Subglottic Mass With Hoarseness and Difficulty Breathing.

A man in his 70s was referred for a 5-cm submandibular mass, hoarseness, and difficulty breathing with no cough, blood in sputum, or dysphagia. What is your diagnosis?

Centric Sc(HPO3)(H2PO3)(H2O) and Acentric Sc(H2PO3)3: Two Ultraviolet Scandium Phosphite Optical Crystals.

Exploring ultraviolet (UV) nonlinear-optical (NLO) materials is significant for the conversion of a high-frequency laser. Two scandium phosphites, Sc(HPO3)(H2PO3)(H2O) and Sc(H2PO3)3, were successfully synthesized. Centric Sc(HPO3)(H2PO3)(H2O) exhibits a short UV cutoff edge (<200 nm) and a unique double-layer structure of [Sc2(HPO3)2(H2PO3)2(H2O)2]∞. The acentric Sc(H2PO3)3 exhibits a three-dimensional [Sc(H2PO3)3]∞ structure with a large band gap of 4.05 eV, and it demonstrates a moderately phase-matchable second-harmonic-generation response [0.60 × KDP (KH2PO4)] at 1064 nm. The crystal structures, optical properties, and theoretical calculations of the two compounds are discussed. This work will promote the exploration of new NLO phosphite materials.

Increased SERPINB2 potentiates 15LO1 expression via STAT6 signalling in epithelial cells in eosinophilic chronic rhinosinusitis with nasal polyps.

BACKGROUND: SERPINB2, a biomarker of Type-2 (T2) inflammatory processes, has been described in the context of asthma. Chronic rhinosinusitis with nasal polyps (CRSwNP) is also correlated with T2 inflammation and elevated 15LO1 induced by IL-4/13 in nasal epithelial cells. The aim of this study was to evaluate the expression and location of SERPINB2 in nasal epithelial cells (NECs) and determine whether SERPINB2 regulates 15LO1 and downstream T2 markers in NECs via STAT6 signalling. METHODS: SERPINB2 gene expression in bulk and single-cell RNAseq database was analysed by bioinformatics analysis. SERPINB2, 15LO1 and other T2 markers were evaluated from CRSwNP and HCs NECs. The colocalization of SERPINB2 and 15LO1 was evaluated by immunofluorescence. Fresh NECs were cultured at an air-liquid interface with or without IL-13, SERPINB2 Dicer-substrate short interfering RNAs (DsiRNAs) transfection, exogenous SERPINB2, 15-HETE recombinant protein and pSTAT6 inhibitors. 15LO1, 15-HETE and downstream T2 markers were analysed by qRT-PCR, western blot and ELISA. RESULTS: SERPINB2 expression was increased in eosinophilic nasal polyps compared with that in noneosinophilic nasal polyps and control tissues and positively correlated with 15LO1 and other downstream T2 markers. SERPINB2 was predominantly expressed by epithelial cells in NP tissue and was colocalized with 15LO1. In primary NECs in vitro, SERPINB2 expression was induced by IL-13. Knockdown or overexpression SERPINB2 decreased or enhanced expression of 15LO1 and 15-HETE in NECs, respectively, in a STAT6-dependent manner. SERPINB2 siRNA also inhibited the expression of the 15LO1 downstream genes, such as CCL26, POSTN and NOS2. STAT6 inhibition similarly decreased SERPINB2-induced 15LO1. CONCLUSIONS: SERPINB2 is increased in NP epithelial cells of eosinophilic CRSwNP (eCRSwNP) and contributes to T2 inflammation via STAT6 signalling. SERPINB2 could be considered a novel therapeutic target for eCRSwNP.

Unraveling CO adsorption behaviors and its poisoning effects on ZrCo surface.

