Multifunctional Dy Complexes with Triphenylmethanolates: Structural Diversity, Luminescence, and Magnetic Relaxation.

The coordination environment of magneto-luminescent Dy-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (PhCO), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear -[Dy(OCPh)(THF)][BPh]·(2,6-MeCHN) (), -Dy(OCPh)(THF) (), -Dy(OCPh)(py) () and dinuclear [(PhCO)Dy(THF){(μ-Cl)Li(THF)}μ-Cl] () complexes where the Dy ion presents five- or six-coordinate geometries.

Influence of the Structure of Hydrothermal-Synthesized TiO Nanowires Formed by Annealing on the Photocatalytic Reduction of CO in HO Vapor.

The present study investigates the photocatalytic properties of hydrothermally synthesized TiO nanowires (NWs) for CO reduction in HO vapor. It has been demonstrated that TiO NWs, thermally treated at 500-700 °C, demonstrate an almost tenfold higher yield of products compared to the known commercial powder TiO P25. It has been found that the best material is a combination of anatase, TiO-B and rutile.

Giant ultrafast dichroism and birefringence with active nonlocal metasurfaces.

Switching of light polarization on the sub-picosecond timescale is a crucial functionality for applications in a variety of contexts, including telecommunications, biology and chemistry. The ability to control polarization at ultrafast speed would pave the way for the development of unprecedented free-space optical links and of novel techniques for probing dynamical processes in complex systems, as chiral molecules. Such high switching speeds can only be reached with an all-optical paradigm, i.

Impact of Hydroxyapatite on Gelatin/Oxidized Alginate 3D-Printed Cryogel Scaffolds.

Fabrication of scaffolds via 3D printing is a promising approach for tissue engineering. In this study, we combined 3D printing with cryogenic crosslinking to create biocompatible gelatin/oxidized alginate (Gel/OxAlg) scaffolds with large pore sizes, beneficial for bone tissue regeneration. To enhance the osteogenic effects and mechanical properties of these scaffolds, we evaluated the impact of hydroxyapatite (HAp) on the rheological characteristics of the 2.

TADF Blue Emitters with Balanced π-Conjugation─Design, Synthesis, Spectral Characterization, and a Model OLED with 8-(5-(-Butyl)-1,3,4-oxadiazol-2-yl)-,-bis(4-(-butyl)phenyl)dibenzo[,]furan-2-amine.

Blue organic light-emitting diodes (OLED) suffer from relatively short lifetimes and a comparatively low lighting efficiency. One of the approaches to improving their characteristics is the development of luminophores with the potential for thermally activated delayed fluorescence (TADF). Herein, a set of donor-spacer-acceptor compounds with potential for TADF are designed, synthesized, and computationally and spectroscopically characterized.

Luminescent Er based single molecule magnets with fluorinated alkoxide or aryloxide ligands.

We report the synthesis, structures, and magnetic and luminescence properties of a series of new mono- and dinuclear Er complexes derived from sterically demanding aryloxide and fluorinated alkoxide ligands: [4-Bu-2,6-(PhCH)CHO]Er(THF) (1), [(CF)CO]Er(MeSiOH) (2), [(CF)CO]Er[(MeSi)NH] (3), [(CF)CO]Er(CHCH) (4), [(CF)CO]Er(-MeNCHCH) (5) and {[Ph(CF)CO]Er(μ-OC(CF)Ph)} (6). In compounds 1, 2, and 4, the Er ion is four-coordinated and adopts a distorted trigonal pyramidal geometry, while in 3, 5, and 6, the coordination geometry of Er is impacted by the presence of several relatively short Er⋯F distances, making them rather 6-coordinated. All compounds behave as field-induced Single Molecule Magnets (SMMs) and exhibit an Er characteristic near infrared (NIR) emission associated with the I → I transition with a remarkably long lifetime going up to 73 μs, which makes them multifunctional luminescent SMMs.

Reasoning on Pore Terminology in 3D Bioprinting.

Terminology is pivotal for facilitating clear communication and minimizing ambiguity, especially in specialized fields such as chemistry. In materials science, a subset of chemistry, the term "pore" is traditionally linked to the International Union of Pure and Applied Chemistry (IUPAC) nomenclature, which categorizes pores into "micro", "meso", and "macro" based on size. However, applying this terminology in closely-related areas, such as 3D bioprinting, often leads to confusion owing to the lack of consensus on specific definitions and classifications tailored to each field.

Ultrasensitive Detection of PSA Using Antibodies in Crowding Polyelectrolyte Multilayers on a Silicon Nanowire Field-Effect Transistor.

