Fiber Integrated Metal-Organic Frameworks as Functional Components in Smart Textiles

Owing to high modularity and synthetic tunability, metal–organic frameworks (MOFs) on textiles are poised to contribute to the development of state-of-the-art wearable systems with multifunctional performance. While these composite materials have demonstrated promising functions in sensing, filtration, detoxification, and biomedicine, their applicability in multifunctional systems is only beginning to materialize. This review highlights the multifunctionality and versatility of MOF-integrated textile systems. It summarizes the operational goals of MOF@textile composites, encompassing sensing, filtration, detoxification, drug delivery, UV protection, and photocatalysis. Building upon these recent advances, this review concludes with an outlook on emerging opportunities for the diverse applications of MOF@textile systems in the realm of smart wearables.     

Strong Direct Magnetic Coupling in a Dinuclear CoII Tetrazine Radical Single‐Molecule Magnet

The ligand‐centered radical complex [(CoTPMA)₂‐μ‐bmtz^.?](O₃SCF₃)₃ ? CH₃CN (bmtz=3,6‐bis(2′‐pyrimidyl)‐1,2,4,5‐tetrazine, TPMA=tris‐(2‐pyridylmethyl)amine) has been synthesized from the neutral bmtz precursor. Single‐crystal X‐ray diffraction studies have confirmed the presence of the ligand‐centered radical. The Co^II complex exhibits slow paramagnetic relaxation in an applied DC field with a barrier to spin reversal of 39 K. This behavior is a result of strong antiferromagnetic metal–radical coupling combined with positive axial and strong rhombic anisotropic contributions from the Co^II ions.     

10‐Step Asymmetric Total Synthesis and Stereochemical Elucidation of (+)‐Dragmacidin D

The asymmetric synthesis of dragmacidin D ( 1 ) was completed in 10 steps. Its sole stereocenter was set by using direct asymmetric alkylation enabled by a C₂‐symmetric tetramine and lithium N‐(trimethylsilyl)‐tert‐butylamide as the enolization reagent. A central Larock indole synthesis was employed in a convergent assembly of the heterocyclic subunits. The stereochemical evidence from this work strongly supports the predicted S configuration at the 6′′′ position, which is consistent with other members of the dragmacidin family of natural products.     

Preliminary Study of a 1,5-Benzodiazepine-Derivative Labelled with Indium-111 for CCK-2 Receptor Targeting

The cholecystokinin-2 receptor (CCK-2R) is overexpressed in several human cancers but displays limited expression in normal tissues. For this reason, it is a suitable target for developing specific radiotracers. In this study, a nastorazepide-based ligand functionalized with a 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelator (IP-001) was synthesized and labelled with indium-111. The radiolabeling process yielded >95% with a molar activity of 10 MBq/nmol and a radiochemical purity of >98%. Stability studies have shown a remarkable resistance to degradation (>93%) within 120 h of incubation in human blood. The in vitro uptake of [¹¹¹In]In-IP-001 was assessed for up to 24 h on a high CCK-2R-expressing tumor cell line (A549) showing maximal accumulation after 4 h of incubation. Biodistribution and single photon emission tomography (SPECT)/CT imaging were evaluated on BALB/c nude mice bearing A549 xenograft tumors. Implanted tumors could be clearly visualized after only 4 h post injection (2.36 ± 0.26% ID/cc), although a high amount of radiotracer was also found in the liver, kidneys, and spleen (8.25 ± 2.21%, 6.99 ± 0.97%, and 3.88 ± 0.36% ID/cc, respectively). Clearance was slow by both hepatobiliary and renal excretion. Tumor retention persisted for up to 24 h, with the tumor to organs ratio increasing over-time and ending with a tumor uptake (1.52 ± 0.71% ID/cc) comparable to liver and kidneys.     

Controlling the Surface Functionalization of Ultrasmall Gold Nanoparticles by Sequence-Defined Macromolecules

Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by ¹H NMR spectroscopy, ¹H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative ¹H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm² per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.     

A Facile Route to Substituted Dimethoxy Phosphonothionates Using Dimethyl Thiophosphite

Dimethyl thiophosphite reacts with aliphatic aldehydes and ketones, Michael acceptors, and N-benzyl imines to afford excellent yields of f -hydroxy phosphonothionates, g -substituted phosphonothionates and f -amino phosphonothionates, respectively. Dealkylation of f -amino phosphonothionates affords N-benzyl f -amino phosphonothioic acids. Dimethyl thiophosphite reacts with electrophiles at a significantly greater rate than dimethyl phosphite.     

Observation of defect clustering in Gd-doped calcium fluoride

Abstract

Solid solutions Ca_1-xGd_xF_2+x for 3 × 10^?7≤ x ≤10^?1 have been studied by electron paramagnetic resonance (EPR) and ionic thermal currents (ITC). The EPR experiments show the presence of two single-ion sites a cubic and a tetragonal Gd³⁺ center which co-exist with comparable abundances for intermediate impurity concentrations. The cubic center predominates at very low and high concentrations. Seven different relaxation processes have been identified from the ITC spectra and the variation of their intensity vs. x was measured. The absolute concentrations of the cubic and nn Gd³⁺ dipoles were calculated. The scavenging of interstitial fluorines by the neutral clusters explains both the abundance of cubic sites at high concentration and the variety of orientable clusters detected by ITC.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

Franck-Condon Factors and R-Centroids for the B-X Transition of La18O and La16O,Including Rotation-Vibration Interaction

FRANCK-CONDON FACTORS AND R-CENTROIDS FOR THE GREEN-YELLOW SYSTEM OF LA¹⁶O AND LA¹⁸O ARE REPORTED. CALCULATION INCLUDES ROTATION-VIBRATION INTERACTION, AND A SIGNIFICANT VARIATION WHEN THE ROTATIONAL QUANTUM NUMBER CHANGES HAS BEEN FOUND.