3D-Continuous Nanoporous Covalent Framework Membrane Nanoreactors with Quantitatively Loaded Ultrafine Pd Nanocatalysts.

The confinement effect of catalytic nanoreactors containing metal catalysts within nanometer-sized volumes has attracted significant attention for their potential to enhance reaction rate and selectivity. Nevertheless, unregulated catalyst loading, aggregation, leaching, and limited reusability remain obstacles to achieving an efficient nanoreactor. A robust and durable catalytic membrane nanoreactor prepared by incorporating palladium nanocatalysts within a 3D-continuous nanoporous covalent framework membrane is presented. The reduction of palladium precursor occurs on the pore surface within 3D nanochannels, producing ultrafine palladium nanoparticles (Pd NPs) with their number density adjustable by varying metal precursor concentrations. The precise catalyst loading enables controlling the catalytic activity of the reactor while preventing excess metal usage. The facile preparation of Pd NP-loaded free-standing membrane materials allows hydrodechlorination in both batch and continuous flow modes. In batch mode, the catalytic activity is proportional to the loaded Pd amount and membrane area, while the membrane retains its activity upon repeated use. In continuous mode, the conversion remains above 95% for over 100 h, with the reactant solution passing through a single 50 µm-thick Pd-loaded membrane. The efficient nanoporous film-type catalytic nanoreactor may find applications in catalytic reactions for small chemical devices as well as in conventional chemistry and processes.

Efficacy of tocilizumab in patients with moderate-to-severe corticosteroid-resistant thyroid eye disease: a prospective study.

PURPOSE: To evaluate the clinical outcomes of intravenous tocilizumab (TCZ) injection in patients with moderate-to-severe active thyroid eye disease (TED). METHODS: Patients with active and moderate-to-severe TED who did not respond to conventional therapies were treated with TCZ from June 2019 to January 2021. The medical records of the patients were evaluated before the treatment. We analyzed patient demographics, including the duration of Graves' disease and TED, and assessed subjective symptoms, such as diplopia and ocular movement, clinical activity score (CAS), modified NOSPECS score, and exophthalmos before treatment and at 4, 8, 12, and 16 weeks after the first drug injection. Blood tests, including TSH Rc Ab and TS Ab, were performed before treatment and 24 weeks after the first injection. And orbital computed tomography (CT) was performed and Barrett's Index was calculated at baseline and after completion of all injections. RESULTS: Nineteen completed the scheduled treatment. There were no significant side effects, other than herpes zoster in one case and headache and dermatitis in another. Clinical symptoms before and 16 weeks after the treatment showed mean CAS decreased by 2.4 points, mean modified NOSPECS score decreased by 3.7 points, and mean exophthalmos decreased by 0.4 mm. Diplopia and extraocular muscle limitation improved in ten and remained stationary in five of the 15 patients, who presented with extraocular motility abnormalities. Six of 11 patients who underwent orbit CT showed improvement in muscle size. The mean TSH Rc Ab decreased by 7.5 IU/L and TS-Ab decreased by 162.9%. CONCLUSION: TCZ can treat active moderate-to-severe TED, showing high drug compliance and reasonable response to inflammation and extraocular motility abnormality.

Early response to intravenous methylprednisolone therapy for restrictive myopathy in patients with thyroid eye disease.

PURPOSE: To report the therapeutic efficacy of intravenous methylprednisolone (IVMP) in patients with restrictive myopathy caused by thyroid eye disease (TED). METHODS: The present prospective uncontrolled study comprised 28 patients with TED and restrictive myopathy who presented with diplopia that had developed within 6 months before their visit. All patients were treated with IVMP for 12 weeks. Deviation angle, limitation of extraocular muscle (EOM) movement, binocular single vision score, Hess score, clinical activity score (CAS), modified NOSPECS score, exophthalmometric value, and the size of EOMs on computed tomography were evaluated. The patients were divided into two groups: those whose deviation angle had decreased or remained unchanged 6 months after treatment (group 1; n = 17) and those whose deviation angle had increased in that time (group 2; n = 11). RESULTS: The mean CAS of the whole cohort significantly decreased from baseline to 1 month and 3 months after treatment (P = 0.03 and P = 0.02, respectively). The mean deviation angle significantly increased from baseline to 1, 3, and 6 months (P = 0.01, P < 0.01, and P < 0.01, respectively). The deviation angle decreased in 10 (36%), remained constant in seven (25%), and increased in 11 (39%) of the 28 patients. When groups 1 and 2 were compared, no single variable was identified as a cause of deviation angle deterioration (P > 0.05). CONCLUSIONS: When treating patients with TED who have restrictive myopathy, physicians should be aware that some patients show worsening of the strabismus angle despite inflammation control with IVMP therapy. Uncontrolled fibrosis can result in motility deterioration.