Theoretical calculations are performed to elucidate the adsorption behaviors and poisoning effects of CO gas on the ZrCo surface, which drastically limits its application in hydrogen isotopic storage. Specifically, the ionic Zr-Co bond on the surface leads to unique CO adsorption structures on different sites. The CO molecule tends to prefer a tilted adsorption configuration on the Co-Co bridge site. The electronic structures, charge distributions, and bonding characteristics are further explored to study the CO adsorption properties, which obey the electron density donation and back-donation mechanism. For different CO coverages, the stepwise adsorption energies of CO increase with the increasing of coverage, reaching the saturated coverage at nCO = 11. Then, the effects of temperature and partial pressure on CO coverage are evaluated using atomic thermodynamics. The computed phase diagram shows that the ZrCo(110) surface has a stable coverage of nCO = 6 at ambient temperature under ultrahigh vacuum conditions. The pre-adsorbed CO molecules lead to the charge redistribution and the d-band center downshift on the surface, which significantly affect hydrogen adsorption and dissociation. Our results provide insights into the poisoning mechanisms of the impurity gas on ZrCo alloys, which can be beneficial for designing high-performance ZrCo-based alloys with improved poisoning tolerance.

Centrosymmetric CaBaMF8 and Noncentrosymmetric Li2CaMF8 (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design.

Zirconium/hafnium fluorides have recently been recognized as potential nonlinear optical (NLO) materials with short ultraviolet (UV) cutoff edges, which is significant in laser science and industry. The synthesis of noncentrosymmetric (NCS) materials based on centrosymmetric (CS) compounds by an isovalent cation substitution-oriented design is an emerging strategy in the NLO territory. Here, two isostructural and novel fluorides, CaBaMF8 (M = Zr (1), Hf (2)), have been synthesized through the combination of alkaline earth metals, zirconium/hafnium, and fluorine elements. They feature zero-dimensional and CS structures composed by an isolated MF8 (M = Zr, Hf) dodecahedron and dissociative Ca2+ and Ba2+ cations, and they display short UV cutoff edges (<200 nm) as well. Two three-dimensional fluorides Li2CaMF8 (M = Zr (3), Hf (4)) are obtained by replacing Ba with alkali metal Li atom, which not only represent phase-matchable second-harmonic-generation activities (0.36, 0.30× KH2PO4 (KDP)) at 1064 nm but also maintain short UV cutoff edges with high reflectance. This work has largely enriched the family of NCS zirconium/hafnium fluorides reaching the short UV region.

Hg16O12(NO3)6F2(H2O): A Mercury-Rich Nitrate Oxyfluoride with Diverse Triple-Coordinated Mercury-Based Units That Exhibits an Unparalleled [(Hg16O12F2(H2O))6+]∞ Cationic Framework and a Large Birefringence.

Designing new compounds based on anion regulation has been widely favored due to the production of diverse crystal structures and excellent optical properties. Here, a new nitrate oxyfluoride, Hg16O12(NO3)6F2(H2O), has been obtained through a hydrothermal reaction. It crystallizes in the centric Ibca space group and shows a novel three-dimensional [(Hg16O12F2(H2O))6+]∞ cationic framework composed of interconnected HgO2F, HgO3, and HgO2(H2O) units, with isolated NO3- groups as balanced anions to build the whole structure. Notably, the HgO2F and HgO2(H2O) units are first presented here among mercury (Hg)-based compounds. Additionally, Hg16O12(NO3)6F2(H2O) exhibits a large birefringence of 0.17 at 546 nm. This work enriches the multiformity of Hg-based compounds and provides a route for developing promising birefringent materials.

[C(NH2)3]6Mo7O24: A Guanidinium Molybdate as a UV Nonlinear Optical Crystal with Large Birefringence.

The key to searching novel nonlinear optical (NLO) crystals was effectively combining the NLO-active units to obtain a noncentrosymmetric structure. Nevertheless, the present predicament lies in the growing challenge of discovering novel crystals within conventional inorganic frameworks that surpass the properties of the current NLO materials. In view of this, researchers expanded their research focus to the organic-inorganic hybridization system; it is foreseeable to concentrate the advantages from several kinds of NLO-active units to acquire novel NLO crystals with superior properties. We herein report an organic-inorganic hybrid molybdate crystal, namely, [C(NH2)3]6Mo7O24 (GMO). It was successfully obtained via combining inorganic NLO-active MoO6 octahedra and organic π-conjugated [C(NH2)3]+ groups. GMO demonstrates a moderate second-harmonic-generation response, specifically measuring about 1.3 times the value of KDP. Additionally, it exhibits a significant birefringence value of 0.203 at the wavelength of 550 nm and possesses a wide band gap of 3.31 eV. Theoretical calculations suggest that the optical properties of the GMO are primarily influenced by the synergy effect of [C(NH2)3]+ groups between MoO6 octahedra.

Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis-[Zr6F34]10- clusters.

Traditional fluorides are rarely reported as candidates for nonlinear optical (NLO) materials featuring a deep-ultraviolet cutoff edge. Theoretical investigations suggest that the ZrF8 dodecahedron shows large polarizability anisotropy and benefits for large birefringence. Herein, a new fluorine-rich fluoride, K3Ba2Zr6F31, was synthesized by coupling the ZrF8 group, featuring acentric cis-[Zr6F34]10- clusters with a 63-screw axis. Significantly, K3Ba2Zr6F31 exhibits a short UV cutoff edge (below 200 nm) and moderate second-harmonic generation (SHG) response (0.5 × KH2PO4). It also possesses a relatively large birefringence (0.08@1064 nm), together with a broad transparency window (2.5-21.1 µm). First-principles calculations suggest that the cis-[Zr6F34]10- cluster built by ZrF8 dodecahedra are the dominant contributors to the large band gap (7.89 eV, cal.) and SHG response simultaneously. Such systematic work highlights that Zr-based fluorides afford a new paradigm for the development of efficient NLO materials with a short UV cutoff edge.

Safety and efficacy of protective stent insertion to prevent carotid blowout syndrome at the distal internal carotid artery in nasopharyngeal carcinoma patients: a comparison with endovascular occlusion.

Background: Carotid blowout syndrome (CBS) frequently occurs at the distal internal carotid artery (distal-ICA) in patients with nasopharyngeal carcinoma (NPC), and remedial treatments run a high risk for neurologic complications. A case-control study was conducted to evaluate the safety and efficacy of protective stent insertion at the distal-ICA to prevent CBS in NPC patients, with a comparison to endovascular coil occlusion. Methods: A total of 28 consecutive NPC patients at high risk of CBS from June 2019 to December 2021 in Shanghai Sixth People's Hospital (a tertiary institution) were retrospectively included and divided into a stent protection group and occlusion group. Technique feasibility, treatment outcomes and neurological deficiency were compared between the two groups by two-sample test. Kaplan-Meier analysis compared patients' survival rates at mid-term follow-up. Results: Stent insertion was performed in 15 patients and ICA occlusion in 13 patients. The technical success rate was 100% in both groups. Procedure-related ischemic stroke was identified in 2 patients (15.4%) in the occlusion group, compared with none in the stent protection group. Bleeding was encountered in one patient in the stent protection group and one patient in the occlusion group, each. During a median follow-up of 10.5 (range, 2-31) months, 3 patients (20%) showed asymptomatic in-stent occlusion in the stent protection group. Notably, the median survival time was significantly longer in the stent protection group than in the occlusion group (23.3 vs. 15.8 months, P=0.04). Conclusions: Protective stenting the distal-ICA was similarly effective in preventing CBS in NPC patients but was safer than endovascular occlusion of ICA.

[C(NH2)3][B(C2O2H4)2]: An Organic-Inorganic Hybrid Borate Containing Nonlinear-Optical Active Unit [B(C2O2H4)2]- with Solar-Blind-Region Optical Nonlinearity.

We herein report an unprecedented organic-inorganic hybrid borate incorporating a novel nonlinear-optical (NLO) active unit, namely, [C(NH2)3][B(C2O2H4)2]. The novel NLO active unit was derived from the condensation reaction between two glycol molecules and one (BO4)5- group. The title compound exhibits a moderate second-harmonic-generation effect (0.7 × KDP), a significant band gap (5.76 eV), and a suitable birefringence (0.078 at 550 nm). The optical properties are determined by the synergistic interaction between the C(NH2)3+ cation and the [B(C2O2H4)2]- group, as indicated by theoretical calculations.

