Biomimetic nanoplatforms constructed from dialkylaminostyryl hetarene dyes and phospholipids exhibiting selective fluorescent response to specific proteins.

The present work explores the specificity of supramolecular assemblies comprising dialkylaminostyrylhetarene dye molecules incorporated into phosphatidylcholine (PC) or phosphatidylserine (PS) aggregates. In PS-based assemblies, the dyes demonstrate a concentration-dependent fluorescent response, distinguishing anionic proteins such as bovine serum albumin (BSA) and pepsin from lysozyme (LYZ) in aqueous solutions. Conversely, no significant response is observed when the dyes are incorporated into the well-organized bilayers of neutral PC.

Can Re cluster complexes be an efficient catalyst for hydrogen evolution reaction? Insights from experiments and computations.

To date, researchers in chase of economic cost-efficiency are faced with the problem of developing effective catalysts for water splitting without the use of platinoids. Herein, catalytic properties of hexanuclear rhenium cluster complexes are investigated in application to the hydrogen evolution reaction (HER). A paste composite electrode containing the cluster complexes was obtained, producing a current density of 10 mA cm at an extraordinarily low overpotential of 90 mV (RHE).

Increased endocytosis rate and enhanced lysosomal pathway of silica-coated superparamagnetic nanoparticles into M-HeLa cells compared with cultured primary motor neurons.

The unique properties of superparamagnetic iron oxide nanoparticles (SPIONs) enable their use as magnetic biosensors, targeted drug delivery, magnetothermia, magnetic resonance imaging, etc. Today, SPIONs are the only type of metal oxide nanoparticles approved for biomedical application. In this work, we analyzed the cellular response to the previously reported luminescent silica coated SPIONs of the two cell types: M-HeLa cells and primary motor neuron culture.

Expanding Mn loading capacity of BSA via mild non-thermal denaturing and cross-linking as a tool to maximize the relaxivity of water protons.

Development of nanoparticles (NPs) serving as contrast enhancing agents in MRI requires a combination of high contrasting effect with the biosafety and hemocompatibility. This work demonstrates that bovine serum albumin (BSA) molecules bound to paramagnetic Mn ions are promising building blocks of such NPs. The desolvation-induced denaturation of BSA bound with Mn ions followed by the glutaraldehyde-facilitated cross-linking provides the uniform in size 102.

Linkage of the Dinuclear Gold(I) Complex Luminescence and Origin of Endocyclic Amino Group of Cyclic PN-Bridging Ligands.

Gold(I) complexes of LAuCl composition based on PN ligands, namely 1,5-diaza-3,7-diphosphacyclooctanes, containing ethylpyridyl substituents at the phosphorus atoms and sp- or sp-hybridized endocyclic nitrogen atoms were synthesized. The SCXRD analysis indicated the strong impact of the geometry of the nitrogen atom on the structure and conformational flexibility of the complexes. The -aryl substituted ligand with the planar endocyclic nitrogen atom provides higher flexibility of the complex and an ability to bind the solvent molecules in the "host-guest" mode, whereas that kind of behavior is forbidden for the complex with an -alkyl substituted ligand with a pyramidal nitrogen atom.

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.

Manipulation of New Fluorescent Magnetic Nanoparticles with an Electromagnetic Needle, Allowed Determining the Viscosity of the Cytoplasm of M-HeLa Cells.

Magnetic nanoparticles (MNPs) have recently begun to be actively used in biomedicine applications, for example, for targeted drug delivery, in tissue engineering, and in magnetic resonance imaging. The study of the magnetic field effect on MNPs internalized into living cells is of particular importance since it allows a non-invasive influence on cellular activity. There is data stating the possibility to manipulate and control individual MNPs utilizing the local magnetic field gradient created by electromagnetic needles (EN).

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.

Supramolecular Optimization of Sensory Function of a Hemicurcuminoid through Its Incorporation into Phospholipid and Polymeric Polydiacetylenic Vesicles: Experimental and Computational Insight.

