Electrocatalytic Nitrate Reduction on Metallic CoNi-Terminated Catalyst with Industrial-Level Current Density in Neutral Medium.

Green ammonia synthesis through electrocatalytic nitrate reduction reaction (eNO3RR) can serve as an effective alternative to the traditional energy-intensive Haber-Bosch process. However, achieving high Faradaic efficiency (FE) at industrially relevant current density in neutral medium poses significant challenges in eNO3RR. Herein, with the guidance of theoretical calculation, a metallic CoNi-terminated catalyst is successfully designed and constructed on copper foam, which achieves an ammonia FE of up to 100% under industrial-level current density and very low overpotential (-0.15 V versus reversible hydrogen electrode) in a neutral medium. Multiple characterization results have confirmed that the maintained metal atom-terminated surface through interaction with copper atoms plays a crucial role in reducing overpotential and achieving high current density. By constructing a homemade gas stripping and absorption device, the complete conversion process for high-purity ammonium nitrate products is demonstrated, displaying the potential for practical application. This work suggests a sustainable and promising process toward directly converting nitrate-containing pollutant solutions into practical nitrogen fertilizers.

Multi-Stimuli-Responsive Chromic Behaviors of an All-in-One Viologen-Based Cd(II) Complex.

A one-dimensional Cd(II) chain coordination polymer constructed by an electron-deficient viologen-anchored carboxylate ligand was successfully synthesized. Owing to the favorable stimuli-chromic properties of viologen, the title compound shows reversible photochromism, thermochromism, electrochromism, and naked-eye-detectable differentiable vapochromic response to different volatile amines. The chromic behaviors of it are ascribed to the formation of viologen radicals triggered by external stimuli. And the differentiated response to volatile amines is attributed to the size effect of the amines as well as the steric hindrance effect of forming α/ß Cv-H···Namines interactions of the viologen unit to further affect the occurrence of electron transfer. Such an all-in-one crystalline material might have more practical applications in photoelectric, erasable inkless printing, light printing, and volatile amine detection fields.

A naphthalimide-based and Golgi-targetable fluorescence probe for quantifying hypochlorous acid.

The Golgi apparatus (GA) is a vital organelle in biological systems and excess reactive oxygen species (ROS) is produced during stress in the Golgi apparatus. Hypochlorous acid (HOCl) is a significant reactive oxygen species and has strong oxidative and antibacterial activity, but excessive secretion of hypochlorous acid can affect Golgi structure or function abnormally, it will lead to a series of diseases including Alzheimer's disease, neurodegenerative diseases, autoimmune diseases, and Parkinson's disease. In present work, a novel fluorescent probe for Golgi localization utilizing naphthalimide derivatives was constructed to detect hypochlorous acid. The fluorescent probe used a derivatived 1,8-naphthalimide as the emitting fluorescence group, phenylsulfonamide as the localization group and dimethylthiocarbamate as the sensing unit. When HOCl was absent, the intramolecular charge transfer (ICT) process of the developed probe was hindered and the probe exhibited a weak fluorescence. When HOCl was present, the ICT process occurred and the probe showed strong green fluorescence. When the HOCl concentration was altered from 5.0 × 10-7 to 1.0 × 10-5 mol·L-1, the fluorescence intensity of the probe well linearly correlated with the HOCl concentration. The detection limit of 5.7 × 10-8 mol·L-1 was obtained for HOCl. The HOCl fluorescent probe possessed a rapid reaction time, a high selectivity and a broad working pH scope. In addition, the probe possessed good biocompatibility and had been magnificently employed to image Golgi HOCl in Hela cells. These characteristics of the probe demonstrated its ability to be used for sensing endogenous and exogenous hypochlorous acids within the Golgi apparatus of living cells.

Clinical observation and genetic analysis of a SYNS1 family caused by novel NOG gene mutation.

OBJECTIVE: Analyze the clinical and genetic characteristics of a rare Chinese family with Multiple synostoses syndrome and identify the causative variant with the high-throughput sequencing approach. METHODS: The medical history investigation, physical examination, imaging examination, and audiological examination of the family members were performed. DNA samples were extracted from the family members. The candidate variant was identified by performing whole-exome sequencing of the proband, then verified by Sanger sequencing in the family. RESULTS: The family named HBSY-018 from Hubei province had 18 subjects in three generations, and six subjects were diagnosed with conductive or mixed hearing loss. Meanwhile, characteristic features including short philtrum, hemicylindrical nose, and hypoplastic alae nasi were noticed among those patients. Symptoms of proximal interdigital joint adhesion and inflexibility were found. The family was diagnosed as Multiple synostoses syndrome type 1 (SYNS1).The inheritance pattern of this family was autosomal dominant. A novel mutation in the NOG gene c.533G>A was identified by performing whole-exome sequencing of the proband. The substitution of cysteine encoding 178th position with tyrosine (p.Cys178Tyr) was caused by this mutation, which was conserved across species. Co-segregation of disease phenotypes was demonstrated by the family verification. CONCLUSION: The family diagnosed as SYNS1 was caused by the novel mutation (c.533G>A) of NOG. The combination of clinical diagnosis and molecular diagnosis had improved the understanding of this rare disease and provided a scientific basis for genetic counseling in the family.