From ZnF2 to ZnF2(H2O)4: Partial Substitution Achieves Structural Transformation and Nonlinear Optical Activity while Keeping Short Ultraviolet Cutoff Edge.

Exploring nonlinear optical (NLO) materials with short ultraviolet cutoff edges are significant for developing an all-solid-state laser. Here, a noncentrosymmetric zinc fluoride hydrate, ZnF2(H2O)4, was synthesized by a hydrothermal method. It crystallizes in the polar space group of Pca21. The compound consists of the central Zn2+ combined with F- and coordination water to form the [ZnF2(H2O)4] octahedra, and each octahedron is isolated from each other to form a 0-dimensional structure. As an acentric compound, ZnF2(H2O)4 shows a phase-matchable second-harmonic-generation (SHG) activity with an intensity about 0.5 times that of KH2PO4. More attractively, it also shows a short ultraviolet cutoff edge below 200 nm, which is rare in reported halide hydrate systems. Interestingly, from ZnF2 to ZnF2(H2O)4, the partial substitution of the coordinated F atoms by H2O molecules leads to the structural transformation from centric to acentric with SHG activity off to on. Structural analyses, NLO activity, and theoretical calculations are presented in this work.

Endoscopic endonasal combined transoral medial approach to the nasopharynx, parapharyngeal space, and jugular foramen.

OBJECTIVE: This study aimed to validate the feasibility of an endoscopic endonasal combined transoral medial approach for treating lesions in the nasopharynx, parapharyngeal space (PPS), and jugular foramen. METHODS: Anatomical and imaging information of six patients who underwent surgery via this approach were reviewed and analyzed. RESULTS: The feasibility and advantages of the endoscopic endonasal combined transoral medial approach, which uses an inside-to-outside medial surgical corridor, were identified. Total resection was achieved in 3 cases with benign tumors. Safe resection margins were obtained in 2 cases with recurrent nasopharyngeal carcinoma (NPC). Pathological biopsy of NPC lesion between the Eustachian tube and arterial sheath was achieved. The internal carotid artery (ICA) was accurately located and protected in all cases and no complications occurred. CONCLUSION: Lesions in the nasopharynx, PPS, and jugular foramen can be directly assessed via this approach. The ICA can be well identified during the surgery.

Ba4B14O25: A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron-Rich Closed-Loop Strategy.

Discovering new deep ultraviolet (DUV) nonlinear optical (NLO) materials is the current research hotspot. However, how to perfectly integrate several stringent performances into a crystal is a great challenge because of the natural incompatibility among them, particularly wide band gap and large NLO coefficient. To tackle the challenge, a boron-rich closed-loop strategy is supposed, based on which a new barium borate, Ba4B14O25, is designed and synthesized successfully via the high-temperature solid-state melting method. It features a highly polymeric 3D geometry with the closed-loop anionic framework [B14O25]8- constructed by the fundamental building blocks [B14O33]24-. The high-density π-conjugated [BO3]3- groups and the fully closed-loop B-O-B connections make Ba4B14O25 possess excellent NLO properties, including short UV cutoff edge (<200 nm), large second harmonic generation response (3.0 × KDP) and phase-matching capability, being a promising DUV-transparent NLO candidate material. The work provides a creative design strategy for the exploration of DUV NLO crystals.

C(NH2)3Cd(C2O4)Cl(H2O)·H2O and BaCd(C2O4)1.5Cl(H2O)2: Two Oxalate Chlorides Obtained by Chemical Scissors Strategy Exhibiting Low-Dimensional Structural Networks and Balanced Overall Optical Properties.

