Effect of fluorine doping on the NO2-sensing properties of MoS2nanoflowers.

The somewhat slow recovery kinetics of NO2sensing at low temperatures are still challenging to overcome. To enhance the gas sensing property, fluorine is doped to MoS2nanoflowers by facile hydrothermal method. Extensive characterization data demonstrate that F was effectively incorporated into the MoS2nanoflowers, and that the microstructure of the MoS2nanoflowers did not change upon F doping. The two MoS2doped with varying concentrations of fluorine were tested for their sensing property to NO2gas. Both of them show good repeatability and stability. A smaller recovery time was seen in the F-MoS2-1 sample with a little amount of F loading, which was three times quicker than that of pure MoS2. The key reason for the quicker recovery time of this material was found to be the fluorine ions that had been adsorbed on the surface of F-MoS2-1 would take up some of the NO2adsorption site. Additionally, the sample F-MoS2-2 with a higher F doping level demonstrated increased sensitivity. The F-MoS2-2 sensor's high sensitivity was mostly due to the lattice fluorine filled to the sulfur vacancy, which generated impurity levels and reduced the energy required for its electronic transition. This study might contribute to the development of new molybdenum sulfide based gas sensor.

Purification, Immunological Identification, and Characterization of the Novel Silkworm Pupae Allergen Bombyx mori Lipoprotein 3 (Bomb m 6).

Allergic reactions caused by silkworm pupae greatly limit their utilization, and studies suggest that silkworm pupae proteins of 25-30 kDa may be the principal allergens. To further understand these allergens, we attempted to purify a protein of about 30 kDa by ammonium sulfate salting, pH-graded precipitation, and ion-exchange chromatography. The protein was identified by mass spectrometry and characterized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), western blot, enzyme-linked immunosorbent assays, circular dichroism, and fluorescence spectroscopy analyses. We identified the purified protein as Bombyx mori lipoprotein 3 (Bmlp3), which has high IgE reactivity and is a novel uncharacterized allergen that we named Bomb m 6 according to the WHO/IUIS Allergen Nomenclature Sub-Committee. This allergen is stable against heat, acids, bases, and digestion. In conclusion, we successfully purified and characterized a novel silkworm pupa allergen, which may inform the diagnosis and treatment of silkworm pupa allergies.

Connexin 43 overexpression induces lung cancer angiogenesis in vitro following phosphorylation at Ser279 in its C-terminus.

Blocking angiogenesis can inhibit tumor growth and metastasis. However, the mechanism underlying regulation of lung cancer angiogenesis remains unclear. The gap junction protein connexin 43 (Cx43) is implicated in angiogenesis. The aim of the present study was to determine the role of Cx43 in angiogenesis in vitro and its signaling pathways. Human pulmonary microvascular endothelial cells were transfected with Cx43-targeting siRNA or Cx43-overexpressing recombinant plasmid vector. Reverse transcription-quantitative polymerase chain reaction and western blotting were performed to determine Cx43, zonula occludens-1 (ZO-1), E-cadherin, ß-catenin, von Willebrand factor (vWF), and plasminogen activator inhibitor-1 (PAI-1) mRNA and protein expression levels, respectively. Tyr265, Ser279, Ser368, and Ser373 phosphorylation levels in the C-terminus of Cx43 and intracellular and membranal Cx43 contents were determined using western blotting. Additionally, immunofluorescence, tube formation, Cell Counting Kit-8, and Transwell migration assays were performed. The results revealed that compared with that in the control samples, Cx43, ZO-1, E-cadherin, ß-catenin, vWF, and PAI-1 mRNA and protein expression were significantly increased in the Cx43 overexpression group and significantly decreased in the Cx43-knockdown group. Moreover, the phosphorylation level of Ser279 as well as cell proliferation and migration rates were markedly increased in the Cx43 overexpression group, and tube formation revealed that the potential of angiogenesis was also increased. Conversely, in the Cx43-knockdown group, the phosphorylation level of Ser279 and cell proliferation and migration rates were reduced, and the potential of angiogenesis was greatly impaired. Under Cx43 overexpression, membranal Cx43 content was significantly increased, whereas under Cx43 knockdown, it was significantly reduced. Therefore, Cx43 overexpression could induce pulmonary angiogenesis in vitro by promoting cell proliferation and migration and activating ZO-1, E-cadherin, ß-catenin, vWF, and PAI-1. This may be achieved by promoting phosphorylation and activation of the intracellular signal site Ser279 at the C-terminus of Cx43.

