Hybrid metal–organic frameworks (MOFs) with core/shell-like hierarchical structure comprised of zirconium metal and porphyrin (e.g., TPP) and its isomer, N-confused porphyrin (NCP), were synthesized ...through a seed-mediated reaction. The hierarchical structures of hybrid MOFs were characterized by the microscopic image analyses (e.g., scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectrometry, and confocal laser scanning microscope (CLSM)). Taking advantage of the intrinsic light-harvesting properties of the porphyrin dye and the N-confused isomer, changing the core/shell layer structures of hybrid MOFs allows for tuning of the visible-to-near-infrared (NIR) absorption/emission characters, excited-state energy migrations, and photosensitization capabilities. The Förster energy transfer event occurring in the bulk MOF samples by photoexcitation enabled us to control the photoinduced singlet oxygen generation through the comprehensive light-harvesting ability of these hybrid porphyrinic MOFs. Therefore, implementation of a precisely designed porphyrin “substitute” into the MOF-based materials indeed provides a new mimic of the photosynthetic pigment system and should be potentially applicable for solar-light-driven devices.
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IJS, KILJ, NUK, PNG, UL, UM
Oxidative electropolymeization of an axially bound, bithiophene–pyridine complex of ruthenium(III)–porphycene Ru(TPrPc) (btp)2PF6 (1) gives a submicrometer-thick, polymeric film on an ITO ...electrode with a crystalline morphology. The polymeric film, the first example of axially linked multimetalloporphycene coordination arrays, exhibits highly stable and reproducible electrochromic response with high electrochromic efficiency upon electrochemical control over the metal-centered electron transfer process (RuII/RuIII).
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IJS, KILJ, NUK, PNG, UL, UM
Humidity‐responsive ON/OFF switching of CO2 inclusion, associated with cooperative structural changes of heterogeneous cavities in crystalline peptide NiII macrocycles, 1⋅NO3, is demonstrated. The ...structural transformation between an “open form” and a “closed form” was caused by reversible water uptake into one of the cavities. The adsorption behavior of CO2 was studied with and without water vapor, combined with gas‐composition analysis by using gas chromatography. The studies revealed that the open form of 1⋅NO3 adsorbs CO2 gas up to 34 g mol−1, whereas the closed form adsorbs only a negligible amount of CO2 gas. Also, structural studies (X‐ray and IR spectroscopies) and investigation of water‐content dependence of CO2 adsorption revealed that the switching of gas inclusion occurred abruptly over a narrow range of water‐vapor pressure and was caused by the cooperative opening of vacant space to give the open form due to the structural transformation by water uptake.
Let's cooperate! Humidity‐responsive ON/OFF switching of CO2 inclusion by using cooperative structural changes of heterogeneous cavities in crystalline peptide NiII macrocycles is demonstrated. The opening/closing of vacant cavities triggered by water uptake/release into the other cavities caused the switching of CO2 inclusion (see scheme).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Abstract
The detection of circulating cell-free DNA (cfDNA) by liquid biopsy is reported to provide prognostic information in colorectal cancer (CRC). Although the frequency of
BRAF
V600E mutation in ...CRC is less than 10%, it is associated with poor responses to conventional chemotherapy. We conducted a prospective study to investigate the relationship between the perioperative mutant allele frequency (MAF) of
BRAF
V600E and tumor recurrence, and to evaluate the possibility of early detection of recurrence. Among 362 patients who underwent radical resection, cfDNA was extracted from the perioperative blood of 11 CRC patients with
BRAF
V600E mutation and analyzed using the digital polymerase chain reaction (dPCR) system. The median follow-up time was 22 months, and there were four cases of recurrence. Although there was no correlation between recurrence and the perioperative MAF of
BRAF
V600E, tumor diameter was correlated with the MAF (p = 0.024), and the MAF increased with time in two patients from whom additional samples were obtained prior to recurrence. In this study, we identified a correlation between the pathological tumor diameter and the MAF, but it was difficult to predict recurrence by measuring cfDNA with
BRAF
V600E mutation in the perioperative period of radical resection of CRC.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Solid-state ionic conductors are actively studied for their large application potential in batteries and sensors. From the view of future nanodevices, nanoscaled ionic conductors are attracting much ...interest. Silver iodide (AgI) is a well-known ionic conductor for which the high-temperature α-phase shows a superionic conductivity greater than 1 Ω−1 cm−1 (ref. 6). Below 147 C, α-AgI undergoes a phase transition into the poorly conducting β- and γ-polymorphs, thereby limiting its applications. Here, we report the facile synthesis of variable-size AgI nanoparticles coated with poly-N-vinyl-2-pyrrolidone (PVP) and the controllable tuning of the α- to β-/γ-phase transition temperature (Tc↓). Tc↓ shifts considerably to lower temperatures with decreasing nanoparticle size, leading to a progressively enlarged thermal hysteresis. Specifically, when the size approaches 10-11 nm, the α-phase survives down to 30 C-the lowest temperature for any AgI family material. We attribute the suppression of the phase transition not only to the increase of the surface energy, but also to the presence of defects and the accompanying charge imbalance induced by PVP. Moreover, the conductivity of as-prepared 11 nm β-/γ-AgI nanoparticles at 24 C is ∼1.5×10−2 Ω −1 cm−1-the highest ionic conductivity for a binary solid at room temperature. The stabilized superionic phase and the remarkable transport properties at a practical temperature reported here suggest promising applications in silver-ion-based electrochemical devices.