This work presents the synthesis of a new representative of hemicurcuminoids with a nonyloxy substituent () as a fluorescent amphiphilic structural element of vesicular aggregates based on phosphatidylcholine (PC), phosphatidylserine (PS), and 10,12-pentacosadiynoic acid (PCDA). Both X-ray diffraction analysis of the single crystal and H NMR spectra of in organic solvents indicate the predominance of the enol-tautomer of . DFT calculations show the predominance of the enol tautomer in supramolecular assemblies with PC, PS, and PCDA molecules.

Phosphineoxide-Chelated Europium(III) Nanoparticles for Ceftriaxone Detection.

The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and β-ketophosphine oxide representatives for efficient coordination of Tb and Eu ions with the formation of the complexes exhibiting high Tb- and Eu-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb and Eu ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes.

Non-Noble-Metal Mono and Bimetallic Composites for Efficient Electrocatalysis of Phosphine Oxide and Acetylene C-H/P-H Coupling under Mild Conditions.

The present work describes an efficient reaction of electrochemical phosphorylation of phenylacetylene controlled by the composition of catalytic nanoparticles based on non-noble-metals. The sought-after products are produced via the simple synthetic protocol based on room temperature, atom-economical reactions, and silica nanoparticles (SNs) loaded by one or two d-metal ions as nanocatalysts. The redox and catalytic properties of SNs can be tuned with a range of parameters, such as compositions of the bimetallic systems, their preparation method, and morphology.

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb-Luminescence via Upper-Rim Substitution.

The present work introduces the series of thiacalix[4]arenes (HL) bearing different upper-rim substituents (R = H, Br, NO) for rational design of ligands providing an antenna-effect on the NIR Yb-centered luminescence of their Yb complexes. The unusual inclusive self-assembly of HL (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb:2HL] leads to efficient sensitizing of the Yb luminescence for HL (Br, NO), while poor sensitizing is observed for ligand HL (H).

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.

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.

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.

1,3-Diketone Calix[4]arene Derivatives-A New Type of Versatile Ligands for Metal Complexes and Nanoparticles.

The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims.

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.

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.

Impact of oppositely charged shell and cores on interaction of core-shell colloids with differently charged proteins as a route for tuning of the colloids cytotoxicity.

The present work represents interactions between the core-shell nanoparticles and different proteins, exemplified by lysozyme (LSZ), pepsin, bovine serum albumin (BSA), thioredoxin (TRX) and yellow fluorescent protein (YFP). The core-shell morphology derives from the non-covalent deposition of polyethyleneimine (PEI) onto nanoprecipitated luminescent complex (AuCl)L (L is cyclic PNNP ligand). Analysis of the data obtained by DLS, CD spectroscopy, luminescence derived from both (AuCl)L and YFP reveal the electrostatically driven interaction of negatively charged proteins with the shell of PEI-(AuCl)L.

Correction: A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb complexes with thiacalix[4]arene derivatives through upper-rim bromination.

Correction for 'A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb3+ complexes with thiacalix[4]arene derivatives through upper-rim bromination' by Sergey N. Podyachev, et al., Dalton Trans.

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 simple synthetic approach to enhance the thermal luminescence sensitivity of Tb complexes with thiacalix[4]arene derivatives through upper-rim bromination.

The present work for the first time reports an application of the thiacalix[4]arene scaffold for the preparation of Tb3+ complexes possessing high thermal luminescence sensitivity in the physiological temperature range of 20-50 °C. Non-substituted thiacalix[4]arenes form luminescent complexes with Tb3+ ions, but they do not reveal any meaningful thermal sensitivity. To solve this problem, an upper-rim bromination of thiacalix[4]arenes, as well as distal bromination along with the embedding of two 1,3-diketone substituents are proposed as new simple synthetic approaches to enhance the thermal luminescence sensitivity of the Tb3+ complexes.