Successful Assembly Research Articles

Total synthesis of (−)-haploscleridamine

Asymmetric total synthesis of the imidazole containing β-carboline natural product, haploscleridamine, from histidine is described. Key to the successful assembly of this alkaloid is a ring-closing metathesis reaction of an imidazole derived allylic alcohol to construct a 3-piperidinone. Application of the Buchwald-modification of the classical Fischer indolization and deprotection of the N-tosyl moiety delivered haploscleridamine.

Assembly and Characterization of HBc Derived Virus-like Particles with Magnetic Core.

Core-virus like particles (VLPs) assembly is a kinetically complex cascade of interactions between viral proteins, nanoparticle’s surface and an ionic environment. Despite many in silico simulations regarding this process, there is still a lack of experimental data. The main goal of this study was to investigate the capsid protein of hepatitis B virus (HBc) assembly into virus-like particles with superparamagnetic iron oxide nanoparticles (SPIONs) as a magnetic core in relation to their characteristics. The native form of HBc was obtained via agroinfection of Nicotiana benthamiana with pEAQ-HBc plasmid. SPIONs of diameter of 15 nm were synthesized and functionalized with two ligands, providing variety in ζ-potential and hydrodynamic diameter. The antigenic potential of the assembled core-VLPs was assessed with enzyme-linked immunosorbent assay (ELISA). Morphology of SPIONs and core-VLPs was evaluated via transmission electron microscopy (TEM). The most successful core-VLPs assembly was obtained for SPIONs functionalized with dihexadecyl phosphate (DHP) at SPIONs/HBc ratio of 0.2/0.05 mg/mL. ELISA results indicate significant decrease of antigenicity concomitant with core-VLPs assembly. In summary, this study provides an experimental assessment of the crucial parameters guiding SPION-HBc VLPs assembly and evaluates the antigenicity of the obtained structures.

Improved reductive transformation of iopromide by magnetite containing reduced graphene oxide nanosacks as electron shuttles

The novel application of magnetite containing reduced graphene oxide nanosacks (MrGO-N) as electron shuttles to improve the reductive degradation of the pharmaceutical pollutant, iopromide (IOP), was evaluated. MrGO-N were synthesized by ultrasonicated nebulization process, and their physicochemical characterization was performed by potentiometric titrations, zeta potential, high resolution transmission electron microscopy (HR-TEM), X-ray diffraction, as well as by Raman and Fourier transform infrared spectroscopies. Results demonstrated the thermal reduction of precursor graphene oxide sheets, the removal of different oxygenated groups, and the successful assembly of magnetite nanoparticles (MNP) in the graphene sacks. Also, reduction experiments revealed 72% of IOP removal efficiency and up to 2.5-fold faster degradation of this pollutant performed with MrGO-N as redox catalysts in batch assays and with sulfide as electron donor. Chemical transformation pathway of IOP provides evidence of complete dehalogenation and further transformation of aromatic ring substituents. Greater redox-mediating ability of MrGO-N was observed, which was reflected in the catalytic activity of these nanomaterials during the reductive degradation of IOP. Transformation byproducts with simpler chemical structure were identified, which could lead to complete degradation by conventional methodologies in a complementary treatment process. Redox-mediating activity of MrGO-N could potentially be applied in wastewater treatment systems in order to facilitate the biodegradation of priority contaminants.

Supramolecular nanocatalyst in water: successive click-driven assembly of click-derived rod amphiphiles

An aqueous supramolecular nanocatalyst with interfacial curvature controlled by a click reaction was developed based on the self-assembly of a rod amphiphile containing a triazole moiety that chelates CuI ions for successive and efficient click-to-click reactions.

Engineering Antibodies with C-Terminal Sortase-Mediated Modification for Targeted Nanomedicine.