Template-Free Preparation of a Mesopore-Rich Hierarchically Porous Carbon Monolith from a Thermally Rearrangeable Polyurea Network.

A mesopore-rich, hierarchically porous carbon monolith was prepared by carbonizing a polyisocyanurate network derived by thermal rearrangement of a polyurea network. The initial polyurea network was synthesized by the cross-linking polymerization of tetrakis(4-aminophenyl)methane (TAPM) and hexamethylene diisocyanate (HDI) in the sol-forming condition, followed by precipitation into nanoparticulate solids in a nonsolvent. The powder was molded into a shape and then heated at 200-400 °C to obtain the porous carbon precursor composed of the rearranged network. The thermolysis of urea bonds to amine and isocyanate groups, the subsequent cyclization of isocyanates to isocyanurates, and the vaporization of volatiles caused sintering of the nanoparticles into a monolithic network with micro-, meso-, and macropores. The rearranged network was carbonized to obtain a carbon monolith. It was found that the rearranged network, with a high isocyanurate ratio, led to a porous carbon with a high mesopore ratio. The electrical conductivity of the resulting carbon monoliths exhibited a rapid response to carbon dioxide adsorption, indicating efficient gas transport through the hierarchical pore structure.

Orbital decompressive effect of endoscopic transorbital surgery for sphenoorbital meningioma.

PURPOSE: This study was aimed at evaluating the orbital decompressive effect of endoscopic transorbital approach (TOA) in the management of sphenoorbital meningioma involving the orbit. METHODS: Patients treated with TOA for this tumor from December 2016 to December 2019 were included, and the data were reviewed. Pre- and postoperative clinical and imaging findings were compared with a volumetric study. RESULTS: Eighteen patients (two men and 16 women) were included. Lateral wall hyperostosis (13 patients), extraconal tumor infiltration (18 patients), intraconal tumor infiltration (seven patients), and superior and lateral rectus encasement (nine patients) were found. Intraconal tumor infiltration in the posterior orbit affected compressive optic neuropathy (CON) more often than other tumor manifestations. The orbital soft tissue volume decreased to 91.18% ± 8.19% compared to that in the contralateral side preoperatively. The postoperative volume increased to 113.73% ± 12.92% compared to the preoperative volume. The average values of LogMAR visual acuity and visual field index score of ten patients with CON improved from 0.80 to 0.42 and 48.9 to 65.9%, respectively. All 17 patients with proptosis showed improvement after surgery. There were no significant complications associated with the surgery. Additional treatment, including gamma knife surgery, was applied to 12 cases for the remaining tumor. CONCLUSION: This minimally invasive surgical debulking procedure was successful in treating sphenoorbital meningioma without significant adverse events. Lateral orbital wall decompression and limited intraorbital tumor resection were effective for compressive orbitopathy from the tumor.

Use of Meshed Acellular Dermal Allograft as a Lining Material After Orbital Exenteration.

PURPOSE: To evaluate the surgical outcome and safety of acellular human dermal allograft as a new lining material to the exposed orbit after exenteration. METHODS: Retrospective case series of patients who underwent orbital exenteration followed by reconstruction with meshed-type acellular dermal allograft from 2009 to 2018 in a single tertiary institution. RESULTS: There were 14 eyes (2 right, 12 left) of 14 patients (6 men, 8 women). Mean age at operation was 69.1 ± 16.5 years. Indication for surgery was malignancy in all patients. One patient underwent subtotal exenteration, while the rest underwent total exenteration. SureDerm Meshed was used in 12 patients, AlloDerm Meshed in 1, and CGDerm Meshed in 1. Mean follow-up period was 12.1 months. Full or nearly full epithelialization occurred in 10 of 14 patients (71.4%) at 1 month and 9 of 12 patients (75.0%) at 3 months. There was delayed epithelialization in 3 patients due to poor wound care (n = 1), adjuvant radiotherapy (n = 1), and adjuvant radiotherapy followed by cerebrospinal fluid leak (n = 1). CONCLUSIONS: Meshed acellular human dermal allograft showed good success in reconstruction after orbital exenteration and may be considered as an alternative lining material to split-thickness skin graft after orbital exenteration.