Successful resolution of ectopic Cushing syndrome by minimally invasive thoracoscopic resection of the neuroendocrine tumor of the thymus: a rare case report.

BACKGROUND: Ectopic Cushing syndrome (ECS) is a sporadic condition. Even uncommon is an ECS that derives from a carcinoid tumor of the thymus. These tumors may pose several diagnostic and therapeutic conundrums. This report discusses the differential diagnosis, clinicopathological findings, and effective treatment of a rare case of ECS using a minimally invasive approach. CASE PRESENTATION: A 29-year-old woman with Cushing syndrome presented with facial flushing. Physical examination revealed hypertension (blood pressure: 141/100 mmHg). A mediastinal tumor was discovered to be the cause of the patient's chronic hypokalemia and hypercortisolemia. Cortisol levels increased in the morning, reaching 47.7 ug/dL. The levels of the hormones ACTH, aldosterone, and renin were determined to be 281 pg/mL, 3.0 ng/dL, and 2.1 pg/mL, respectively. The presence of hypertension, hypokalemia, and alkalinity suggested Cushing's syndrome, which was proven to be ACTH-dependent ECS by a dexamethasone suppression test. A chest CT scan revealed inflammation in the posterior basal region of the right lower lobe. The superior anterior mediastinum was characterized by round-shaped isodensity lesions with distinct borders. She underwent thoracoscopic anterior mediastinal tumor excision via the subxiphoid technique (R0 resection); following surgery, her blood pressure returned to normal, and the hypernatremia/hypopotassemia resolved. The tumor was determined to be a thymic carcinoid. Most notably, cortisol levels fell to half of their presurgical levels after one hour of surgery, and other abnormalities corrected substantially postoperatively. CONCLUSION: Thoracoscopic excision of thymic tumors by subxiphoid incision may be a useful treatment option for ECS caused by neuroendocrine tumors of the thymus.

Connexins and angiogenesis: Functional aspects, pathogenesis, and emerging therapies (Review).

Connexins (Cxs) play key roles in cellular communication. By facilitating metabolite exchange or interfering with distinct signaling pathways, Cxs affect cell homeostasis, proliferation, and differentiation. Variations in the activity and expression of Cxs have been linked to numerous clinical conditions including carcinomas, cardiac disorders, and wound healing. Recent discoveries on the association between Cxs and angiogenesis have sparked interest in Cx­mediated angiogenesis due to its essential functions in tissue formation, wound repair, tumor growth, and metastasis. It is now widely recognized that understanding the association between Cxs and angiogenesis may aid in the development of new targeted therapies for angiogenic diseases. The aim of the present review was to provide a comprehensive overview of Cxs and Cx­mediated angiogenesis, with a focus on therapeutic implications.

Two new members in the quaternary Cs-Ag-As-S family with different arrangements of Ag-S and As-S asymmetric building units: syntheses, structures, and theoretical studies.