The current advances in nanoengineered materials coupled with the precise targeting capability of recombinant antibodies can create nanoscale diagnostics and therapeutics which show enhanced accumulation and extended retention at a target tissue. Smaller antibodies such as single-chain variable fragments (scFv) preserve the selective and strong binding of their parent antibody to their antigen with the benefits of low immunogenicity, more efficient tissue penetration and easy introduction of functional residues suitable for site-specific conjugation. This is of high importance as nonspecific antibody modification often involves attachment to free cysteine or lysine amino acids which may reside in the active site, leading to reduced antigen binding.In this chapter, we outline a facile and versatile chemoenzymatic approach for production of targeted nanocarrier scFv conjugates using the bacterial trans-peptidase Sortase A (Srt A). Srt A efficiently mediates sequence-specific peptide ligation under mild conditions and has few undesirable side reactions. We first describe the production, purification and characterization of Srt A enzyme and a scFv construct which targets activated platelets, called scFvanti-GPIIb/IIIa. Following this, our protocol illustrates the chemoenzymatic modification of the antibody at the C-terminus with an orthogonal click chemistry linker. This avoids any random attachment to the biologically active antigen binding site of the antibody. Finally, we describe the modification of a nanoparticle surface with scFv attachment via two methods: (1) direct Sortase-mediated conjugation; or (2) a two-step system which consists of scFv Sortase-mediated conjugation followed by strain promoted azide-alkyne cycloaddition. Finally, methodology is described to assess the successful assembly of targeted particles.

Continuous assembly of supramolecular polyamine-phosphate networks on surfaces: preparation and permeability properties of nanofilms.

Supramolecular self-assembly of molecular building blocks represents a powerful "nanoarchitectonic" tool to create new functional materials with molecular-level feature control. Here, we propose a simple method to create tunable phosphate/polyamine-based films on surfaces by successive assembly of poly(allylamine hydrochloride) (PAH)/phosphate anions (Pi) supramolecular networks. The growth of the films showed a great linearity and regularity with the number of steps. The coating thickness can be easily modulated by the bulk concentration of PAH and the deposition cycles. The PAH/Pi networks showed chemical stability between pH 4 and 10. The transport properties of the surface assemblies formed from different deposition cycles were evaluated electrochemically by using different redox probes in aqueous solution. The results revealed that either highly permeable films or efficient anion transport selectivity can be created by simply varying the concentration of PAH. This experimental evidence indicates that this new strategy of supramolecular self-assembly can be useful for the rational construction of single polyelectrolyte nanoarchitectures with multiple functionalities.

PH-Responsive polymeric nanocarriers for efficient killing of cariogenic bacteria in biofilms.

Traditional antibacterial treatments, such as chlorhexidine (CHX), destroy cariogenic biofilms. However, they exert negative effects in clinical applications, for example, teeth staining, taste disturbance and harm to oral tissue after a long-term exposure. Therefore, biocompatible strategies for efficient antibacterial drug delivery are in high demand. In this study, aimed at dental caries therapy enhancement, we designed a pH-responsive nanocarrier system, capable of releasing CHX in an acidic environment within cariogenic biofilms. Cationic poly(ethylene glycol)-block-poly(2-(((2-aminoethyl)carbamoyl)oxy)ethyl methacrylate) (PEG-b-PAECOEMA) was synthesized first. Modification of PAECOEMA by citraconic anhydride (CA) forms negatively charged PEG-b-PAECOEMA/CA, which could assemble into core-shell polyionic complex micelles (PICMs) when mixed with cationic CHX via electrostatic interactions. PICMs are stable in healthy neutral oral microenvironments with CHX encapsulated in the core and PEG shell exposed. Once in acidic milieu within caries-producing biofilms, they rapidly disassemble and release CHX cargo owing to degradation of citraconic amide groups. Molecular structures of the above copolymers were confirmed using 1H NMR and gel permeation chromatography (GPC) analysis. The pH-dependent degradation rates of citraconic amide in PEG-b-PAECOEMA/CA copolymer were measured by fluorescamine method. Atomic force microscopy (AFM) studies confirmed successful assembly of well-defined spherical PICMs in aqueous solution. The disassembly of PICMs in acidic microenvironment was observed using dynamic light scattering (DLS). PICMs showed an obvious pH-dependent drug release profile when the pH changed from 7.4 to 5.5. More importantly, the micellar system could reduce drug toxicity of CHX and exhibited outstanding antibacterial capability in the biofilm of Streptococcus mutans. Micelles constructed from pH-sensitive PEG-b-PAECOEMA/CA are highly promising for dental caries therapy and provide guidelines for drug-delivery system design in other acidic pathologic systems.