Low-dimensional crystalline materials have attracted much attention due to their special physical and chemical properties. Herein, two new oxalate chlorides, C(NH2)3Cd(C2O4)Cl(H2O)·H2O and BaCd(C2O4)1.5Cl(H2O)2, were synthesized. C(NH2)3Cd(C2O4)Cl(H2O)·H2O presents the unique {[Cd(C2O4)Cl(H2O)]-}∞ zigzag chain, while BaCd(C2O4)1.5Cl(H2O)2 shows a novel {[Cd(C2O4)1.5Cl]2-}∞ layer. They showed large measured band gaps, which were 3.76 and 4.53 eV, respectively, and the latter was the largest band gap in the A-M-C2O4-X (A = Monovalent cationic or alkaline earth metals, X = F, Cl, Br, I) family. They exhibit a large calculated birefringence of 0.075 and 0.096 at 1064 nm, respectively. This study promotes the exploration of synthesizing low-dimensional crystalline materials with balanced overall optical performances by a chemical scissors strategy.

Increased prevalence of aspiration pneumonitis in spontaneous cerebrospinal fluid leaks.

BACKGROUND: Aspiration pneumonitis (AP) secondary to cerebrospinal fluid (CSF) leak is underestimated and rarely discussed. This study aimed to evaluate the association between AP and CSF leaks. METHODS: Clinical and surgical characteristics of CSF leak patients with and without AP between January 2010 and December 2022 were included and compared. RESULTS: This study included 159 patients, 16 with CSF otorrhea and 143 with CSF rhinorrhea. Among them, 40 (25.2%) had AP. Bilateral pneumonitis was identified in 32 cases, of which 11 showed severe pneumonitis in the right upper lung lobe. Twenty-one (52.5%) asymptomatic and 19 (47.5%) symptomatic cases were documented. The major clinical manifestations included cough (n = 19, 47.5%) and expectoration (n = 9, 22.5%). The prevalence of pneumonitis was significantly higher in the spontaneous group than in the traumatic group. High-flow CSF leak was associated with AP (42.5% vs. 16.8%, p = 0.001). No significant differences were identified in defect locations between patients with and without AP. Patients with pneumonitis had a higher prevalence of meningitis (32.5% vs. 12.6%, p = 0.003). Multiple logistic regression results revealed that meningitis, spontaneous and high-flow CSF leaks are independent factors for AP occurrence. Both the CSF leak and pulmonary complications resolved following successful surgical repair. CONCLUSIONS: AP secondary to CSF leaks is frequently underdiagnosed, with a higher incidence identified in spontaneous cases. The occurrence of AP was associated with high-flow CSF leak.

Na2 CeF6 : A Highly Laser Damage-Tolerant Double Perovskite Type Ce(IV) Fluoride Exhibiting Strong Second-Harmonic Generation Effect.

Perovskite structure compounds are significant candidates for designing new optical function materials due to their structural variability. Here, an inorganic tetravalent cerium fluoride, Na2 CeF6 , is derived from the perovskite structure through double-site cation co-substitution. Na2 CeF6 crystalizes in the non-centrosymmetric space group P 6 ¯ 2 m ${P}^{\bar{6}}2m$ . Edge-sharing connected NaF9 and CeF9 polyhedra build the whole 3D structure of Na2 CeF6 . Importantly, it represents the first Ce(IV) fluoride nonlinear optical (NLO) crystal and can produce a strong and phase-matchable second-harmonic generation (SHG) effect of ≈2.1 times that of KH2 PO4 (KDP), making it the strongest among non-lone pair electron metal fluoride system. Further, it exhibits a high laser-induced damage threshold (LIDT) of 74.65-76.25 MW cm-2 , which is over 20 times that of AgGaS2 . It also exhibits a wide transparent region (0.5-14.3 µm). This work provides a facile route for exploring high-performance halide NLO materials.

Single-Layer GaInSe3: Promising Water-Splitting Photocatalyst with Solar Conversion Efficiency over 30% from Theoretical Calculations.