New functional materials of As-based multinary chalcogenidometalates have received special attention due to their different oxidation states and flexible building blocks. In this work, two new quaternary thioarsenates(iii), namely Cs2Ag2As2S5 (I) and Cs3AgAs4S8 (II), have been obtained by a simple surfactant-thermal technique. Their structures were determined on the basis of single-crystal X-ray diffraction; compound I belongs to the triclinic space group P1[combining macron] (no. 2) [a = 7.49(2) Å, b = 9.30(2) Å, c = 9.94(2) Å, α = 63.28(3)°, ß = 82.11(3)°, γ = 87.78(3)°, V = 612.4(2) Å3 and Z = 2], whereas compound II crystallizes in the monoclinic space group C2/c (no. 12) [a = 27.76(6) Å, b = 6.98(2) Å, c = 19.68(4) Å, ß = 109.85(3)°, V = 3586.7(2) Å3 and Z = 8]. Both structures are shown to feature two-dimensional (2D) layers with different arrangements of Ag-S and As-S asymmetric building units (ABUs). In compound I, the layer is constructed from vertex-sharing dimeric [As2S5] units linked by tetrameric [Ag4S8] moieties. The layered structure in compound II is formed by 21 helical chains based on [As4S9] groups which are further interconnected by tetrahedral [AgS4] chains. The analysis of the quaternary X-Ag-As-S (X = cations) system shows that various combination ways of Ag-S and As-S ABUs in these sulfides can be attributed to the cation-cation repulsion and stereochemically active lone-pair effect. The UV-vis/NIR absorption spectrum indicates that the optical band energy (Eg) of compounds I and II is 2.48 eV and 2.24 eV, respectively. Moreover, theoretical calculations indicate that the As-S and Ag-S bonding states determine the optical properties of the title compounds. This work not only enriches the structural chemistry of thioarsenates, but also opens up a new avenue for exploring novel multinary chalcogenidometalates.

One-Dimensional Chains in Pentanary Chalcogenides A2Ba3Cu2Sb2S10 (A = K, Rb, Cs) Displaying a Photocurrent Response.

The discovery of new inorganic functional chalcogenides is of fundamental importance in structure chemistry and materials science. Herein, a new type of pentanary thioantimonates, A2Ba3Cu2Sb2S10 (A = K, Rb, Cs), has been discovered by a solvothermal method at low temperature. These isostructural compounds belong to the monoclinic space group C2/m (No. 12) and comprise unique one-dimensional (1D) [Cu2Sb2S10]8- chains surrounded by discrete A+ and Ba2+ cations. Such a 1D chain structure is the first case of chalcogenides in the X/Cu/Sb/Q (X = cations; Q = chalcogen) system. The energy gaps range from 1.90 to 1.98 eV for A2Ba3Cu2Sb2S10 (A = K, Rb, Cs) were obtained from the UV-visible reflectance spectroscopy. Moreover, Rb2Ba3Cu2Sb2S10 displays an intriguing photocurrent response under simulated solar-light illumination. The theoretical calculations were also carried out to understand the interrelationship of the optical performance and electronic structure.

Enhanced Transparency of Rough Surface Sapphire by Surface Vitrifaction Process.

A novel, simple, and low-cost in situ surface vitrification method has been effectively developed to enhance the optical transparency of rough surface sapphire at UV-visible-IR regions. This method is to obtain a glass layer on the sapphire surface through vitrifaction process. The thickness, refractive index, components and transition temperature of the glass layer have been investigated and discussed respectively by XRD, DSC, SEM and EDS elemental analysis. The experimental results show that the vitrified sapphire has high transparency even after 1000 °C annealing at UV-visible-IR regions.

Facile Hydrazine-Hydrothermal Syntheses and Characterizations of Two Quaternary Thioarsenates(III): Two-Dimensional SrAg4 As2 S6 ⋠2 H2 O and One-Dimensional BaAgAsS3.

Two new quaternary thioarsenates(III), SrAg4 As2 S6 ⋅2 H2 O (1) and BaAgAsS3 (2), have been prepared through a hydrazine-hydrothermal method at low temperature. Compound 1 possesses a two-dimensional (2D) layer network, while compound 2 features a one-dimensional (1D) column structure. The detailed structure analysis indicates that Sr(2+) and Ba(2+) cations have different directing effects on the structures of thioarsenates(III). Both experimental and theoretical studies demonstrate that compounds 1 and 2 are narrow-gap semiconductors. Our success in synthesizing these two quaternary thioarsenates(III) proves that the hydrazine-hydrothermal technique is a powerful yet facile synthetic method for exploring new complex chalcogenides with diverse crystal structures and interesting physical properties.