Immunosensors based on field-effect transistors with nanowire channels (NWFETs) provide fast and real-time detection of a variety of biomarkers without the need for additional labels. The key feature of the developed immunosensor is the coating of silicon NWs with multilayers of polyelectrolytes (polyethylenimine (PEI) and polystyrene sulfonate (PSS)). By causing a macromolecular crowding effect, it ensures the "soft fixation" of the antibodies into the 3-D matrix of the oppositely charged layers.

The development of a clinical research educational training for community health workers using the joint task force for clinical trial competency framework.

The NYU Clinical & Translational Science Institute, in collaboration with a number of community-engaged initiatives, developed a training for community health workers (CHWs) to enhance health literacy about clinical research. This innovative research training provides CHWs with a basic level of competency in clinical research to convey the importance of research to communities and better advocate for their health needs. CHWs are an underutilized resource to engage diverse populations in clinical research.

Ca(II) and Yb(II) complexes featuring M(C≡C) structural motif: enforced proximity or genuine η -bonding?

Bis(carbazolide) complexes M[3,6-tBu -1,8-(RC≡C) Carb] (THF) (R=SiMe , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe ) ] (THF) with two molar equivalents of carbazoles. The complexes feature M(η -C≡C) structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution.

gem-Difluoroolefination of Amides.

A metal-free one-pot process for the gem-difluoroolefination of amides is described. The reaction is based on interaction of generated in situ α-chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine. The olefination involves nucleophile-assisted dephosphorylation and proceeds within one hour at low temperature.

Long-Lived Exciton Coherence in Mixed-Halide Perovskite Crystals.

Compositional engineering of the optical properties of hybrid organic-inorganic lead halide perovskites is crucial for the realization of efficient solar cells and light-emitting devices. We study the effect of band gap fluctuations on coherent exciton dynamics in a mixed FACsPbIBr perovskite crystal by using photon echo spectroscopy. We reveal a narrow homogeneous exciton line width of 16 μeV at a temperature of 1.

The Composite TiO-CuO Layers Formed by Electrophoretic Method for CO Gas Photoreduction.

This study demonstrates the ability to control the properties of TiO-CuO composite layers for photocatalytic applications by using a simple electrophoretic deposition method from isopropanol-based suspension. To obtain uniform layers with a controlled composition, the surfactant sodium lauryl sulfate was used, which influenced the electrophoretic mobility of the particles and the morphology of the deposited layers. The TiO-CuO composite layers with different CuO contents (1.

Multi-millijoule class, high repetition rate, Yb:CALYO regenerative amplifier with sub-130 fs pulses.

We demonstrate a high-energy, 1 kilohertz, Yb-based, femtosecond regenerative amplifier in a chirped pulse amplification (CPA) architecture by using a single disordered Yb:CALYO crystal, providing 125 fs pulses of 2.3 mJ energy per pulse at a central wavelength of 1039 nm. The amplified compressed pulses, with a spectral bandwidth of 13.

Synthesis and Anticancer Evaluation of Novel 7-Aza-Coumarine-3-Carboxamides.

Herein, we report the design and synthesis of novel 7-aza-coumarine-3-carboxamides via scaffold-hopping strategy and evaluation of their in vitro anticancer activity. Additionally, the improved non-catalytic synthesis of 7-azacoumarin-3-carboxylic acid is reported, which features water as the reaction medium and provides a convenient alternative to the known methods. The anticancer activity of the most potent 7-aza-coumarine-3-carboxamides against the HuTu 80 cell line is equal to that of reference Doxorubicin, while the selectivity towards the normal cell line is 9-14 fold higher.

Dual-Crosslinking of Gelatin-Based Hydrogels: Promising Compositions for a 3D Printed Organotypic Bone Model.

Gelatin-based hydrogels have emerged as a popular scaffold material for tissue engineering applications. The introduction of variable crosslinking methods has shown promise for fabricating stable cell-laden scaffolds. In this work, we examine promising composite biopolymer-based inks for extrusion-based 3D bioprinting, using a dual crosslinking approach.

Self-Assembling Enzymatic Nanocomplexes with Polypeptides and Low-Weight Organic Compounds: Preparation, Characterization, and Application of New Antibacterials.

The self-assembling of nanosized materials is a promising field for research and development. Multiple approaches are applied to obtain inorganic, organic and composite nanomaterials with different functionality. In the present work, self-assembling nanocomplexes (NCs) were prepared on the basis of enzymes and polypeptides followed by the investigation of the influence of low-molecular weight biologically active compounds on the properties of the NCs.

A self-powered ingestible wireless biosensing system for real-time in situ monitoring of gastrointestinal tract metabolites.

Information related to the diverse and dynamic metabolite composition of the small intestine is crucial for the diagnosis and treatment of various diseases. However, our current understanding of the physiochemical dynamics of metabolic processes within the small intestine is limited due to the lack of in situ access to the intestinal environment. Here, we report a demonstration of a battery-free ingestible biosensing system for monitoring metabolites in the small intestine.