Pilosebaceous Malignant Transformation of Dermoid Cyst in the Orbit.

Dermoid cysts may occur in the orbit, most commonly in the superolateral area. Malignant transformation of such lesions has been previously reported; however, most turn out to be squamous cell carcinoma. The authors' patient initially presented with mild proptosis and limitation in extraocular movements. Preliminary biopsy showed whitish amorphous material and abundant hairs filling the thin-walled cyst, consistent with dermoid cyst. The patient underwent tumor resection via lateral orbitotomy with bone window and transorbital endoscopic approach for the dural involvement. Final biopsy showed dermoid cyst with pilosebaceous malignant transformation showing p53 expression and 30% of Ki-67 index. Adjuvant radiotherapy was performed. To the best of the authors' knowledge, this is the first reported case of this type. Despite its rarity, there should always be a high index of suspicion and complete work-up for an accurate diagnosis.

Analysis of various factors affecting pupil size in patients with glaucoma.

BACKGROUND: Pupil size is an important factor in predicting post-operative satisfaction. We assessed the correlation between pupil size, measured by Humphrey static perimetry, and various affecting factors in patients with glaucoma. METHODS: In total, 825 eyes of 415 patients were evaluated retrospectively. Pupil size was measured with Humphrey static perimetry. Comparisons of pupil size according to the presence of glaucoma were evaluated, as were correlations between pupil size and various factors, including age, logMAR best corrected visual acuity (BCVA), retinal nerve fiber layer (RNFL) thickness, spherical equivalent, intraocular pressure, axial length, central corneal thickness, white-to-white, and the kappa angle. RESULTS: Pupil size was significantly smaller in glaucoma patients than in glaucoma suspects (p < 0.001) or the normal group (p < 0.001). Pupil size decreased significantly as age (p < 0.001) and central cornea thickness (p = 0.007) increased, and increased significantly as logMAR BCVA (p = 0.02) became worse and spherical equivalent (p = 0.007) and RNFL thickness (p = 0.042) increased. In patients older than 50 years, pupil size was significantly larger in eyes with a history of cataract surgery. CONCLUSIONS: Humphrey static perimetry can be useful in measuring pupil size. Pupil size was significantly smaller in eyes with glaucoma. Other factors affecting pupil size can be used in a preoperative evaluation when considering cataract surgery or laser refractive surgery.

In situ Generation of Reticulate Micropores through Covalent Network/Polymer Nanocomposite Membranes for Reverse-Selective Separation of Carbon Dioxide.

We demonstrate the synthesis of a microporous covalent-network membrane derived from co-continuous blends of a porogenic urea network and a polyimide (PI). We show that the urea networks in the PI matrix may be thermally rearranged while selectively expelling small molecular fragments, thereby forming a new network bearing reticular microporous molecular pathways. The porous structures enable reverse-selective gas separation, efficiently blocking carbon dioxide to which most polymeric membranes exhibit selective permeability. The proposed method for fabricating microporous organic membranes with highly tunable porosities using a variety of chemical structures and processing parameters is facile and shows promise for the creation of new membrane-based molecular-separation techniques.

Bicontinuous Nanoporous Frameworks: Caged Longevity for Enzymes.

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three- dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme-loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.

Two nuclear export signals of Cdc6 are differentially associated with CDK-mediated phosphorylation residues for cytoplasmic translocation.

