Photochemistry and Photophysics of Charge-Transfer Excited States in Emissive d10/d0 Heterobimetallic Titanocene Tweezer Complexes.

Transition-metal complexes that undergo ligand-to-metal charge transfer (LMCT) to d0 metals are of interest as possible photocatalysts due to the lack of deactivating d-d states. Herein, the synthesis and characterization of nine titanocene complexes of the formula Cp2Ti(C2Ar)2·MX (where Ar = phenyl, dimethylaniline, or triphenylamine; and MX = CuCl, CuBr, or AgCl) are presented. Solid-state structural characterization demonstrates that MX coordinates to the alkyne tweezers and CuX coordination has a greater structural impact than AgCl. All complexes, including the parent complexes without coordinated MX, are brightly emissive at 77 K (emission max between 575 and 767 nm), with the coordination of MX redshifting the emission in all cases except for the coordination of AgCl into Cp2Ti(C2Ph)2. TDDFT investigations suggest that emission is dominated by arylalkynyl-to-titanium 3LMCT in all cases except Cp2Ti(C2Ph)2·CuBr, which is dominated by CuBr-to-Ti charge transfer. In room-temperature fluid solution, only Cp2Ti(C2Ph)2 and Cp2Ti(C2Ph)2·AgCl are emissive, albeit with photoluminescent quantum yields ≤2 × 10-4. The parent complexes photodecompose in room-temperature solution with quantum yields, Φrxn, between 0.25 and 0.99. The coordination of MX decreases Φrxn by two to three orders of magnitude. There is a clear trend that Φrxn increases as the emission energy increases. This trend is consistent with a competition between energy-gap-law controlled nonradiative decay and thermally activated intersystem crossing between the 3LMCT state and the singlet transition state for decomposition.

An overview of multiplexed analyses of CAR T-cell therapies: insights and potential.

INTRODUCTION: Cancer immunotherapy is a rapidly growing field with exponential advancement in engineered immune cell-based therapies. For instance, an engineered chimeric antigen receptor (CAR) can be introduced in T-cells or other immune cells and adoptively transferred to target and kill cancer cells in hematologic malignancies or solid tumors. The first CAR-T-cell (CAR-T) therapy has been developed against CD19, a B-cell marker expressed on lymphoma and lymphoblastic leukemia. To allow for personalized treatment, proteomics approaches could provide insights into biomarkers for CAR-T therapy efficacy and toxicity. AREAS COVERED: We researched the most recent technology methods of biomarker evaluation used in the laboratory and clinical setting. Publications of CAR-T biomarkers were then systematically reviewed to provide a narrative of the most validated biomarkers of CAR-T efficacy and toxicity. Examples of biomarkers include CAR-T functionality and phenotype as well as interleukin-6 and other cytokines. EXPERT COMMENTARY: Biomarkers of CAR-T efficacy and toxicity have been identified, but still need to be validated and standardized across institutions. Moreover, few are used in the clinical setting due to limitations in real-time technology. Expansion of biomarker research could provide better understanding of patient response and risk of life-threatening side effects with potential for improved precision medicine.

A trans-bidentate bis-pyridinyl ligand with a transition metal hinge.

A titanocene based metalloligand, Cp*2Ti(C22-py)2, was synthesized and coordinated to either Cu(i) or Pd(ii). The metalloligand binds Cu(i) between its alkynes and Pd(ii) between its pyridinyl rings, acting as a trans-bidentate ligand. In order to bind Pd(ii), significant structural rearrangements were necessary, which required the flexibility of the C-Ti-C hinge on the titanocene metalloligand.