The electrochemical synthesis of hetero7helicenes including pyrrole and furan rings has been established. A single electrochemical operation led to an oxidative heterocoupling and dehydrative ...cyclization sequence to afford oxaza7helicenes in 50–86% yields with 45–77% Faradic efficiencies. Their derivatization and chiroptical properties were also investigated.
A series of optically active bisbenzofuro2,3-
:3',2'-
pyridine (BBZFPy) derivatives was synthesized starting with the readily available (
)- and (
)-1,1'-bi-2-naphthols through a palladium-catalyzed ...multiple intramolecular C-H/C-H coupling as the key ring-closure step. The effect of terminal
-butyl substituents on the BBZFPy skeleton was systematically investigated to uncover a unique aggregation-induced enhancement of CPL characteristics in the solid state. The crystal structures of the coupling products were also evaluated by single crystal X-ray analysis and the well-ordered intermolecular stacking arrangements appeared to be responsible for the enhanced CPL.
Pure organic materials with the circularly polarized luminescence (CPL) property have attracted significant research interest over the past few decades. In this study, a series of axially chiral ...bibenzobcarbazole derivatives were synthesized by adopting palladium- and iridium-catalyzed direct C–H functionalization reactions as the key steps. These compounds exhibited CPL characteristics with considerably large dissymmetry factors up to 2.81 × 10–2 in the solid state, indicating the formation of well-ordered aggregates.
The electrochemical synthesis of hetero7helicenes including pyrrole and furan rings has been established. A single electrochemical operation led to an oxidative heterocoupling and dehydrative ...cyclization sequence to afford oxaza7helicenes in 50–86% yields with 45–77% Faradic efficiencies. Their derivatization and chiroptical properties were also investigated.
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•Predictive PC-SAFT approach for metal precursor solubilities in scCO2.•PC-SAFT parameters determined by fitting solubilities in organic solvents.•PC-SAFT approach reproduces metal ...precursor solubilities in scCO2 without kij.•Generalized kij parameter improves calculated reliabilities of solubilities in scCO2.
Solubilities of metal precursors in supercritical carbon dioxide (scCO2) are needed to effectively design the scCO2-based deposition method. Herein, a method for predicting the solubilities of metal acetylacetonate (acac) precursors in scCO2 was developed using the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state. Three PC-SAFT pure-component parameters viz., the segment diameter, segment number, and dispersion energy, for two metal acetylacetonates (Cr(acac)3 and Cu(acac)2) were determined by adjusting their values to the measured solubilities in organic solvents. The PC-SAFT parameters of Cr(acac)3 and Cu(acac)2 were then applied to predict the experimentally determined metal precursor solubilities in scCO2 from the literature. The PC-SAFT predictions accurately described the experimental solubilities in scCO2 over a wide range of pressures and temperatures even if the binary interaction parameter kij was set to 0. The isobaric solubilities in scCO2 were also calculated with the generalized kij values, which provided a successful PC-SAFT description.
Developing a modeling method for determining the solubilities of metal complexes in supercritical CO2 is crucial for designing an effective supercritical CO2-based deposition technique. This study ...aimed to model the solubility of ferrocene, a typical precursor of metallic iron, in supercritical CO2, which was achieved using perturbed-chain statistical associating fluid theory (PC-SAFT) in conjunction with experimental solubility data for metal complexes in organic solvents. Pure-component PC-SAFT parameters for ferrocene were derived by fitting solubility data for the metal complex in organic solvents, and these parameters were subsequently used to estimate the solubility of ferrocene in supercritical CO2. The resulting isothermal and isobaric solubilities of the metal complex in supercritical CO2 were accurately described over a wide range of pressures using this PC-SAFT model in comparison with experimental values.
A methodology to model the solubilities of metal complexes in supercritical CO2 is indispensable for effectively designing the supercritical CO2-based deposition method. Herein, the solubility of two ...metal acetylacetonates (acac), Co(acac)3 and Fe(acac)3, in supercritical CO2 was modeled based on the perturbed-chain statistical associating fluid theory (PC-SAFT) and experimentally-determined solid–liquid equilibria in organic solvents. This modeling approach is more predictive than conventional cubic-type equations of state or semi-empirical correlation models. The pure-component parameters of PC-SAFT for metal acetylacetonates are obtained by fitting the obtained solubility data to four typical organic solvents (toluene, acetone, 2-butanone, and ethyl acetate). By applying these PC-SAFT parameters, the model satisfactorily reproduced the solubilities of the metal complexes in supercritical CO2, particularly under low-temperature conditions even with the kij (binary interaction parameter) set to 0 in the combining rule. The isobaric solubilities can also be described by PC-SAFT by generalizing the temperature dependence of kij.
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•Predictive PC-SAFT approach for metal acetylacetonates solubilities in scCO2.•PC-SAFT parameters determined by fitting newly measured solubilities in organic solvents.•PC-SAFT approach reproduces metal acetylacetonates solubilities in scCO2 without kij.•Generalized kij parameter improves calculated accuracies of isobaric and isothermal solubilities in scCO2.