Application of edible nanolaminate coatings with antimicrobial extract of Flourensia cernua to extend the shelf-life of tomato (Solanum lycopersicum L.) fruit

Edible coatings have potential to reduce postharvest losses of fruit such as tomato. In this study, the effects of nanolaminate coatings incorporated with extracts of Flourensia cernua, an endemic plant of the arid and semi-arid regions of Mexico, has been investigated. Ethanol extracts of F. cernua (FcE) were prepared and incorporated into polyelectrolyte solutions of alginate and chitosan. The nanolaminates were characterized by determining the zeta potential, contact angle and water vapor and oxygen permeabilities. Shelf-life analyses (20 °C for 15 d) were carried out with uncoated fruit (UCF), nanolaminate coating (NL) and nanolaminate coating with FcE (NL + FcE). Physicochemical analyses, gas exchange rates of O2 and CO2 and ethylene production, as well as microbiological analyses of treated fruit were measured. Zeta potential and contact angle measurements confirmed the successful assembly of successive nanolayers of alginate and chitosan, as well as those with F. cernua. The nanolaminate coatings resulted in decreased permeabilities to water and O2. The best treatment of NL + FcE, extended the shelf-life of fruit by reducing weight loss and microbial growth, reducing gas exchange and ethylene production, and maintaining firmness and color. The NL + FcE treatment are an alternative to extend the shelf-life of tomato fruit.

Amplified MicroRNA Detection and Intracellular Imaging Based on an Autonomous and Catalytic Assembly of DNAzyme.

Abnormal microRNAs (miRNAs) expression is demonstrated to associate with various important biological processes, including tumorigenesis, metastasis, and progression. Given the low miRNA expression at the earlier stage of diseases, its amplified detection still requires more efforts. Inspired by the two-stage arithmetic amplifier of electric devices, we reported an autonomous and catalytic assembly of DNAzyme strategy by integrating a DNAzyme biocatalyst and catalytic hairpin assembly (CHA) circuit. Here the catalytically inactive DNAzyme subunits were respectively grafted into these metastable CHA hairpin reactants that were kinetically impeded without false cross-hybridizations. The target catalyzed the nonenzymatic CHA-mediated successive assembly of dumbbell-like bis-DNAzyme nanostructures, leading to the efficient DNAzyme-mediated cleavage of fluorophore/quencher-modified substrate and to the generation of an amplified fluorescence signal. The present CHA-DNAzyme amplifier can be employed as a versatile and general sensing platform for analyzing other analytes (e.g., miRNA) by introducing a sensing module into the present system. Moreover, the homogeneous CHA-DNAzyme method could realize the sensitive intracellular miRNA imaging in living cells, which is attributed to the inherently synergistic amplification property between DNAzyme and CHA reactions. Given the attractive analytical features of the autonomous CHA-DNAzyme system, the present strategy shows great promise for analyzing additional different analytes in clinical research fields.

МОДЕЛИРОВАНИЕ ПРОСТРАНСТВЕННЫХ ДОПУСТИМЫХ ОТКЛОНЕНИЙ СБОРОЧНЫХ ЕДИНИЦ С ПОМОЩЬЮ БИКВАТЕРНИОНОВ

Dimensional deviations arising in mechanical assemblies result from the change in the shape, orientation or position of assembly geometrical elements. If these deviations occur between the mating surfaces of assembly components they affect the final result of the assembly. One of the main conditions of successful assembly and assemblability is accounting for these deviations as early as the design stage of assembly units. The purpose of the article is representation of the general approach for the formalized description of permissible spatial tolerances of assembly unit geometrical elements. The study employs mathematical modeling using the biquaternion theory. A new approach has been developed for formalized imaging of the fields of assembly unit geometrical tolerances using the mathematical apparatus of biquaternions. Configuration manifolds of orientation and position tolerances are built and classified. Biquaternions used to describe permissible spatial deviations of assembly unit geometric elements enable comprehensive description of these deviations and consideration of their correlation. The constructed configuration manifolds allow to take into account the permissible spatial tolerances of assembly units at the stage of geometric design.

