Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn₅(OH)₈]Cl₂·yH₂O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10–12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.     

Syntheses of methylpyridine and methylpyridine N-oxide decorated benzoxazine and naphthoxazine platforms

Simple, aqueous-based syntheses of methylpyridine and methylpyridine N-oxide decorated 3,4-dihydro-2H-naphthoxazine and 2,3-dihydro-1H-naphthoxazine monomers, as well as thermally promoted syntheses of 3,4-dihydro-2H-benzoxazine monomers and bisoxazine methylpyridine derivatives of substituted 1,5-, 2,6-, and 2,7-dihydroxynaphthalenes are described. The crystal structures of two derivatives are presented.     

A Lysosome‐Compatible Near‐Infrared Fluorescent Probe for Targeted Monitoring of Nitric Oxide

The requirement for nitric oxide (NO) of lysosomes has motivated the development of a sophisticated fluorescent probe to monitor the distribution of this important biomolecule at the subcellular level in living cells. A near‐infrared (NIR) fluorescent Si‐rhodamine (SiRB)‐NO probe was designed based on the NO‐induced ring‐opening process of Si‐rhodamine. The probe exhibits fast chromogenic and fluorogenic responses, and high sensitivity and selectivity toward trace amounts of NO. Significantly, the spirolactam in Si‐rhodamine exhibits very good tolerance to H⁺, which in turn brings extremely low background fluorescence not only in the physiological environment but also under acidic conditions. The stability of the highly fluorescent product in acidic solution provides persistent fluorescence emission for long‐term imaging experiments. To achieve targeted imaging with improved spatial resolution and sensitivity, an efficient lysosome‐targeting moiety was conjugated to a SiRB‐NO probe, affording a tailored lysosome‐targeting NIR fluorescent Lyso‐SiRB‐NO probe. Inheriting the key advantages of its parent SiRB‐NO probe, Lyso‐SiRB‐NO is a functional probe that is suited for monitoring lysosomal NO with excellent lysosome compatibility. Imaging experiments demonstrated the monitoring of both exogenous and endogenous NO in real time by using the Lyso‐SiRB‐NO probe.     

Rare Earth Ion Mediated Fluorescence Accumulation on a Single Microbead: An Ultrasensitive Strategy for the Detection of Protein Kinase Activity at the Single‐Cell Level

A single microbead‐based fluorescence imaging (SBFI) strategy that enables detection of protein kinase activity from single cell lysates is reported. We systematically investigated the ability of various rare earth (RE) ions, immobilized on the microbead, for specific capturing of kinase‐induced phosphopeptides, and Dy³⁺ was found to be the most prominent one. Through the efficient concentration of kinase‐induced fluorescent phosphopeptides on a Dy³⁺‐functionalized single microbead, kinase activity can be detected and quantified by reading the fluorescence on the microbead with a confocal fluorescence microscope. Owing to the extremely specific recognition of Dy³⁺ towards phosphopeptides and the highly‐concentrated fluorescence accumulation on only one microbead, ultrahigh sensitivity has been achieved for the SBFI strategy which allows direct kinase analysis at the single‐cell level.     

High‐contrast Noninvasive Imaging of Kidney Clearance Kinetics Enabled by Renal Clearable Nanofluorophores

Noninvasive imaging of kidney clearance kinetics (KCK) of renal clearable probes is key to studying unilateral kidney function diseases, but such imaging is highly challenging to achieve with in vivo fluorescence. While this long‐standing challenge is often attributed to the limited light penetration depth, we found that rapid and persistent accumulation of conventional dyes in the skin “shadowed” real fluorescence signals from the kidneys and prevented noninvasive imaging of KCK, which, however, can be addressed with renal clearable nanofluorophores. By integrating near infrared emission with efficient renal clearance and ultralow background interference, the nanofluorophores can increase kidney‐contrast enhancement and imaging‐time window by approximately 50‐ and 1000‐fold over conventional dyes, and significantly minimize deviation between noninvasive and invasive KCK, laying down a foundation for translating in vivo fluorescence imaging in preclinical noninvasive kidney function assessments.     

The Quest for Polysulfides in Lithium–Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study

Confocal Raman spectra of a lithium–sulfur battery electrolyte are recorded operando in a depth‐of‐discharge resolved manner for an electrochemical cell with a realistic electrolyte/sulfur loading ratio. The evolution of various possible polysulfides is unambiguously identified by combining Raman spectroscopy data with DFT simulations.