Preparation of Porous Three-Dimensional Quaternary Thioantimonates(III) ACuSb2 S4 (A = Rb, Cs) through a Surfactant-Thermal Method.

Two novel porous three-dimensional (3D) quaternary thioantimonates(III) ACuSb2S4 (A = Rb, Cs) were successfully synthesized by employing the neutral surfactant PEG-400 (PEG = polyethyleneglycol) as reaction media, these are significantly different from the known quaternary A-Cu-Sb-S thioantimonates(III) with two-dimensional (2D) crystal structures. This is the first time that crystalline quaternary chalcogenides have been prepared in surfactant media. Both experimental and theoretical studies confirm they are semiconductors with narrow band gaps. Our results demonstrated that the surfactant-thermal strategy could offer a new opportunity to explore novel chalcogenides with diverse crystal structures and interesting physicochemical properties.

Hydrazine-hydrothermal synthesis and characterization of the two new quaternary thioantimonates(III) BaAgSbS3 and BaAgSbS3·H2O.

The two new quaternary thioantimonates(III) BaAgSbS3 (1) and BaAgSbS3·H2O (2) have been synthesized through a hydrazine-hydrothermal method at low temperature. Compound 1 possesses a two-dimensional (2D) layer structure, while compound 2 features a three-dimensional (3D) channel framework. The optical band gaps of 1 and 2 are approximately 2.2 and 2.4 eV, respectively. Our results clearly indicated that the hydrazine-hydrothermal method could offer exciting opportunities for exploring novel multinary chalcogenides with diverse crystal structures and interesting physical properties.

Three reversible polymorphic copper(I) complexes triggered by ligand conformation: insights into polymorphic crystal habit and luminescent properties.

Three luminescent polymorphs based on a new copper(I) complex Cu(2-QBO)(PPh3)PF6 (1, PPh3 = triphenylphosphine, 2-QBO = 2-(2'-quinolyl)benzoxazole) have been synthesized and characterized by FT-IR, UV-vis, elemental analyses, and single-crystal X-ray diffraction analyses. Each polymorph can reversibly convert from one to another through appropriate procedures. Interestingly, such interconversion can be distinguished by their intrinsic crystal morphologies and colors (namely α, dark yellow plate, ß, orange block, γ, light yellow needle) as well as photoluminescent (PL) properties. X-ray crystal structure analyses of these three polymorphs show three different supramolecular structures from 1D to 3D, which are expected to be responsible for the formation of three different crystal morphologies such as needle, plate, and block. Combination of the experimental data with DFT calculations on these three polymorphs reveals that the polymorphic interconversion is triggered by the conformation isomerization of the 2-QBO ligand and can be successfully controlled by the polarity of the process solvents (affecting the molecular dipole moment) and thermodynamics (affecting the molecular total energy). It is also found that the different crystal colors of polymorphs and their PL properties are derived from different θ values (dihedral angle between benzoxazolyl and quinolyl group of the 2-QBO ligand) and P-Cu-P angles based on TD-DFT calculations. Moreover, an interesting phase interconversion between γ and ß has also been found under different temperature, and this result is consistent with the DFT calculations in which the total energy of ß is larger than that of γ. This polymorphism provides a good model to study the relationship between the structure and the physical properties in luminescent copper(I) complexes as well as some profound insights into their PL properties.

A new heteroleptic cuprous complex with strong yellow photoluminescence.