Highly Electrically Conductive Three-Dimensional Ti3C2T x MXene/Reduced Graphene Oxide Hybrid Aerogels with Excellent Electromagnetic Interference Shielding Performances.

Two-dimensional transition-metal carbides/carbonitrides (MXenes) with both superb electrical conductivity and hydrophilicity are promising for fabricating multifunctional nanomaterials and nanocomposites. However, the construction of three-dimensional (3D) and lightweight MXene macroscopic assemblies with excellent electrical conductivity and mechanical performances has not been realized due to the weak gelation capability of MXene sheets. Herein, we demonstrate an efficient approach for constructing highly conductive 3D Ti3C2T x porous architectures by graphene oxide assisted hydrothermal assembly followed by directional freezing and freeze-drying. The resultant hybrid aerogels exhibit aligned cellular microstructure, in which the graphene sheets serve as the inner skeleton, while the compactly attached Ti3C2T x sheets present as shells of the cell walls. The porous and highly conductive architecture (up to 1085 S m-1) is highly efficient in endowing epoxy nanocomposite with a high electrical conductivity of 695.9 S m-1 and an outstanding electromagnetic interference (EMI)-shielding effectiveness of more than 50 dB in the X-band at a low Ti3C2T x content of 0.74 vol %, which are the best results for polymer nanocomposites with similar loadings of MXene so far. The successful assembly methodology of 3D and porous architectures of Ti3C2T x would greatly widen the practical applications of MXenes in the fields of EMI shielding, supercapacitors, and sensors.

IUPAC seeks Expressions of Intent to host 2025 General Assembly and World Chemistry Congress

Abstract In 2017, IUPAC completed a very successful General Assembly (GA) and World Chemistry Congress in São Paulo, Brazil. Council decided the 2021 WCC/GA will be held in Montréal, Canada 2021 and The Hague, Netherlands in 2023. In 2019, the IUPAC GA and Congress will be held in Paris, France and will celebrate IUPAC’s Centenary.

Multicompartmentalized Microreactors Containing Nuclei and Catalase-Loaded Liposomes.

Multicompartmentalized microreactors are considered as cell mimics with hierarchical structures inspired by mammalian cells. We report the successful assembly and encapsulation of purified nuclei from RAW 264.7 cells (pNuc) into alginate-based microreactors. We demonstrate the preserved function of nuclei within the microreactors for mRNA production. Further, we load catalase-loaded liposomes (Lcat) into the microreactors to break down hydrogen peroxide (H2O2) into oxygen and water. Assemblies containing both natural pNuc and synthetic Lcat show significantly higher mRNA production in the presence of H2O2 compared to microreactors without Lcat or no H2O2 present, suggesting a beneficial effect of the locally enzymatically produced oxygen for transcription. This novel type of microreactors, containing both natural and synthetic compartments, presents a substantial advancement from assemblies equipped with solely synthetic units and offers opportunities as hypoxia models or for cell-free protein synthesis.

A Family of $$\left\{ {{\text{Ni}}^{\text{II}}_{2} {\text{Ln}}^{\text{III}}_{2} } \right\}$$ Ni 2 II Ln 2 III Butterfly Complexes: Lanthanide Contraction Effect on the Structures Magnetic Properties

