Specificity of hexarhenium cluster anions for synthesis of Mn-based nanoparticles with lamellar shape and pH-induced leaching for specific organ selectivity in MRI contrasting.

The present work demonstrates the structure variation of hexarhenium anionic cluster units [{ReS}(CN)(OH)] (n = 0, 2, 4) as the strategy to develop Mn-containing nanoparticles (NPs) exhibiting pH-dependent leaching. The dicyanotetrahydroxo complex [{ReS}(CN)(OH)] is the optimal for the synthesis of the Mn-based NPs with a lamellar shape exhibiting the pH-dependent aggregation and magnetic relaxation behavior. The pH-dependent behavior of the NPs derives from the easy protonation of the apical hydroxo ligands of [{ReS}(CN)(OH)] cluster, which triggers partial leaching of Mn ions and aggregation of the NPs driven by the surface neutralization.

ROS-producing nanomaterial engineered from Cu(I) complexes with PN-ligands for cancer cells treating.

The work presents core-shell nanoparticles (NPs) built from the novel Cu(I) complexes with cyclic PN-ligands (1,5-diaza-3,7-diphosphacyclooctanes) that can visualize their entry into cancer and normal cells using a luminescent signal and treat cells by self-enhancing generation of reactive oxygen species (ROS). Variation of P- and N-substituents in the series of PN-ligands allows structure optimization of the Cu(I) complexes for the formation of the luminescent NPs with high chemical stability. The non-covalent modification of the NPs with triblock copolymer F-127 provides their high colloidal stability, followed by efficient cell internalization of the NPs visualized by their blue (⁓450 nm) luminescence.

Carbonized Nickel Complex of Sodium Pectate as Catalyst for Proton-Exchange Membrane Fuel Cells.

Sodium pectate derivatives with 25% replacement of sodium ions with nickel ions were obtained by carbonization to temperatures of 280, 550, and 800 °C, under special protocols in an inert atmosphere by carbonization to temperatures of 280, 550, and 800 °C. The 25% substitution is the upper limit of substitution of sodium for nickel ions, above which the complexes are no longer soluble in water. It was established that the sample carburized to 550 °C is the most effective active element in the hydrogen-oxidation reaction, while the sample carbonized up to 800 °C was the most effective in the oxygen-reduction reaction.

Doping of Transparent Electrode Based on Oriented Networks of Nickel in Poly(3,4-Ethylenedioxythiophene) Polystyrene Sulfonate Matrix with P-Toluenesulfonic Acid.

This work aimed to obtain an optically transparent electrode based on the oriented nanonetworks of nickel in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. Optically transparent electrodes are used in many modern devices. Therefore, the search for new inexpensive and environmentally friendly materials for them remains an urgent task.

Covalent Functionalization of Black Phosphorus Nanosheets with Dichlorocarbenes for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

Two-dimensional black phosphorus (BP) has emerged as a perspective material for various micro- and opto-electronic, energy, catalytic, and biomedical applications. Chemical functionalization of black phosphorus nanosheets (BPNS) is an important pathway for the preparation of materials with improved ambient stability and enhanced physical properties. Currently, the covalent functionalization of BPNS with highly reactive intermediates, such as carbon-free radicals or nitrenes, has been widely implemented to modify the material's surface.

In-Situ Electrochemical Exfoliation and Methylation of Black Phosphorus into Functionalized Phosphorene Nanosheets.

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates.

Specific nanoarchitecture of silica nanoparticles codoped with the oppositely charged Mn and Ru complexes for dual paramagnetic-luminescent contrasting effects.

The silica nanoparticles (SNs) co-doped with paramagnetic ([Mn(HL)],) and luminescent ([Ru(dipy)]) complexes are represented. The specific distribution of [Mn(HL)] within the SNs allows to achieve about ten-fold enhancing in magnetic relaxivities in comparison with those of [Mn(HL)] in solutions. The leaching of [Mn(HL)] from the shell can be minimized through the co-doping of [Ru(dipy)] into the core of the SNs.

Thymine-Modified Nanocarrier for Doxorubicin Delivery in Glioblastoma Cells.

Brain tumor glioblastoma is one of the worst types of cancer. The blood-brain barrier prevents drugs from reaching brain cells and shields glioblastoma from treatment. The creation of nanocarriers to improve drug delivery and internalization effectiveness may be the solution to this issue.

Complexes of Sodium Pectate with Nickel for Hydrogen Oxidation and Oxygen Reduction in Proton-Exchange Membrane Fuel Cells.