In the title heteroleptic cuprous complex, (acetonitrile-κN)({2-[2-(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane-κ(2)P,P')[2-(pyridin-4-yl-κN)-1,3-benzoxazole]copper(I) hexafluoridophosphate, [Cu(C(36)H(28)OP(2))(CH(3)CN)(C(12)H(8)N(2)O)]PF6, conventionally abbreviated [Cu(POP)(CH3CN)(4-PBO)]PF6, where POP is the diphosphane ligand {2-[2-(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane and 4-PBO is the N-containing ligand 2-(pyridin-4-yl)-1,3-benzoxazole, the asymmetric unit consists of a hexafluoridophosphate anion and a whole mononuclear cation, where the Cu(I) centre is coordinated by two P atoms from the POP ligand, by one N atom from the 4-PBO ligand and by the N atom of the coordinated acetonitrile molecule, giving rise to a CuP2N2 distorted tetrahedral coordination geometry. The electronic absorption, photoluminescence and thermal stability properties of this complex have been studied on as-synthesized samples, which had previously been examined by powder X-ray diffraction. A yellow emission signal is attributed to an excited state arising from metal-to-ligand charge transfer (MLCT).

A square-pyramidal copper(II) complex with strong intramolecular hydrogen bonds: diaqua(N,N'-dimethylformamide-κO)bis[2-(diphenylphosphoryl)benzoato-κO]copper(II).

In the title Cu(II) complex, [Cu(C19H14O3P)2(C3H7NO)(H2O)2], the molecule is bisected by a twofold axis relating the two 2-(diphenylphosphoryl)benzoate (ODPPB) ligands. The asymmetric unit consists of a Cu(II) metal centre on the symmetry axis, an ODPPB ligand, one water ligand and one dimethylformamide (DMF) ligand (disordered around the twofold axis). The Cu(II) ion has fivefold coordination provided by two carboxylate O atoms from two ODPPB ligands, two O atoms from two coordinated water molecules and another O atom from a (disordered) DMF molecule, giving a CuO5 square-pyramidal coordination geometry. The ODPPB ligand adopts a terminal monocoordinated mode with two free O atoms forming two strong intramolecular hydrogen bonds with the coordinated water molecules, which may play a key role in the stability of the molecular structure, as shown by the higher release temperature for the coordinated water molecules than for the coordinated DMF molecule. The optical absorption properties of powder samples of the title compound have also been studied.

A new potential NLO compound with a supramolecular layered structure: aqua(hexamethylenetetramine-κN)(iminodiacetato-κ3O,N,O')copper(II).

In the noncentrosymmetric title compound, [Cu(C(4)H(5)NO(4))(C(6)H(12)N(4))(H(2)O)] or [Cu(IDA)(HMTA)(H(2)O)], where IDA is iminodiacetate and HMTA is hexamethylenetetramine, the asymmetric unit consists of a whole mononuclear neutral molecule, where the Cu(II) cation is coordinated by two carboxylate O atoms and one N atom from the IDA ligand, by one N atom from the HMTA ligand and by the O atom of the coordinated water molecule, giving rise to a CuN(2)O(3) distorted square-pyramidal coordination geometry. The IDA and HTMA ligands adopt terminal tri- and monocoordinated modes, respectively. All adjacent molecules within the ac plane are connected to each other via two pairs of O-H···O and one N-H...O hydrogen bond, forming a (4,4) supramolecular two-dimensional network. In the unit cell, these layers stack alternately in an …ABABAB… sequence along the b axis. The optical absorption properties of this compound have been studied on powder samples, which had previously been examined by powder X-ray diffraction.

rac-2,2'-Bis(diphenyl-phosphan-yl)-1,1'-binaphth-yl: a racemic diphosphine ligand.

The asymmetric unit of the title compound, C(44)H(32)P(2), conventionally abbreviated BINAP, is one half of the complete chiral BINAP mol-ecule, which adopts a C2 crystallographic point-group symmetry with a twofold axis splitting the mol-ecule in two identical halves; a center of symmetry between mol-ecules further determines the racemic pairs. There are no obvious supra-molecular inter-actions between adjacent BINAP mol-ecules.

A double salt of iodo-bis-muthate: cis-aqua-iodidobis(1,10-phenanthroline)cobalt(II) tris-(1,10-phenanthroline)cobalt(II) trans-hexa-µ(2)-iodido-hexa-iodidotribismuthate(III).