Photo/Electrochromic Dual Responsive Behavior of a Cage-like Zr(IV)-Viologen Metal-Organic Polyhedron (MOP).

Stable stimulus-responsive materials are highly desirable due to their widespread potential applications and growing demand in recent decades. Despite the fact that viologen derivatives have long been known as excellent photochromic and electrochromic materials, the development of stable viologen-based multifunctional smart materials with short coloration times remains an exciting topic. To obtain photochromic and electrochromic dual responsive materials, embedding the viologen ligand into a robust metal oxide cluster to increase its stability and sensitivity is an effective strategy. Herein, a viologen-based metal-organic polyhedron (MOP) {[Zr6L3(µ3-O)2(µ2-OH)6Cp6]·8Cl·CH3OH·DMF} [Zr-MOP-1; H2L·2Cl = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium dichloride, and Cp = η5-C5H5] was successfully prepared and characterized. It consists of trinuclear Zr-oxygen secondary building units and exhibits reversible photochromic and electrochromic dual responsive behaviors. As expected, the designed robust viologen-based nanocage with a V2E3 (V = vertex, and E = edge) topology can maintain its stability and rapid photo/electrochromic behaviors with an obvious reversible change in color from purple (brown) to green, mainly due to the enclosed cluster structure and the abundant free viologen radicals that originate from the effective Cl → N and O → N electron transfers. Spectroelectrochemistry and theoretical calculations of this Zr-MOP were also performed to verify the chromic mechanism.

A multi-responsive indium-viologen hybrid with ultrafast-response photochromism and electrochromism.

A novel 0D organic-inorganic metal halide hybrid (C13H16N2O2)2InCl6·Cl (1) has been obtained by integrating the mono-viologen derivative with InCl3. Compound 1 exhibits reversible and ultrafast UV/sunlight/X-ray induced photochromic properties, as well as excellent electrochromic performance, which is the first example of an indium-based organic-inorganic chromic hybrid.

Hydrazone connected stable luminescent covalent-organic polymer for ultrafast detection of nitro-explosives.

Developing promising luminescent probes for the selective sensing of nitro-explosives remains a challenging issue. Porous luminescent covalent-organic polymers are one of the excellent sensing probes for trace hazardous materials. Herein, fluorescent monomers 1,1,2,2-tetrakis(4-formyl-(1,1'-biphenyl))ethane (TFBE) and 1,3,5-benzenetricarboxylic acid trihydrazide (BTCH) were selected to build a novel hydrazone connected stable luminescent covalent-organic polymer (H-COP) of high stability by typical Schiff-base reaction. The N2 sorption study, BET surface area analysis, and TGA profile indicate the porosity and stability of this H-COP material. Such properties of the H-COP material enable a unique sensing platform for nitro-explosives with great sensitivity (Ksv ∼ 106 M) and selectivity up to µM. This polymer material shows attractive selectivity and sensitivity towards phenolic nitro-explosives and other common explosives among earlier reported COP-based sensors.

A viologen-based multifunctional Eu-MOF: photo/electro-modulated chromism and luminescence.

A novel viologen-based multifunctional Eu-MOF was obtained by integrating a luminescent component Eu(NO3)3·6H2O and a viologen-functionalized ligand. The Eu-MOF not only exhibited reversible photochromic and electrochromic properties, but also displayed photoluminescent and electroluminochromic properties.

A new silver cluster that emits bright-blue phosphorescence.

A new hexanuclear silver(i) cluster (NC-Ag6) that emits bright-blue phosphoresce with a lifetime of 22.4 µs and a quantum yield (QY) of 22% under ambient conditions was synthesized. A film combining NC-Ag6 with yellow cerium(iii)-doped yttrium aluminum garnet phosphors (YAG:Ce3+) displays "chameleon"-like emission (including white), which is related to excitation-dependent Förster resonance energy transfer (FRET) between dual phosphors. The mechanoresponsive luminescence colour of this silver cluster ranges from blue to green virtually without loss of QY.

Intraoperative Repair of Cerebrospinal Fluid Rhinorrhea in Skull Base Tumor Resection: A Retrospective Study of Acellular Dermal Matrix Versus Turbinate Flap.

