A rare and exclusive endoperoxide photoproduct derived from thiacalix[4]arene crown-shaped derivative bearing 9,10-substituted anthracene moiety

A rare and exclusive endoperoxide photoproduct was quantitatively obtained from a thiacalix[4]arene crown-shaped derivative upon irradiation at λ=365 nm; the structure was unambiguously confirmed by 1H/13C NMR spectroscopy and X-ray crystallography. The prerequisites for the formation of the endoperoxide photoproduct have also been discussed. Furthermore, the photochemical reaction rate could be greatly enhanced in the presence of the thiacalix[4]arene platform because it served as a host to capture oxygen

1-Bromo-2,7-di-tert-butyl­pyrene

In the title mol­ecule, C24H25Br, one of two tert-butyl groups is rotationally disordered between two orientations in a 0.59 (3):0.41 (3) ratio. The crystal packing exhibits no π–π inter­actions; however, relatively short inter­molecular Br⋯Br contacts of 3.654 (1) Å are observed

Pyrene-fused pyrazaacenes with eight rectilinearly arranged aromatic rings

A series of pyrene-fused azaacene-type conjugated molecules containing two pyrazine units and up to eight rectilinearly arranged aromatic rings were prepared by condensation coupling reactions in moderate yields. The geometries and electronic structures associated with 2 and 5 were evaluated by DFT calculations. Photophysical properties indicated that these systems possess delocalized structures, and their optoelectronic properties can be tuned by extending the π-conjugated length and introducing electronic-withdrawing groups. The compounds were thoroughly investigated by XRD studies, electrochemistry and DFT calculations. High thermal stability and tunable energy levels make them excellent candidates as a class of organic molecular materials

Two-photon-absorption properties of pyrene-based dipolar D-π-A fluorophores

Two-photon absorption (TPA) properties of pyrene-based derivatives are rare as a result of the limited number of controllable synthetic methods to prepare them. However, these materials are in great demand given their potential practical application in photics and biological imaging. Herein, we present a set of pyrene-based dipolar donor-π-acceptor (D-π-A) fluorophores with a wide-range of color tuning and large TPA cross-sections (up to 2200 GM at 780 nm) by regioselective substitution at the 1,3- and 6,8-positions under the perspective of theoretical analysis. The linear and nonlinear optical properties of these compounds have been studied. The near-identical emission wavelengths between the two-photon-excited fluorescence (TPEF) and one-photon excited fluorescence (OPEF) indicated that they are generated from the same fluorescent excited state by either one- or two-photon excitation. With the exception of the strong donor [N(CH3)2] appended fluorophore, the TPEF exhibited a large red-shift compared with the OPEF spectra as a result of the complicated working mechanisms in operation, including intramolecular charge transfer (ICT) and twisted intramolecular charge transfer (TICT). All fluorophores exhibit high two-photon cross-sections (or two-photon brightness, δΦ), especially for 1348 GM, which indicated that these materials can be used as colorants for probe and bioimaging applications

Preoperative and Postoperative Pulmonary Function in Elderly Patients with Thoracolumbar Kyphoscoliosis

Study DesignCase series.PurposeThe objective of this study was to investigate the change in pulmonary function in adult patients with a spinal deformity who underwent spinal corrective surgery.Overview of LiteratureDegenerative lumbar and/or thoraco-lumbar deformities are is often prominent in adult spinal deformity cases, whereas a thoracic deformity involving the chest wall is inconspicuous. A lumbar spine deformity could affect the pulmonary function; however, few reports have investigated pulmonary function in adult patients with a spinal deformity.MethodsThis study included 14 adult patients with a spinal deformity who underwent posterior corrective fusion (3 males, 11 females; mean age, 67.4 years). We measured percent vital capacity (%VC) and percent forced expiratory volume in 1 second (%FEV1) before surgery and six months after surgery. We investigated the change in pulmonary function after corrective surgery and the correlation between radiographic parameters and pulmonary function.ResultsMean preoperative %VC and %FEV1 values were 99.9% and 79.3%, respectively. Two cases were diagnosed with restrictive impairment, and two cases were diagnosed with obstructive impairment before surgery. %VC improved in the restrictive impairment cases six months after surgery. However, %FEV1 did not improve significantly after surgery in the obstructive impairment cases.ConclusionsRestrictive impairment was improved in adult patients with a spinal deformity by corrective spinal surgery. However, spinal surgery did not improve obstructive impairment

Novel Measurement Technique for the Sagittal Vertical Axis and Its Clinical Application in Adult Spinal Deformity