A number of nickel complexes of sodium pectate with varied Ni content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates.

pH-Driven Intracellular Nano-to-Molecular Disassembly of Heterometallic [AuL]{ReQ} Colloids (L = PNNP Ligand; Q = S or Se).

The present work introduces a simple, electrostatically driven approach to engineered nanomaterial built from the highly cytotoxic [AuL] complex (Au, L = 1,5-bis(p-tolyl)-3,7-bis(pyridine-2-yl)-1,5-diaza-3,7-diphosphacyclooctane (PNNP) ligand) and the pH-sensitive red-emitting [{ReQ}(OH)] (Re-Q, Q = S or Se) cluster units. The protonation/deprotonation of the Re-Q unit is a prerequisite for the pH-triggered assembly of Au and Re-Q into AuRe-Q colloids, exhibiting disassembly in acidic (pH = 4.5) conditions modeling a lysosomal environment.

Molecular and Nano-Structural Optimization of Nanoparticulate Mn-Hexarhenium Cluster Complexes for Optimal Balance of High T- and T-Weighted Contrast Ability with Low Hemoagglutination and Cytotoxicity.

The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the μ (inner) ligands within a series of hexarhenium cluster complexes [{Re(μ-Q)}(CN)] (ReQ, Q = S, Se or Te) and interfacial decoration of the nanoparticles (NPs) KMnReQ ( = 1.3 - 1.8) by a series of pluronics (F-68, P-123, F-127).

Role of PSS-based assemblies in stabilization of Eu and Sm luminescent complexes and their thermoresponsive luminescence.

The present work introduces self-assembled polystyrenesulfonate (PSS) molecules as soft nanocapsules for incorporation of Eu-Sm complexes by the solvent exchange procedure. The high levels of Eu- and Sm-luminescence of the complexes derives from the ligand-to-metal energy transfer, in turn, resulted from the complex formation of Euand Sm ions with the three recently synthesized cyclophanic 1,3-diketones. The structural features of the ligands are optimized for the high thermal sensitivity of Eu- luminescence in DMF solutions.

Cationic Imidazolium Amphiphiles Bearing a Methoxyphenyl Fragment: Synthesis, Self-Assembly Behavior, and Antimicrobial Activity.

Novel cationic amphiphiles of the 3-alkyl-1-(4-methoxyphenyl)-1-imidazol-3-ium bromide series bearing methoxyphenyl fragments (MPI-) have been synthesized. Their aggregation properties in aqueous solutions, solubilization capacity, and hemolytic and antimicrobial activities have been investigated by a number of physicochemical methods. Using tensiometry, conductometry, and fluorescence spectroscopy, it was shown that the MPI- have lower CMCs than their nonfunctionalized counterparts.

Self-Assembling Metallocomplexes of the Amphiphilic 1,4-Diazabicyclo[2.2.2]octane Derivative as a Platform for the Development of Nonplatinum Anticancer Drugs.

New 1-cetyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide complexes with copper(II) bromide and lanthanum(III) nitrate were characterized using dynamic light scattering and transmission electron microscopy, with self-assembly and the morphological behavior elucidated.

Single Excited Dual Band Luminescent Hybrid Carbon Dots-Terbium Chelate Nanothermometer.

The report introduces hybrid polyelectrolyte-stabilized colloids combining blue and green-emitting building blocks, which are citrate carbon dots (CDs) and [TbL] chelate complexes with 1,3-diketonate derivatives of calix[4]arene. The joint incorporation of green and blue-emitting blocks into the polysodium polystyrenesulfonate (PSS) aggregates is carried out through the solvent-exchange synthetic technique. The coordinative binding between Tb centers and CD surface groups in initial DMF solutions both facilitates joint incorporation of [TbL] complexes and the CDs into the PSS-based nanobeads and affects fluorescence properties of [TbL] complexes and CDs, as well as their ability for temperature sensing.

Structure impact on photodynamic therapy and cellular contrasting functions of colloids constructed from dimeric Au(I) complex and hexamolybdenum clusters.

Electrostatically driven self-assembly of [AuL] (L is cyclic PNNP ligand) with [{MoI}(L')] (L' = I, CHCOO) in aqueous solutions is introduced as facile route for combination of therapeutic and cellular contrasting functions within heterometallic colloids (Mo-Au). The nature of L' affects the size and aggregation behavior of crystalline Mo-Au aggregates, which in turn affect the luminescence of the cluster units incorporated into Mo-Au colloids. The spin trap facilitated electron spin resonance spectroscopy technique indicates that the level of ROS generated by Mo-Au colloids is also affected by their size.