Hydrogen energy from solar water-splitting is known as an ideal method with which to address the energy crisis and global environmental pollution. Herein, the first-principles calculations are carried out to study the photocatalytic water-splitting performance of single-layer GaInSe3 under biaxial strains from -2% to +2%. Calculations reveal that single-layer GaInSe3 under various biaxial strains has electronic bandgaps ranging from 1.11 to 1.28 eV under biaxial strain from -2% to +2%, as well as a completely separated valence band maximum and conduction band minimum. Meanwhile, the appropriate band edges for water-splitting and visible optical absorption up to ~3 × 105 cm-1 are obtained under biaxial strains from -2% to 0%. More impressively, the solar conversion efficiency of single-layer GaInSe3 under biaxial strains from -2% to 0% reaches over 30%. The OER of unstrained single-layer GaInSe3 can proceed without co-catalysts. These demonstrate that single-layer GaInSe3 is a viable material for solar water-splitting.

Na4[B6O9 (OH)3](H2O) Cl: A Deep-Ultraviolet Transparent Nonlinear Optical Borate Chloride with {[B6O9 (OH)3]3-}∞ Chains.

The development of nonlinear-optical (NLO) crystals with short ultraviolet cutoff edges is significant and challenging. Here, a new sodium borate chloride, Na4[B6O9 (OH)3](H2O) Cl, was successfully obtained by the mild hydrothermal method, which crystallizes in a polar space group Pca21. The structure of the compound is characterized by {[B6O9 (OH)3]3-}∞ chains. Measurements of optical properties indicate the compound exhibits a deep-ultraviolet (DUV) cutoff edge (≤200 nm) and moderate second harmonic generation response (0.4 × KH2PO4). It presents the first DUV hydrous sodium borate chloride NLO crystal and the first sodium borate chloride possessing a one-dimensional B-O anion framework. Probing into the connection of structure and optical properties has been performed based on theoretical calculations. These results are instructive for designing and obtaining new DUV NLO materials.

A Ni(II) Coordination Polymer as a Multifunctional Luminescent Sensor for Detection of UO22+, Cr2O72-, CrO42- and Nitrofurantoin.

A new Ni coordination polymer [Ni(MIP)(BMIOPE)]n (1) was constructed (BMIOPE = 4,4'-bis(2-methylimidazol-1-yl)diphenyl ether, and H2MIP = 5-methylisophthalic acid), possessing two-dimensional (2D) twofold parallel interwoven net structure with a 44∙62 point symbol. Complex 1 has been successfully obtained based on mixed-ligand strategy. The fluorescence titration experiments revealed that complex 1 could act as multifunctional luminescent sensor to simultaneously detect UO22+, Cr2O72- and CrO42-, and NFT (nitrofurantoin). The limit of detection (LOD) values for complex 1 are 2.86 × 10-5, 4.09 × 10-5, 3.79 × 10-5 and 9.32 × 10-5 M for UO22+, Cr2O72-, CrO42- and NFT. The Ksv values are 6.18 × 103, 1.44 × 104, 1.27 × 104 and 1.51 × 104 M-1 for NFT, CrO42-, Cr2O72- and UO22+. Finally, the mechanism of its luminescence sensing is studied in detail. These results manifest that complex 1 is a multifunctional sensor for sensitive fluorescent UO22+, Cr2O72-, CrO42- and NFT detection.

SrCl2·6H2O: An Alkaline-Earth-Metal Chloride Hexahydrate as Deep-Ultraviolet Nonlinear-Optical Crystal with the {[Sr(H2O)6]2+}∞ Cationic Framework.

Exploring deep-ultraviolet (DUV) nonlinear-optical (NLO) materials is significant for the conversion of high-frequency laser. Herein, two alkali-earth-metal halide hexahydrates, SrX2·6H2O (X = Cl, Br), were obtained, and the centimeter-sized single crystals of SrCl2·6H2O were grown by a slow evaporation method. Both of them crystallize in the trigonal space group P321, and their crystal structures show {[Sr(H2O)6]2+}∞ cationic chains, with isolated Cl- or Br- anions interspersed between the chains. SrCl2·6H2O exhibits a moderate second-harmonic-generation response (0.4 × KDP) at 1064 nm and can realize phase matching. Importantly, SrCl2·6H2O has a short ultraviolet cutoff edge (<200 nm). Crystal growth, crystal structures, optical performances, and theoretical calculations of the title and related compounds have been discussed in this work. This study enriches the understanding of metal halide hydrates as NLO materials in the DUV region.