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Metal organic frameworks (MOFs) have yet to appreciably become ubiquitous, manufacturable chemical products, despite their impressive functional versatility, particularly in the fields of separation, adsorption, and catalysis. Processing demands and high energetic costs contribute to suppressed material adoption. Eco-friendly substitutions at the process level must focus on the preserved performance (e.g. maximized storage capacity or conversion yield) of sustainably fabricated MOFs, with special consideration paid to the material defect character and metal cation active site valency. In this work, redox engineering was used as a strategy to tune the metal active site valency and, as a result, defect amount, for the well-known transition metal MOF, MIL-100(Fe). Tuning of redox equilibria, achieved via pH and reaction temperature reciprocity, permitted control of Fe2+/Fe3+, as verified by UV-vis and XPS analyses. With increasing amounts of Fe2+ framework cations, MOF defect content was likewise observed to increase, imbuing advantageous performance metrics when within an identified optimal range. CO2 adsorption capacity served to evaluate active site identity and accessibility. 19% improved CO2 uptake was achieved with optimum Fe2+/Fe3+ ratio, attributed to the presence of beneficial defects which expanded the material micro- and mesoporous area for accessible CO2 coordination. Framework structural degradation, leading to decreased BET surface area and depressed CO2 adsorption and selectivity, was observed in samples with the highest Fe2+ amounts, highlighting the narrow separation between productive and detrimental defects. Uniquely, defects originated at the metal node itself, rather than arising from heterogeneous mixed-linker or modulated approaches. Our redox pathway preserves green product quality by balancing valency/defect tradeoffs, thus alleviating industrial scaling demands and culminating in a flexible, more energetically conscious MOF generation pathway. [ABSTRACT FROM AUTHOR]

Checkpoint immunotherapy has made great strides in the treatment of solid tumors, but many patients do not respond to immune checkpoint inhibitors. Identification of tumor‐infiltrating cytotoxic T cells (CTLs) has the potential to stratify patients and monitor immunotherapy responses. In this study, the design of cluster of differentiation (CD8+) T cell‐targeted nanoprobes that emit shortwave infrared (SWIR) light in the second tissue‐transparent window for noninvasive, real‐time imaging of CTLs in murine models of breast cancer is presented. SWIR‐emitting rare‐earth nanoparticles encapsulated in human serum albumin are conjugated with anti‐CD8α to target CTLs with high specificity. CTL targeting is validated in vitro through binding of nanoprobes to primary mouse CTLs. The potential for the use of SWIR fluorescence intensity to determine CTL presence is validated in two syngeneic mammary fat pad tumor models, EMT6 and 4T1, which differ in immune infiltration. SWIR imaging using CD8‐targeted nanoprobes successfully identifies the presence of CTLs in the more immunogenic EMT6 model, while imaging confirms the lack of substantial immune infiltration in the nonimmunogenic 4T1 model. In this work, the opportunity for SWIR imaging using CD8‐targeted nanoprobes to assess CTL infiltration in tumors for the stratification and monitoring of responders to checkpoint immunotherapy is highlighted. [ABSTRACT FROM AUTHOR]

CuInSe2 quantum dots (QDs) are one of the most important Cd-free fluorescent probes; they usually exhibited low fluorescence intensity, suggesting that a considerable amount of absorbed photon energy was lost as heat. In this study we aimed to improve the fluorescence intensity of CuInSe2 QDs and investigate their photoacoustic (PA) signal resulting from the heat dissipation, which was previously rarely reported. Cu–In–Zn–Se/ZnSe QDs were synthesized by adopting two strategies of Zn doping and ZnSe shell growth. It was found that there was an upper limit for Zn concentration beyond which the fluorescence intensity began to decrease. In addition, a blue shift of the emission peak of Cu–In–Zn–Se/ZnSe QDs was observed at high concentrations of ZnSe precursor due to the diffusion of excessive Zn. To prepare the dual-modal fluorescence and PA imaging probe, poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with polyethylene glycol (PEG) was coated on the QDs, which led to a slight reduction in fluorescence. Cellular labeling on HeLa cells was performed to demonstrate the utility of these probes for fluorescence imaging. We further studied the in vitro PA imaging capabilities of the Cu–In–Zn–Se/ZnSe/PMAO-g-PEG nanoparticles, which showed a distinct PA signal beyond 1.0 mg ml−1. The current work demonstrated that a moderate amount of Zn doping is necessary for enhancing fluorescence and there is a limit beyond which the fluorescence will be diminished. We also demonstrated the proof of concept that Cu–In–Zn–Se/ZnSe QDs are able to serve as a potential PA imaging contrast agent. [ABSTRACT FROM AUTHOR]

Nd3+-doped YF3 (YF3:Nd) nanoparticles with a size of ∼20 nm were synthesized by solvothermal decomposition of yttrium and neodymium trifluoroacetate precursors in oleylamine. Using the 4f-energy matrix diagonalization procedure various interaction parameters: Slater–Condon (F2, F4, and F6), spin-orbit (ξ), two body interaction (α, β, and γ), Judd parameters (T2, T3, T4, T6, T7, and T8), spin-other-orbit parameters (M0, M2, and M4) and electrostatically correlated spin-orbit interaction parameters (P2, P4, and P6), and the crystal-field parameters (Bqk) were evaluated. The potential of YF3:Nd as a laser host for 1052 nm emission was evaluated by quantitative analysis of the absorption, emission spectra, and fluorescence decay characteristics. Judd–Ofelt parametrization was employed to compute the radiative spectral parameters such as radiative transition probabilities, fluorescence branching ratios, stimulated emission cross sections, and quantum efficiencies of the observed bands in the fluorescence spectrum. Using the measured radiative properties, 75% quantum efficiency was obtained for the principal emission band at 1052 nm when the Nd dopant concentration was 0.25 mol %, with an emission cross section of 0.74×10-20 cm2. Analysis of the energy transfer kinetics showed that at low dopant concentrations of 0.25 mol % dipole-dipole interactions were dominant, whereas energy migration was the leading process at higher dopant concentrations. Quenching by OH impurities was found to be within the limit of optimum amplifier performance where multiphonon relaxation losses were negligible. Preliminary optical characterization showed that these nanocrystalline materials can be potentially used as optical amplifiers and in applications like infrared imaging, security and authentication. [ABSTRACT FROM AUTHOR]