Cationic liposomes mediated transdermal delivery of meloxicam and ketoprofen: Optimization of the composition, in vitro and in vivo assessment of efficiency.

New liposomes modified with pyrrolidinium surfactants containing a hydroxyethyl fragment (CPB, n = 12, 14, 16) were prepared for transdermal delivery of non-steroidal anti-inflammatory drugs. In order to obtain the optimal composition, the surfactant/lipid molar ratio (0.02/1; 0.

Surface modification of silica nanoparticles by hexarhenium anionic cluster complexes for pH-sensing and staining of cell nuclei.

The surface deposition of luminescent anionic cluster complex [{ReS}(OH)] advantages to the design and synthesis of composite luminescent silica nanoparticles (SNs) for intracellular imaging and sensing, while the encapsulation of the cluster units into SNs lacks for efficient luminescence. The deposition of the Re clusters resulted from their assembly at the silica surface functionalized by amino-groups provides the synthetic route for the composite SNs with bright cluster-centered luminescence invariable in pH range from 4.0 to 12.

Oriented Nickel Nanonetworks and Their Submicron Fibres as a Basis for a Transparent Electrically Conductive Coating.

The paper demonstrates a technique for applying an oriented nickel network to a glass surface. The method is based on the chemical reduction of nickel salt. The shaping and orientation of the resulting system are carried out using a micellar template of a surfactant and a magnetic field.

Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303-313 K range.

The work introduces hydrophilic PSS-[Tb(TCAn)] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb(TCAn)] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim substituents: unsubstituted TCA1, tert-buthyl-substituted TCA2, di- and tetra-brominated TCA3 and TCA4) with the use of polystyrenesulfonate (PSS) as stabilizer. The temperature responsive luminescence behavior of PSS-[Tb(TCAn)] within 293-333 K range in water is modulated by reversible changes derived from the back energy transfer from metal to ligand (M* → T) correlating with the energy gap between the triplet levels of ligands and resonant D level of Tb ion.

Supraamphiphilic Systems Based on Metallosurfactant and Calix[4]resorcinol: Self-Assembly and Drug Delivery Potential.

Metallic amphiphiles are used as building blocks in the construction of nanoscale superstructures, where the hydrophobic effects induce the self-assembly of the nanoparticles of interest. However, the influence of synergizing multiple chemical interactions on an effective design of these structures mostly remains an open question. In this regard, supraamphiphilic systems based on flexible surfactant molecules and rigid macrocycles are being actively developed, but there are few works on the interaction between metallosurfactants and macrocycles.

ROS-generation and cellular uptake behavior of amino-silica nanoparticles arisen from their uploading by both iron-oxides and hexamolybdenum clusters.

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{MoI}I]) units within amino-decorated silica nanoparticles (SNs) as promising design of the hybrid SNs as efficient cellular contrast and therapeutic agents. The heating generated by SNs doped with SPIONs (FeO@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both FeO@SNs and "empty" silica nanoparticles (SNs) results in FeO@SNs[{MoI}I] and SNs[{MoI}I] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation.

Synthetic Tuning of Co-Doped Silica Nanoarchitecture Towards Electrochemical Sensing Ability.

The present work introduces both synthesis of silica nanoparticles doped with Co ions by means of differently modified microemulsion water-in-oil (w/o) and Stöber techniques and characterization of the hybrid nanoparticles (Co@SiO) by TEM, DLS, XRD, ICP-EOS, SAXS, UV-Vis, and UV-Vis/DR spectroscopy and electrochemical methods. The results reveal the lack of nanocrystalline dopants inside the hybrid nanoparticles, as well as no ligands, when Co ions are added to the synthetic mixtures as Co(bpy) complexes, thus pointing to coordination of Co ions with Si-O groups as main driving force of the doping. The UV-Vis/DR spectra of Co@SiO in the range of d-d transitions indicate that Stöber synthesis in greater extent than the w/o one stabilizes tetrahedral Co ions versus the octahedral ions.

A Glucose-Responsive Polymer Nanocarrier Based on Sulfonated Resorcinarene for Controlled Insulin Delivery.

A nanocarrier (p(6SRA-5B)) for glucose-controlled insulin delivery consists of sulfonated resorcinarenes (SRA) that are assembled into a spherical shell and are attached to each other with phenylboronate linkers. p(6SRA-5B) is stable in water and blood plasma at normal glucose concentrations. At high glucose levels (>5 mM), p(6SRA-5B) dissociates into SRA and phenylboronates through competitive interaction with excess glucose.