Study DesignProspective physical measurement of the sagittal vertical axis (SVA).PurposeTo evaluate a simple method for measuring SVA by analyzing its relationship with radiographic measurements and clinical appearance.Overview of LiteratureNo studies have examined physical measurements using the cranial center of gravity (CCG) in a relaxed standing position.MethodsThe physical measurement of the horizontal distance between CCG and spina iliaca posterior superior (CCG-SIPS) was measured using a straight ruler in 252 healthy volunteers and 56 patients with adult spinal deformity. Health-related quality of life (HRQOL) was evaluated using the Oswestry disability index (ODI), and clinical symptoms were assessed according to standing status and the presence of gastroesophageal reflux disease (GERD).ResultsCCG-SIPS increased with age in the volunteer group and strongly correlated with radiographic SVA in the patient group (r=0.984). Differences increased between CCG-SIPS in patients in the relaxed position and radiographic SVA with an increase in sagittal malalignment (r=0.692, p120 mm) was significantly larger in the patient group than in the group with low sagittal malalignment (59.9±18.8 vs. 45.1±17.0; p=0.004); these patients (CCG-SIPS>120 mm) needed crutches or walkers for standing. The patient group with GERD had significantly larger sagittal malalignment than the group without GERD (160.3 mm vs. 81.0 mm).ConclusionsThe CCG-SIPS correlated with age and strongly reflected radiographic SVA and HRQOL in the patients. Moreover, it reflects a relaxed posture without a backward shift in the radiographic position even in patients with severe sagittal malalignment. The critical limit of CCG-SIPS can be relevant to clinical appearance, including standing assistance (>120 mm) and the existence of GERD (>150 mm). Thus, it will be a useful predictor of true SVA in clinical practice before radiographic evaluation

Hypoglossal Nerve Palsy as a Complication of an Anterior Approach for Cervical Spine Surgery

A recurrent laryngeal nerve injury is known as a complication referring to an anterior cervical spine surgery. However, hypoglossal nerve injury is not well known yet. Herein we report a rare case of a 39-years-old male with a hypoglossal nerve injury after C3/4 osteophyte resection with Smith-Robinson approach. In this case there appeared difficulties of articulation and tongue movement with deviation of the tongue to the left side after the surgery and we diagnosed a hypoglossal nerve injury due to retraction against the nerve during the operation. During the operative approach to the upper cervical spine we had to retract the internal carotid artery and the soft tissue to reach the vertebrae. This retract was the cause of the hypoglossal nerve injury. A gently traction and intermittent release is important to avoid a hypoglossal nerve damage

Preparation, Characterization and Sensitive Gas Sensing of Conductive Core-sheath TiO2-PEDOT Nanocables

Conductive core-sheath TiO2-PEDOT nanocables were prepared using electrospun TiO2 nanofibers as template, followed by vapor phase polymerization of EDOT. Various techniques were employed to characterize the sample. The results reveal that the TiO2 core has an average diameter of ∼78 nm while the PEDOT sheath has a uniform thickness of ∼6 nm. The as-prepared TiO2-PEDOT nanocables display a fast and reversible response to gaseous NO2 and NH3 with a limit of detection as low as 7 ppb and 675 ppb (S/N=3), respectively. This study provides a route for the synthesis of conductive nanostructures which show excellent performance for sensing applications

Elucidation of HHEX in pancreatic endoderm differentiation using a human iPSC differentiation model

ヒトiPS細胞分化モデルを用いた膵内胚葉分化におけるHHEXの役割の解明. 京都大学プレスリリース. 2023-06-09.Identification of HHEX as a crucial factor in pancreatic endoderm differentiation using a human iPS cell differentiation model. 京都大学プレスリリース. 2023-06-15.For pluripotent stem cell (PSC)-based regenerative therapy against diabetes, the differentiation efficiency to pancreatic lineage cells needs to be improved based on the mechanistic understanding of pancreatic differentiation. Here, we aimed to elucidate the molecular mechanisms underlying pancreatic endoderm differentiation by searching for factors that regulate a crucial pancreatic endoderm marker gene, NKX6.1. Unbiasedly screening an siRNA knockdown library, we identified a candidate transcription factor, HHEX. HHEX knockdown suppressed the expression of another pancreatic endoderm marker gene, PTF1A, as well as NKX6.1, independently of PDX1, a known regulator of NKX6.1 expression. In contrast, the overexpression of HHEX upregulated the expressions of NKX6.1 and PTF1A. RNA-seq analysis showed decreased expressions of several genes related to pancreatic development, such as NKX6.1, PTF1A, ONECUT1 and ONECUT3, in HHEX knockdown pancreatic endoderm. These results suggest that HHEX plays a key role in pancreatic endoderm differentiation

Relationship between Spinal Hemangioblastoma Location and Age

Study DesignRetrospective case series.PurposeTo investigate the relationship between tumor location and clinical characteristics.Overview of LiteratureHemangioblastoma is a rare disease that develops in the central nervous system. Magnetic resonance imaging (MRI) is useful to evaluate hemangioblastomas. Hemangioblastoma's location is designated as intramedullary, intramedullary+extramedullary, or extramedullary by MRI.MethodsWe analyzed 11 patients who underwent surgery for spinal hemangioblastoma. Using T1 contrast axial MRI data, the cases were divided into three groups (intramedullary, intramedullary+extramedullary, and extramedullary). Patient demographics, MRI findings, and preoperative neurological status were analyzed and compared for each group.ResultsThe average age of patients with intramedullary, intramedullary+extramedullary, and extramedullary hemangioblastoma was 34.0, 64.4, and 67.5 years, respectively. Patients in the intramedullary hemangioblastoma group were younger than the other groups. Extramedullary cases had a smaller syrinx compared to the other groups.ConclusionsAge may play an important role in the hemangioblastoma tumor location and the subsequent diagnosis by an MRI