Phosphonated Near‐Infrared Fluorophores for Biomedical Imaging of Bone

The conventional method for creating targeted contrast agents is to conjugate separate targeting and fluorophore domains. A new strategy is based on the incorporation of targeting moieties into the non‐delocalized structure of pentamethine and heptamethine indocyanines. Using the known affinity of phosphonates for bone minerals in a model system, two families of bifunctional molecules that target bone without requiring a traditional bisphosphonate are synthesized. With peak fluorescence emissions at approximately 700 or 800 nm, these molecules can be used for fluorescence‐assisted resection and exploration (FLARE) dual‐channel imaging. Longitudinal FLARE studies in mice demonstrate that phosphonated near‐infrared fluorophores remain stable in bone for over five weeks, and histological analysis confirms their incorporation into the bone matrix. Taken together, a new strategy for creating ultra‐compact, targeted near‐infrared fluorophores for various bioimaging applications is described.     

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Fusion of Different Crosslinked Polymers Based on Dynamic Disulfide Exchange

Crosslinked polymers (CLPs) exhibit exceptional mechanical properties as well as good chemical and solvent resistance. However, their reprocessing, recycling, and modification remain difficult. One promising approach to overcome this limitation is to introduce dynamic covalent bonds that enable chain‐exchange reactions and network‐structure rearrangements in identical polymer networks (A–A fusion), resulting in self‐healing and reprocessing properties. Reported here is the fusion of two distinct polymer networks (A–B fusion) by the dynamic behavior of bis(2,2,6,6‐tetramethylpiperidin‐1‐yl)disulfide (BiTEMPS) at the interface between different CLPs. The appearance, swelling behavior, and mechanical properties of the fused samples indicate exchange reactions of the BiTEMPS units and the formation of topological bonds at the interface, commensurate with the generation of a CLP that exhibits tunable properties.     

First preparation and structural determination of 1,1-disubstituted dibenzo[bc,fg][1,4]silathiapentalene derivatives by x-ray crystallographic analysis and MO calculations

1,1-Dimethyldibenzo[bc,fg][1,4]silathiapentalene ( 1a ) was prepared by treatment of 1,9-bis(methyl-sulfinyl)dibenzothiophene with EtMgBr or of dibenzothiophene with n-butyllithium, and then with dimethyl dichlorosilane. The structure of 4,4-dimethyl-dibenzo[bc,fg][1,4]silathiapentalene 1-oxide ( 2 ), obtained by oxidation of compound 1a with mCPBA, was determined by X-ray crystallographic analysis. The structure of compound 2 determined experimentally was compared to the structure obtained by semiempirical molecular orbital calculations (AM1). The MO calculations of compound 1a and its phenyl analog 1b were also performed by AM1 to evaluate their structures. © 1996 John Wiley & Sons, Inc.     

NMR studies on the ligand exchange reactions between diaryl tellurides and phenyllithium: Detection of hypervalent triaryl tellurium ate complexes

Diaryl tellurides undergo rapid ligand exchange and disproportionation reactions on treatment with phenyllithium at −78°C. Triarylteliuranes [10-Te-3(C₃)]⁻ Li⁺ were identified as discrete intermediates during the reactions by ¹²⁵Te, ¹H, ¹³C, and CH-COSY NMR studies.     

Front Cover: Enhancement of Chiroptical Responses of trans‐Bis[(β‐iminomethyl)naphthoxy]platinum(II) Complexes with Distorted Square Planar Coordination Geometry (ChemistryOpen 4/2022)

The Front Cover shows the comparison of circularly polarized luminescence (CPL) properties of square planar platinum(II) complexes with different coordination geometries. Computational studies have revealed that the distortion of the coordination geometry is key to enhancement of the chiroptical responses of these compounds. More information can be found in the Research Article by Masahiro Ikeshita et al.     

Determination of ammonium in river water and sewage samples by capillary zone electrophoresis with direct UV detection

We developed capillary zone electrophoresis (CZE) with direct UV detection for determination of ammonium in environmental water samples. Ammonium in the samples was partly converted into ammonia in the alkaline background electrolyte (BGE) during migration and was detected by molecular absorption of ammonia at 190 nm in approximately 7 min. The limit of detection (LOD) for ammonium was 0.24 mg/l (as nitrogen) at a signal-to-noise ratio of three. The respective values of the relative standard deviation (RSD) of peak area, peak height, and migration time for ammonium were 2.1, 1.8, and 0.46%. Major alkali and alkaline earth metal ions coexisting in the samples did not interfere with ammonium determination by the proposed method. The proposed method determined ammonium in surface water and sewage samples. The results were compared to those obtained using ion chromatography (IC).     

NANOMECHANICAL MAPPING OF CARBON BLACK REINFORCED NATURAL RUBBER BY ATOMIC FORCE MICROSCOPY

Atomic force microscopy （AFM） has the advantage of obtaining mechanical properties as well as topographic information at the same time. By analyzing force-distance curves measured over two-dimensional area using Hertzian contact mechanics, Young＇s modulus mapping was obtained with nanometer-scale resolution. Furthermore, the sample deformation by the force exerted was also estimated from the force-distance curve analyses. We could thus reconstruct a real topographic image by incorporating apparent topographic image with deformation image. We applied this method to carbon black reinforced natural rubber to obtain Young＇s modulus distribution image together with reconstructed real topographic image. Then we were able to recognize three regions; rubber matrix, carbon black （or bound rubber） and intermediate regions. Though the existence of these regions had been investigated by pulsed nuclear magnetic resonance, this paper would be the first to report on the quantitative evaluation of the interfacial region in real space.