Cdc6 is cleaved at residues 442 and 290 by caspase-3 during apoptosis producing p49-tCdc6 and p32-tCdc6, respectively. While p32-tCdc6 is unable to translocate into the cytoplasm, p49-tCdc6 retains cytoplasmic translocation activity, but it has a lower efficiency than wild-type Cdc6. We hypothesized that a novel nuclear export signal (NES) sequence exists between amino acids 290 and 442. Cdc6 contains a novel NES in the region of amino acids 300-315 (NES2) that shares sequence similarity with NES1 at residues 462-476. In mutant versions of Cdc6, we replaced leucine with alanine in NES1 and NES2 and co-expressed the mutant constructs with cyclin A. We observed that the cytoplasmic translocation of these mutants was reduced in comparison to wild-type Cdc6. Moreover, the cytoplasmic translocation of a mutant in which all four leucine residues were mutated to alanine was significantly inhibited in comparison to the translocation of wild-type Cdc6. The Crm1 binding activities of Cdc6 NES mutants were consistent with the efficiency of its cytoplasmic translocation. Further studies have revealed that L468 and L470 of NES1 are required for cytoplasmic translocation of Cdc6 phosphorylated at S74, while L311 and L313 of NES2 accelerate the cytoplasmic translocation of Cdc6 phosphorylated at S54. These results suggest that the two NESs of Cdc6 work cooperatively and distinctly for the cytoplasmic translocation of Cdc6 phosphorylated at S74 and S54 by cyclin A/Cdk2.

DNA Hypermethylation Inhibits the CD82 Metastasis Suppressor Gene in Gastric Cancer.

BACKGROUND/AIM: Gastric cancer, with its high global incidence and mortality rates, poses a significant challenge due to the rapid decline in patient survival upon metastasis. Understanding and combating metastasis are crucial in improving outcomes. The metastasis suppressor gene CD82 has demonstrated efficacy in inhibiting metastasis across various carcinomas but is frequently down-regulated. However, its role and regulatory mechanisms in gastric cancer remain elusive. MATERIALS AND METHODS: Utilizing public data, we assessed patient survival in relation to CD82 expression. CD82 expression in gastric cancer cell lines was evaluated via western blotting, and its impact on cell mobility was assessed through wound healing and Transwell assays. The demethylation of CD82 was induced using 5-aza-deoxycytidine, while methylation levels were detected via methylation-specific PCR. RESULTS: Low CD82 expression correlated with poor prognosis in patients, and down-regulation and over-expression of CD82 significantly affected cell mobility. Treatment with 5-aza-deoxycytidine restored CD82 expression in low-expressing cell lines, highlighting its methylation-dependent regulation. CONCLUSION: CD82 serves as a pivotal regulator of cell mobility in gastric cancer by suppressing metastasis. Its expression is attenuated in gastric cancer cells through promoter hypermethylation.

Phosphorylation of Cdc6 at serine 74, but not at serine 106, drives translocation of Cdc6 to the cytoplasm.

Phosphorylation-dependent cytoplasmic translocation of human Cdc6 during S phase is sufficient to control its activity after origin firing. Export from the nucleus also serves as a mechanism for preventing re-replication in mammalian cells. Phosphorylation of the CDK consensus serine residues 54, 74, and 106 has been suggested to be involved in the cytoplasmic translocation of Cdc6. To determine the relative importance of the three phosphorylation sites, we have generated Cdc6 variants by substituting one or more of the three serine residues with alanine or aspartic acid and have assessed their cytoplasmic translocation behavior. Phosphorylation of serine 74 mainly contributes to the cytoplasmic translocation of Cdc6, while serine 54 phosphorylation provides a minor contribution. In contrast, phosphorylation at serine 106 does not affect the nuclear export of Cdc6. Comparative results were found in cells coexpressing the phosphorylation defective mutants of Cdc6 and cyclin A as well as in non-transfected cells synchronized by their release from a double thymidine block. We conclude that Cdk-mediated phosphorylation of Cdc6 at serine 74 is required for the cytoplasmic translocalization of Cdc6 during the cell cycle. Phosphorylation of Cdc6 at serine 54 plays a minor role and phosphorylation of serine 106 plays no role in the cytoplasmic localization of Cdc6. The phosphorylation of S74 in Cdc6 could be important for binding to the nuclear export protein for translocalization.

Solid-state combinatorial chemistry of Eu(2+)-doped Sr-Al-Si-O-N phosphors.

Sr-Al-Si-O-N composition space was screened by a solid state combinatorial chemistry. For this sake, powder mixtures of Sr3N2, alpha-Si3N4, AIN and Eu3N2 was fired at 1500 degrees C-1900 degrees C for 2 h under 1.0 Mpa N2 using a gas pressurized sintering (GPS) furnace. The resultant phosphors were phase-identified, and the photo luminescence was examined. The Sr-Al-Si-O-N phosphors are blue-Green and orange in color and emit in the region of 520-630 nm depending on synthesized temperature. Considering an intense excitation band in blue LED and emission band, these materials can be used as novel conversion phosphor for White-LEDs, if the luminance was improved.