BACKGROUND: The acellular dermal matrix (ADM) and turbinate flap (TF) have been widely used in the reconstruction of skull base defects. However, owing to the lack of reported data, the therapeutic effects have been controversial. The purpose of the present study was to compare the effect of the ADM and TF on cerebrospinal fluid (CSF) rhinorrhea after nasal endoscopic resection of a skull base tumor. METHODS: The data from 46 patients who had undergone nasal endoscopic resection of a skull base tumor and repair of CSF rhinorrhea were retrospectively analyzed. The patients were divided into ADM and TF groups according to the difference in repair materials used. We compared and analyzed the intraoperative information and postoperative outcomes. RESULTS: The operation time, blood loss, defect area, and need for blood transfusion were not significantly different between the ALT and TF groups. The postoperative length of hospital stay (14.33 ± 3.66 vs. 16.76 ± 5.51 days; P = 0.669) and the incidence of complications, including wound infection (1 vs. 0; P = 0.270), intracranial infection (1 vs. 1; P = 0.900), hemorrhage (2 vs. 3; P = 0.788), 15-day CSF leak (1 vs. 2; P = 0.658), and respiratory infection (2 vs. 1; P = 0.450) were comparable between the 2 groups. The 6-month (0 vs. 0; P = 1.000) and 12-month (0 vs. 0; P = 1.000) incidence of recurrence also showed no significant differences. CONCLUSION: The use of the ADM for patients with CSF rhinorrhea showed comparable results in terms of postoperative outcomes compared with the use of TF. ADM could serve as a safe and feasible alternative for endoscopic repair of CSF rhinorrhea after nasal endoscopic resection of skull base tumors.

Effect of High-Intensity Focused Ultrasound Versus Plasma Radiofrequency Ablation on Recurrent Allergic Rhinitis.

BACKGROUND High-intensity focused ultrasound (HIFU) and plasma radiofrequency ablation (PRA) have been used to treat recurrent allergic rhinitis (AR); however, there is a lack of literature comparing the efficacy of these 2 methods. We assessed and compared the therapeutic effects of HIFU and PRA on recurrent AR. MATERIAL AND METHODS We enrolled 66 patients with recurrent AR at West China Hospital of Sichuan University. Visual analogue score (VAS), pain score, rhinoconjunctivitis quality of life questionnaire (RQLQ), and nasal endoscopy were performed to evaluate the therapeutic effect. RESULTS Nasal endoscopy showed that HIFU and PAR reduced the volume of the inferior turbinate, whereas HIFU reduced the amount of nasal secretions in patients. VAS scores showed that HIFU and PRA nasal congestion symptoms were significantly reduced (P<0.05). The preoperative VAS scores for nasal fluid and sneezing were significantly lower in patients receiving HIFU (P<0.05) than in those receiving PRA (P>0.05). HIFU-treated patients had significantly lower postoperative pain scores than those in the PRA group (P<0.05). RQLQ showed activity, sleep, and non-nasal or ocular symptoms, and both HIFU and PRA patients had significantly lower scores (P<0.05). Nasal symptom scores, actual problems, and mood in the HIFU group were significantly worse than those in the PRA group (P<0.05). However, neither treatment had a significant effect on ocular symptoms (P>0.05). CONCLUSIONS Compared with PRA, HIFU can significantly reduce the nasal symptoms of AR patients, improve the quality of life, and can be used as an adjuvant therapy with better therapeutic effect.

Amino functionalized Zn/Cd-metal-organic frameworks for selective CO2 adsorption and Knoevenagel condensation reactions.

Two amino functionalized Metal-Organic Frameworks (MOFs), {[Zn(Py2TTz)(2-NH2-BDC)]·(DMF)}n (1) and {[Cd(Py2TTz)(2-NH2-BDC)]·(DMF)·0.5(H2O)}n (2) (where Py2TTz = 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole, 2-NH2-BDC = 2-amino-1,4-benzenedicarboxylate, and DMF = N,N-dimethylformamide), were synthesized and characterized using the primary ligand 2-amino-1,4-benzenedicarboxylic acid (2-NH2-H2BDC) and the auxiliary ligand 2,5-bis(4-pyridyl)thiazolo[5,4-d]thiazole (Py2TTz). They possess similar 2-fold interpenetrated three-dimensional bipillared-layer framework structures composed of typical binuclear metal nodes, 2-NH2-BDC two-dimensional layers and Py2TTz bipillars. Notably, thiazole nitrogen atoms and pendant -NH2 groups are present in channels in the two frameworks. Given their good chemical stabilities, high thermal stabilities, and exposed nitrogen sites, gas adsorption and catalytic experiments of the two MOFs were performed. The results demonstrate that MOF 2 can selectively adsorb carbon dioxide gas; moreover, the two MOFs can be employed as recyclable heterogeneous catalysts for Knoevenagel condensation reactions under solvent-free conditions.