The patient was an 81-year-old man. Laparoscopic sigmoidectomy was performed for a sigmoid colon cancer(S, type 2, pT3SS, INF a, Ly0, V0, BD1, Pn0, pPM0, pDM0, RM0, pN0, pM0, pStage Ⅲa, R0, Cur A). ...One year after the surgery, a blood test showed CEA as high as 68.9 ng/mL, and an abdominal enhanced computed tomography revealed a hepatic tumor showing marginal contrast in the 4th liver segment. Positron emission tomography showed an accumulation of SUVmax 19.0 at the same site, and a metastatic liver tumor was diagnosed. A laparoscopic medial hepatectomy was performed. Bleeding from the hepatectomy site increased significantly after completion. Subcutaneous emphysema spreading from the face to the trunk and thigh was observed, and blood tests revealed a pH of 7.172, PaCO2 of 71.0 mmHg, lactate of 67 mg/dL, mixed acidosis, D-dimer of 118 μg/mL, and a disseminated intravascular coagulation(DIC)syndrome was diagnosed. Following the difficulty of hemostasis, the surgery was changed to laparotomy and terminated by gauze packing. We encountered a case of acidosis exacerbated by hypercapnia that progressed to DIC during laparoscopic medial hepatectomy.
Because blood cells can be obtained with relatively easy and safe procedure, they have been routinely used for transfusion and transplantation purposes. And they are now considered as attractive cell ...sources for developing new gene therapies including cancer therapy using various immune cells, and regenerative therapy using hematopoietic stem cells or induced pluripotent stem cells (iPS) cells. For example, chimeric antigen receptor modified autologous T cells have been considered as effective therapy for various cancers. And iPS cells have been easily established from peripheral T cells for the purpose of treating various diseases. However, in spite of these possibilities, the development of the safer and more efficient genetic modification methods of hematopoietic cells is imminent. In this study, we developed the novel measles viral (MV) vector which enables us to transduce multiple genes into immune cells. The wild type measles virus is one of the aerosol-transmitted viruses and has strong infectious capacity to immune cells, and epithelial cells via signaling lymphocyte activation molecule (SLAM) or nectin-4. First, we modified the wild type measles virus genome to non-transmissible and non-lytic, and equipped with the ability of transducing multiple genes, at most six genes, into target cells. Briefly, the intrinsically non-segmented wild type virus genome was divided into two segments and point mutations were introduced into the virus genes encoding hemagglutinin and the matrix protein. Moreover, as the fusion protein gene was removed from the virus genome, the virus could not replicate in neighbor cells. We examined the gene transduction efficiency of the gene modified measles virus (H8-Fd-MV vector) into hematopoietic cells. We first constructed the H8-Fd-MV vector with GFP gene and transduced into hematopoietic progenitor cells and immune cells from human cord blood and peripheral blood. We observed that almost all of HPCs from cord blood (99.7% in floating cells expressed CD34), T cells (99.9% in CD3+ cells), and B cells (98.2% in CD19+ cells) from peripheral blood expressed GFP at two days after the transduction. Especially, to express GFP gene in human peripheral T cells, it was not necessary to pre-stimulate them with CD3/CD28 beads (99.6% in stimulating T cells (72.9% in SLAM+ cells) v.s. 82.6 % in non-stimulating cells (37.4% in SLAM+ cells)). T cells from cord blood showed almost all naïve phenotype (CD4+ cells: 93.2±1.8% in CD45RA+CCR7+ cells, 1.7±1.1% in CD45RA+CCR7- cells; CD8+ cells: 41.6±5.7% in CD45RA+CCR7+ cells, and 41.9±11.0% in CD8+CD45RA+CCR7- cells) and T cells transduced by MV vector expressed GFP more (CD4+ cells: 80.3±13.7%, and CD8+ cells: 82.5±8.5%) than those transduced by Sendai viral vector (CD4+ cells: 15.5±0.7%, and CD8+ cells: 17.4±5.4%). These data suggested that H8-Fd-MV vector could transduce GFP gene efficiently into various T cell lineages including naïve T cells, which had been difficult to be transduced with classical gene transduction methods. We next generated H8-Fd-MV vector for expressing 6 genes (OCT4, SOX2, KLF4, L-MYC, PIN1, and GFP) and transduced into stimulated T cells. After 3 days, GFP+ T cells expressed all of these 6 genes. We also detected that more than 50% of the stimulated T cells with IL-2 expressed GFP at 14 days after the transduction. After 27 days from transfection, embryonic stem cell (ES cell)-like colonies were picked up and analyzed the character. These cells showed ES cell morphology over 20 times passages and expressed pluripotent marker (NANOG, OCT4, Tra-1-60, Tra-1-81). We also found T cell receptor rearrangements in these cells. Embryoid bodies from these cells expressed three germ line markers in vitro. We next examined the hematopoietic differentiation of these cells using coculture system with murine embryonic aorta-gonad-mesonephros region-derived stromal cell line (AGM-3 cells). The co-cultured cells harvested at day 12 expressed CD34 and CD45. These data suggested that we established iPS cells from terminal differentiated T cells using H8-Fd-MV vector for expressing reprogramming factor.
These results indicated that multiple genes were expressed efficiently in immune cells using H8-Fd-MV vector. Highly efficient transduction ability of MV vector for T cells would enable us to develop new gene therapy targeting cancer using gene modified T cells as well as organ regeneration using iPS cells.
No relevant conflicts of interest to declare.
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