Reactions of lanthanide nitrate, nickel nitrate, and polyhydroxyl Schiff-base ligand 2-(((2-hydroxy-3-methoxyphenyl)methylene)amino)-2-(hydroxymethyl)-1,3-propanediol (H4L) gave rise to a family of butterfly heterotetranuclear 3d–4f clusters formulated as [Ln2Ni2(H2L)2(μ3-OCH3)2(CH3CN)2(NO3)4]·2CH3OH·2H2O [Ln = Pr (1), Sm (2), Eu (3), Tb (4), Er (5)]. Single-crystal X-ray diffraction (XRD) reveals these complexes crystallize in the monoclinic space group P21/c. Both Ln1 and its symmetric Ln1A are coordinated to nine oxygen atoms and consist of two ligands with the same coordination mode μ3.η1:η2:η1:η2:η1, two nitrate ions and one μ3-OCH3. The five heterotetranuclear $${\text{Ni}}^{\text{II}}_{2} {\text{Ln}}^{\text{III}}_{2}$$ complexes display a central planar butterfly topology. The vertices of the body positions of the butterfly are occupied by NiII ions in all five complexes, which have been characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analyses, powder X-ray diffraction and thermal gravimetric analyses. The magnetic properties of the complexes have been studied. The results show that complexes 1-3, and 5 exhibit antiferromagnetic exchange between the paramagnetic species, and 4 shows strong ferromagnetic interaction. We have shown the successful design and assembly of a new family of tetranuclear, dicationic, heterometallic $$\left\{ {{\text{Ni}}^{\text{II}}_{2} {\text{Ln}}^{\text{III}}_{2} } \right\}$$ complexes characterized by a butterfly-type topology. The results might be promoting the rational design and synthesis of 3d–4f molecule-base magnets materials with fascinating topologies and magnetic behaviours.

Graphene oxide/Fe3O4 nanorods composite: structural and Raman investigation

The emerging field of organic/inorganic nanocomposites has become the focus of considerable research in recent years. In particular, graphene coated with iron oxide nanostructures are widely required for various applications. In this work, we report the preparation of graphene oxide/magnetite GO/Fe3O4 nanocomposite via a simple hydrothermal method. Our experimental results obtained by transmission electron microscopy (TEM) reveal that well defined Fe3O4 nanorods (NRs), about 8-11 nm in diameter and 50-60 nm in length, were uniformly anchored on graphene oxide nanosheets. X-ray diffraction (XRD) confirms the successful assembly of Fe3O4 on to GO nanosheets. Thermo gravimetric analysis results(TGA) show a good thermal stability for the nanocomposite. Raman laser studies carried out at various laser powers and acquisition times show that all the samples undergo changes in intensities and peak positions which reflect the modification of the electronic structure and electron-phonon interactions.

Enhanced corrosion resistance and cytocompatibility of biomimetic hyaluronic acid functionalised silane coating on AZ31 Mg alloy for orthopaedic applications.

This paper reports the corrosion resistant and cytocompatible properties of the hyaluronic acid-silane coating on AZ31 Mg alloy. In this study, the osteoinductive properties of high molecular weight hyaluronic acid (HA, 1-4 MDa) and the corrosion protection of silane coatings were incorporated as a composite coating on biodegradable AZ31 Mg alloy for orthopaedic applications. The multi-step fabrication of coatings first involved dip coating of a passivated AZ31 Mg alloy with a methyltriethoxysilane-tetraethoxysilane sol-gel to deposit a dense, cross-linked and corrosion resistant silane coating (AZ31-MT). The second step was to create an amine-functionalised surface by treating coated alloy with 3-aminopropyl-triethoxy silane (AZ31-MT-A) which facilitated the immobilisation of HA via EDC-NHS coupling reactions at two different concentrations i.e 1 mg.ml-1 (AZ31-MT-A-HA1) and 2 mg.ml-1 (AZ31-MT-A-HA2). These coatings were characterised by Fourier transform infrared spectroscopy, atomic force microscopy and static contact angle measurements which confirmed the successful assembly of the full coatings onto AZ31 Mg alloy. The influence of HA-silane coating on the corrosion of Mg alloy was investigated by electrical impedance spectroscopy and long-term immersion studies measurements in HEPES buffered DMEM. The results showed an enhanced corrosion resistance of HA functionalised silane coated AZ31 substrate over the uncoated equivalent alloy. Furthermore, the cytocompatibility of MC3T3-E1 osteoblasts was evaluated on HA-coated AZ31-MT-A substrates by live-dead staining, quantification of total cellular DNA content, scanning electron microscope and alkaline phosphatase activity. The results showed HA concentration-dependent improvement of osteoblast cellular response in terms of enhanced cell adhesion, proliferation and differentiation. These findings hold great promise in employing such biomimetic multifunctional coatings to improve the corrosion resistance and cytocompatibility of biodegradable Mg-based alloy for orthopaedic applications.