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IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
PD‐1 expression in peripheral blood T‐cells has been reported in several kinds of cancers, including lung cancer. However, the relationship between PD‐1 expression in peripheral blood T‐cells and ...prognosis after treatment with a cancer vaccine has not been reported. To elucidate this relationship, we analyzed PD‐1 expression in the peripheral blood T‐cells of patients with non‐small cell lung cancer. The blood samples used in this study were obtained from patients enrolled in phase II clinical trials of a personalized peptide vaccine. Seventy‐eight samples obtained before and after a single vaccination cycle (consisting of six or eight doses) were subjected to the analysis. PD‐1 was expressed on lymphocytes in the majority of samples. The relative contents of PD1+CD4+ T‐cells against total lymphocytes before and after the vaccination cycle correlated with overall survival (OS) with a high degree of statistical significance (P < 0.0001 and P = 0.0014). A decrease in PD‐1+CD8+ T‐cells after one cycle of vaccination also correlated with longer OS (P = 0.032). The IgG response to the non‐vaccinated peptides suggested that the epitope spreading seemed to occur more frequently in high‐PD‐1+CD4+ T‐cell groups. Enrichment of CD45RA−CCR7− effector‐memory phenotype cells in PD‐1+ T‐cells in PBMCs was also shown. These results suggest that PD‐1 expression on the peripheral blood T‐cell subsets can become a new prognostic marker in non‐small cell lung cancer patients treated with personalized peptide vaccination.
We found that the relatively high contents of PD‐1+CD4+ T cells in the peripheral blood, as well as a decrease of PD‐1+CD8+ T cells after vaccination, were correlated with longer OS. These results suggest that PD‐1 expression on the peripheral blood T‐cell subsets will become a new prognostic marker of NSCLC patients treated with personalized peptide vaccination
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
A novel chromophoric ionic liquid (IL) with two-dimensional (2D) nanostructural order is developed, and its structure-property relationship is investigated by harnessing photon upconversion based on ...triplet energy migration. An ion pair of 9,10-diphenylanthracene-2-sulphonate (DPAS) and asymmetric quaternary phosphonium ion exhibited both ionic crystal (IC) and supercooled IL phases at room temperature. Single crystal X-ray analysis of the IC phase showed an alternate alignment of polar (ionic) and non-polar (non-ionic) layers, and this layered structure was basically maintained even in the IL phase. The diffusion length of triplet excitons in the IL phase, obtained by the analysis of upconverted emission in succession to triplet-triplet annihilation (TTA), is larger than the domain size estimated from powder X-ray analysis. This suggests that triplet excitons in chromophoric ILs can diffuse over the nanostructured domains.
A new iron fluorophosphate compound, Fe(H2PO4)2F, was synthesized by a solvent-less method at low temperatures. Its structure was determined from single crystal X-ray diffraction. Fe(H2PO4)2F was ...found to have a 3-dimensional structure built up by parallel chains of corner-sharing octahedra. This novel compound crystallizes in a tetragonal I4/mcm space group with the following lattice parameters: a = b = 9.01870(10) Å and c = 7.8058(2) Å. Further characterization of the material was conducted by TGA and Mössbauer spectroscopy. Proton conductivity measurements under dry condition revealed activation energies of Ea = 0.43 eV (along c-axis) and Ea = 0.41 eV (along a-axis) with corresponding room-temperature conductivities 2.6 × 10−7 S cm−1 and 5.8 × 10−8 S cm−1.
•New Fe(H2PO4)2F compound was synthesized via a solvent-less method.•Fe(H2PO4)2F crystallizes in an open 3D framework structure.•Delimited channels along the c-axis lead to improved proton transport.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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