Heuristics-assisted combinatorial screening of oxynitride phosphors.

Nitride or oxynitride phosphors have been recently acting as key phosphors in the light emitting diode (LED) application. In particular, their superiority to the conventional oxide-based phosphors in terms of efficacy, thermal stability, color rendering, and etc. made it possible to achieve rapid commercialization of several nitride or oxynitride phosphors such as CaAISiN3, alpha- and beta-Sialons, Sr2Si5N8, and etc. However, it is still necessary to discover more nitride or oxynitride phosphors, which meet specific requirements for LED applications. In this regard, heuristics-based combinatorial material search (HCMS) strategies have been applied to multi-compositional inorganic systems to search for new phosphors and to optimize the properties of phosphors in the six dimensional SrCO3-BaCO3-CaCO3-SiO2-Si3N4-Eu2O3 search space. The heuristics strategies include non-dominated sorting genetic algorithm (NSGA) and particle swarm optimization (PSO).

Cervical Myelopathy Due to Epidural Hematoma at the Cervicomedullary Junction Associated With Ventriculoperitoneal Shunt Overdrainage: A Case Report.

We present a case of cervical myelopathy caused by epidural hematoma formation due to chronic cerebrospinal fluid overdrainage. A 55-year-old man who underwent ventriculoperitoneal (V-P) shunt surgery for normal pressure hydrocephalus presented with progressive weakness of both the upper and lower extremities. Magnetic resonance imaging (MRI) revealed compressive myelopathy at the cervicomedullary junction at the C1-C2 level caused by epidural hematoma formation due to intracranial hypotension (IH) caused by a complication of V-P shunt. He underwent decompressive laminectomy and hematoma removal at C1-C2 and replacement of the V-P shunt valve. Follow-up cervical spine MRI showed an improved state of severe central spinal stenosis at the C1-C2 level and an improved state of compression-related cord signal intensity change in the spinal cord. After surgical intervention and intensive rehabilitation, the patient showed clinical improvement. If cervical myelopathy is suspected in patients with a shunt, cord compression due to venous engorgement or hematoma caused by over-shunting and IH should be considered.

Effects of the surface treatment with monolayers of twisted biaryls on the efficiency of pentacene thin-film transistors.

A pentacene thin-film transistor (TFT) was fabricated on a SiO2 gate insulator modified with twisted biaryls. The biaryl monolayer, in particular a binaphthyl (BN) monolayer, is amorphous surface where the naphthalene rings are randomly oriented with no lateral order because of their rigid, twisted, and asymmetric shape. When the BN monolayer was used for the surface treatment of SiO2, large grains were obtained in the early stages of the pentacene crystal growth. The pentacene TFT had a field effect mobility (microm) in excess of 0.4 cm2/Vs and an on/off ratio greater than 10(5). The surface treatment improved the mobility of the pentacene TFT by a factor of 50% compared with non-treated devices. The morphology of the semiconductor layer was investigated using atomic force microscopy (AFM) and X-ray diffraction (XRD).

Electrical switching between vesicles and micelles via redox-responsive self-assembly of amphiphilic rod-coils.

An aqueous vesicular system that is switchable by electric potential without addition of any chemical redox agents into the solution is demonstrated using redox-responsive self-assembly of an amphiphilic rod-coil molecule consisting of a tetraaniline and a poly(ethylene glycol) block. The vesicle membrane is split by an oxidizing voltage into smaller pucklike micelles that can reassemble to form vesicles upon exposure to a reducing voltage. The switching mechanism is explained by the packing behavior of the tetraaniline units constituting the membrane core, which depends on their oxidation states.

Polymeric self-assembled monolayers derived from surface-active copolymers: a modular approach to functionalized surfaces.

Physical or covalent adsorption of surface-active block or random copolymers consisting of anchoring units and functional units onto solid surfaces yields polymeric self-assembled monolayers (PSAMs) with designed chemical and morphological structures and functionalities. This tutorial review provides an overview of PSAMs derived from various types of copolymers. It also discusses design principles for PSAMs to tune interfacial and surface interactions of materials for potential applications.