Size-Dependent Orientational Dynamics of Brownian Nanorods.

Successful assembly of suspended nanoscale rod-like particles depends on fundamental phenomena controlling rotational and translational diffusion. Despite the significant developments in fluidic fabrication of nanostructured materials, the ability to quantify the dynamics in processing systems remains challenging. Here we demonstrate an experimental method for characterization of the orientation dynamics of nanorod suspensions in assembly flows using orientation relaxation. This relaxation, measured by birefringence and obtained after rapidly stopping the flow, is deconvoluted with an inverse Laplace transform to extract a length distribution of aligned nanorods. The methodology is illustrated using nanocelluloses as model systems, where the coupling of rotational diffusion coefficients to particle size distributions as well as flow-induced orientation mechanisms are elucidated.

Catalytic reduction of picric acid, nitrophenols and organic azo dyes via green synthesized plant supported Ag nanoparticles

A facile and single-step green synthesis of silver nanoparticles dispersed on taro (Colocasia esculenta) plant rhizome powder (TP) is reported here. In the current study, we describe for the first time, the successful adsorption-based assembly of the silver/taro power (Ag/TP) nanocomposites using the rhizome of taro as a stabilizing/supporting agent. The Ag/TP nanocomposites exhibited very high efficiency in the catalytic reduction of nitroarenes such as picric acid/trinitrophenol (TNP), 4-nitroaniline (4-NA), 4-nitrophenol (4-NP) and 2-nitrophenol (2-NP) to the corresponding amines. The prepared catalyst also showed a high activity in the catalytic reduction of organic azo dyes such as Methyl Orange (MO), Congo Red (CR), Methyl Red (MR) and Rhodamine B (RhB) by sodium borohydride (NaBH4). The morphology, structure and crystallite size of the prepared nanocomposites were evaluated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photo electron spectroscopy (XPS) and X-ray diffraction analysis (XRD). The calculated turnover frequency was 3.846 min−1 for 4-NP and 1.104 min−1 for 2-NP. However, the pseudo-first-order constant was 5.27 × 10−3 s−1 for 4-NP and 1.23 × 10−3 s−1 for 2-NP. The prepared Ag/TP catalyst was also tested for the reduction of a mixture of nitroarenes and dyes. Ag/TP catalyst emerged as a promising, easily recoverable and reusable, with at least in 5 successive reactions and stable for 3 days.

Self-Assembled Porphyrazine Nucleosides on DNA Templates: Highly Fluorescent Chromophore Arrays and Sizing Forensic Tandem Repeat Sequences.

The formation of chromophore arrays using a DNA templating approach leads to the creation of supramolecular assemblies, where the optical properties of the overall system can be fine‐tuned to a large extent. In particular, porphyrin derivatives have been shown to be versatile building blocks; mostly covalent chemistry was used for embedding the units into DNA strands. Self‐assembly of porphyrin modified nucleosides, on the other hand, has not been investigated as a simplified approach. We report on the synthesis of a magnesium(II) tetraaza porphine (MgTAP) coupled to deoxyuridine, and array formation on DNA templates which contain well‐defined oligo(dA) segments showing strong fluorescence enhancement which is significantly larger than that with a Zn‐porphyrin. The use of the deep‐eutectic solvent glycholine is essential for successful assembly formation. The system allows for sizing of short tandem repeat markers with multiple adenosines, thus the concept could be adaptable to in vitro forensic DNA profiling with a suitable set of different chromophores on all nucleosides.

Land assembly with taxes, not takings

ABSTRACTWe use a novel tax mechanism – ‘rejected offer reassessment’ (ROR) – in laboratory experiments to discourage seller holdout and facilitate land assembly. Under this mechanism, if a landowner rejects a developer’s offer, his taxable property value is reassessed to be equal to the rejected offer, increasing his taxes. We find that, relative to a control treatment, ROR discourages the magnitude of seller holdout (but not its frequency) and increases the rate of successful land assembly by almost 60%. It also increases the gains from trade by 22.1% relative to the control treatment, but the difference is not statistically significant.