In the title complex, [Co(C(12)H(8)N(2))(3)][CoI(C(12)H(8)N(2))(2)(H(2)O)][Bi(3)I(12)], conventionally abbreviated [Co(phen)(3)][CoI(phen)(2)(H(2)O)][Bi(3)I(12)], where phen is 1,10-phenanthroline, the Co(II) atom in one cation is coordinated by six N atoms from three phen ligands in an octa-hedral coordination while the Co(II) atom in the other cation is coordinated octa-hedrally by four N atoms from two phen ligands, one water O atom and one I atom. In the anion, three Bi(III) ions adopt an octa-hedral coordination constructed by six I(-) ligands. The three BiI(6) octa-hedra are fused together through trans face-sharing.

Aqua-[4-(hy-droxy-imino-meth-yl)pyridine-κN](imino-diacetato-κO,N,O')copper(II).

In the title complex, [Cu(C(4)H(5)NO(4))(C(6)H(6)N(2)O)(H(2)O)], conventionally abbreviated Cu(IDA)(4-OXPy)(H(2)O), where IDA is imino-diacetate and 4-OXPy is 4-(hy-droxy-imino-meth-yl)pyridine, the Cu(II) atom exhibits a distorted square-pyramidal coordination geometry, which is constructed from two O atoms and one N atom from a IDA ligand, one N atom from 4-OXPy ligand and one O atom from water. This mol-ecule looks like a space shuttle, the IDA ligand is its empennage (tail), and the 4-OXPy ligand is its airframe. The complexes are linked into two-dimensional supra-molecular layers parallel to (100) by three pairs of O-H⋯O hydrogen bonds. Two pairs of N-H⋯O hydrogen bonds further connect these supra-molecular layers, forming a three-dimensional supra-molecular network.

A photochromic dinuclear compound: aquatetrakis(µ-2,3-diphenylprop-2-enoato)bis(2,3-diphenylprop-2-enoato)ethanolbis(1,10-phenanthroline)dilanthanum(III).

The title dinuclear complex, (aqua-1κO)tetrakis(µ-2,3-diphenylprop-2-enoato-1:2κ(2)O:O')bis(2,3-diphenylprop-2-enoato)-1κO;2κO-(ethanol-2κO)bis(1,10-phenanthroline)-1κ(2)N,N';2κ(2)N,N'-dilanthanum(III), [La(2)(C(15)H(11)O(2))(6)(C(12)H(8)N(2))(2)(C(2)H(5)OH)(H(2)O)], contains two similar La(III) centres with distorted [LaO(6)N(2)] bicapped triganol-prismatic coordination polyhedra formed by six phenylcinnamate (PCA(-) or 2,3-diphenylprop-2-enoate) ligands, two 1,10-phenanthroline (phen) ligands, a coordinating ethanol molecule and a coordinating water molecule. The two metal centres are bridged by four µ-PCA(-) ligands, with the remaining two PCA(-) ligands coordinated in a monodentate fashion. The noncoordinated carboxylate O atoms on the terminal PCA(-) ligands form O-H···O hydrogen bonds with the coordinated solvent molecules. Each La centre is also coordinated by a bidentate phen ligand. The PCA(-) ligands all adopt syn-syn orientations, with the two phenyl rings presenting dihedral angles of about 70°. The compound displays photochromic behaviour both in solution and in the solid state.

2'-Eth-oxy-1,3,3-trimethyl-spiro-[indoline-2,3'-3H-naphtho-[2,1-b][1,4]oxazine].

In the title compound, C(24)H(24)N(2)O(2), the five-membered ring of the indoline ring system adopts an envelope conformation with the spiro C atom at the flap. The dihedral angle between the benzene ring of the indoline ring system and the naphthalene ring system is 71.70 (7)°. In the crystal structure, pair of weak C-H⋯O hydrogen bonds link the mol-ecules into centrosymmetric dimers.