBD in passing from a separated phase to a mixed MBD/lipid phase. In addition, the molecular aggregated states and conformations of MBD depend on the spreading volume and vortex flow rate when applying the vortex LB method. Molecular conformations and aggregated states of MBD could be controlled continuously by applying a mechanical stimulus at the air-water interface.

Hyper 100 °C Langmuir-Blodgett (Langmuir-Schaefer) Technique for Organized Ultrathin Film of Polymeric Semiconductors.

In this study, we advanced the conventional Langmuir-Blodgett (LB) method to a high-temperature range (above 100 °C) using a newly manufactured LB machine, which is adaptable to a high-boiling-point subphase, as a universally usable apparatus. A sophisticated trough design, with homogeneous heating capability up to approximately 200 °C, together with automatic film compression and Langmuir-Schaefer type film transfer, enabled the fabrication of highly aligned thin films of polymeric semiconductors with uniaxial alignment of polymer backbones, which is desirable for efficient charge transport. Herein, ultrathin films of semicrystalline thiophene-based semiconductors were prepared on ethylene glycol and heated to 80 °C. The analyses of the transferred films with pressure-area isotherms, atomic force microscopy (AFM), polarized optical microscopy (POM), and grazing-incidence wide-angle X-ray scattering (GIWAXS) indicated that the proposed high-temperature LB method allows ideal deposition of high-quality ultrathin films with molecular layer precision at the selected high-temperature conditions. Furthermore, preparing thin-film donor-acceptor-type copolymers in ionic liquids at high temperatures (up to 140 °C) was a challenging task that was successfully demonstrated in this study. Highly ordered thin films of donor-acceptor polymers with a uniaxial backbone orientation were obtained only at 140 °C. The obtained semicrystalline thin films with uniaxially aligned polymer backbones significantly contribute to the two-dimensional overlap of molecular orbitals, which is likely to promote charge transport. The use of the manufactured automatic LB machines is advantageous for better quality films prepared at higher temperatures (even above 100 °C) from various technical viewpoints, including homogeneous heating, constant compression, and automatic film transfer. The novel methodology proposed herein expands the possibilities of the Hyper 100 °C Langmuir-Blodgett technique, which has not been accessible by the conventional LB method with the aqueous subphase.

There is still plenty of room for layer-by-layer assembly for constructing nanoarchitectonics-based materials and devices.

Nanoarchitectonics approaches can produce functional materials from tiny units through combination of various processes including atom/molecular manipulation, chemical conversion, self-assembly/self-organization, microfabrication, and bio-inspired procedures. Existing fabrication approaches can be regarded as fitting into the same concept. In particular, the so-called layer-by-layer (LbL) assembly method has huge potential for preparing applicable materials with a great variety of assembling mechanisms. LbL assembly is a multistep process where different components can be organized in planned sequences while simple alignment options provide access to superstructures, for example helical structures, and anisotropies which are important aspects of nanoarchitectonics. In this article, newly-featured examples are extracted from the literature on LbL assembly discussing trends for composite functional materials according to (i) principles and techniques, (ii) composite materials, and (iii) applications. We present our opinion on the present trends, and the prospects of LbL assembly. While this method has already reached a certain maturity, there is still plenty of room for expanding its usefulness for the fabrication of nanoarchitectonics-based materials and devices.

Evaluation of the effects of natural isoquinoline alkaloids on low density lipoprotein receptor (LDLR) and proprotein convertase subtilisin/kexin type 9 (PCSK9) in hepatocytes, as new potential hypocholesterolemic agents.

Nine different isoquinoline alkaloids, berberine, govaniadine, stylopine, adlumine, adlumidine, bicuculline, sanguinarine, protopine and californidine have been evaluated for their effects on a cellular model of hepatocyte for their effect on low density lipoprotein receptor (LDLR) and proprotein convertase subtilisin/kexin type 9 (PCSK9) expression compared to simvastatin. Berberine, californidine and govaniadine induced LDLR with an effect similar to 2.5 µM simvastatin. Californidine and berberine at tested doses reduced the expression of PCSK9, with an opposite behaviour to simvastatin on this target. Govaniadine, on the other hand, showed a statin-like effect, although less potently, by increasing both LDLR and PCSK9 levels. Berberine californidine and govaniadine were then tested on the same cellular model to assess possible effect of reduction of total cholesterol, compared to simvastatin. All compounds were able to reduce total cholesterol level in the hepatocytes.