Single-Step Process for Titanium Surface Micro- and Nano-Structuring and In Situ Silver Nanoparticles Formation by Ultra-Short Laser Patterning.

Ultra-short laser (USL)-induced surface structuring combined with nanoparticles synthesis by multiphoton photoreduction represents a novel single-step approach for commercially pure titanium (cp-Ti) surface enhancement. Such a combination leads to the formation of distinct topographical features covered by nanoparticles. The USL processing of cp-Ti in an aqueous solution of silver nitrate (AgNO) induces the formation of micron-sized spikes surmounted by silver nanoparticles (AgNPs).

-Heterocyclic Carbene-Coordinated M(II) (M = Yb, Sm, Ca) Bisamides: Expanding the Limits of Intermolecular Alkene Hydrophosphination.

A series of NHC-stabilized amido compounds (NHC)M[N(SiMe)] (M = Yb(II), Sm(II), Ca(II); = 1, 2) showed remarkable catalytic efficiency in addition of PhPH and PH to alkenes under mild conditions and low catalyst loading. The effect of σ-donor capacity of NHCs on catalytic activity in hydrophosphination of styrene with PhPH and PH was revealed. For the series of three-coordinate complexes , a tendency to increase the catalytic activity with growth of σ-donating strength of the carbene ligand was clearly demonstrated.

π-Carbazolyl supported bis(alkyl) complexes of Sc, Y and La for α-olefin polymerization and hydrogenation.

A series of new half-sandwich bis(alkyl) rare-earth metal complexes coordinated by a sterically demanding 1,3,6,8-tetra--butyl-carbazol-9-yl ligand [BuCarb]La(CHCH)(THF) (1-La), [BuCarb]Ln(-NMeCHCH) (Ln = Sc (2-Sc), Y (2-Y), La (2-La), [BuCarb]Ln(CHSiMe)(THF) (Ln = Sc (3-Sc), Y (3-Y)), were synthesized. 1-La, 2-La, and 2-Y were prepared by an alkane elimination protocol, while 2-Sc, 3-Sc, and 3-Y became accessible only when salt metathesis reactions of BuCarbK with RLn(THF)[BPh] were employed. X-ray analysis revealed that in all complexes the carbazolyl ligand exhibits π-coordination with metal ions.

Sc and Y bis(alkyl) complexes supported by bidentate and tridentate amidinate ligands. Synthesis, structure and catalytic activity in polymerization of isoprene and 1-heptene.

A series of bis(alkyl) complexes {(Bu)C[N(2,6-MeCH)]}Ln(CHSiMe)(THF) (Ln = Y, = 1 (1); Ln = Sc, = 1 (2)), {2-[PhP(O)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (3), {2-[PhP(NPh)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (4) coordinated by bidentate (N,N) and tridentate (N,N,O; N,N,N) amidinate ligands are synthesized using an alkane elimination approach. Yttrium complex 1 demonstrated a half-life of ∼2.5 days at room temperature in benzene-D6 (CD) solution, whereas scandium complexes proved to be much more stable (25 d (2), 30 d (3) and 42 d (4)).

2-Imino-2,3-dihydrobenzoxazole-a useful platform for designing rare- and alkaline earth complexes with variable di- and trianionic O,N,N, ligands.

The reactions of 2-imino-2,3-dihydrobenzoxazole LH with M[N(SiMe)](THF) (M = Yb and Ca) and Y(CHSiMe)(THF) proceed with the opening of the dihydrobenzoxazole ring and the elimination of HN(SiMe) or SiMe. Besides, in the case of Yb[N(SiMe)](THF), an electron transfer from Yb(II) to L takes place and Yb(III) complex 1 is coordinated by a dianionic phenolate ligand containing a pendant radical-anionic diazabutadiene fragment form. When LH is reacted with Ca[N(SiMe)](THF), C-H bond activation of a methyl fragment by imino nitrogen occurs and affords a dimeric calcium complex 2.

Using N-Heterocyclic Carbenes as Weak Equatorial Ligands to Design Single-Molecule Magnets: Zero-Field Slow Relaxation in Two Octahedral Dysprosium(III) Complexes.

We report the synthesis, structures, and magnetic investigations of two new octahedral dysprosium complexes, based on the original N-heterocyclic carbene (NHC) tridentate bis(phenoxide) ligand, of the respective formulas -[DyL(THF)Cl] () and -[DyL(THF)][BPh] (), where L = 1,3-bis(3,5-di--butyl-2-oxidophenyl)-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium chloride and THF = tetrahydrofuran. The short Dy-O distances in the axial direction in association with the weak donor ability of the NHC moiety provide a suitable environment for slow relaxation of magnetization, overcoming the previous single-molecule magnets based on NHC ligands.