Vacuum-Processed Propylene Urea Additive: A Novel Approach for Controlling the Growth of CH3NH3PbI3 Crystals in All Vacuum-Processed Perovskite Solar Cells.

In this study, we present a novel method for controlling the growth of perovskite crystals in the vacuum thermal evaporation process by utilizing a vacuum-processable additive, propylene urea (PU). By coevaporation of perovskite precursors with PU to form the perovskite layer, PU, acting as a Lewis base additive, retards the direct reaction between the perovskite precursors. This facilitates a larger domain size and reduced defect density. Following the removal of the residual additive, the perovskite layer, exhibiting improved crystallinity, demonstrates reduced charge recombination, as confirmed by a time-resolved microwave conductivity analysis. Consequently, there is a notable enhancement in open-circuit voltage and power conversion efficiency, increasing from 1.05 to 1.15 V and from 17.17 to 18.31%, respectively. The incorporation of a vacuum-processable and removable Lewis base additive into the fabrication of vacuum-processed perovskite solar cells offers new avenues for optimizing these devices.

Regioselective Arylation of Amidoaryne Precursors via Ag-Mediated Intramolecular Oxy-Argentation.

An unprecedented silver-mediated intramolecular oxy-argentation of 3-amidoaryne precursors that quickly generates a heteroarylsilver species is developed. AgF acts as both a stoichiometric fluoride source and a reagent for the formation of a benzoxazolylsilver intermediate via aryne generation. Pd-catalyzed coupling reactions of (hetero)aryl iodides with a silver species, generated in situ, allow for the synthesis of various C7-arylated benzoxazoles. As a result, an aryl group is selectively introduced into the meta-position of 3-amidobenzyne precursors. Mechanistic studies have indicated the presence of a benzoxazolylsilver intermediate and revealed that the reaction proceeds via an intramolecular oxy-argentation process, which is initiated by a direct fluoride attack on the silyl group.

Thoracic CT incidental pulmonary bullae in dogs: Characterization, interobserver variability, and general anesthesia risks.

Ruptures of pulmonary blebs and bullae are the most common cause of spontaneous pneumothorax in dogs. Incidental bullae/blebs have been documented in otherwise healthy people, however information for veterinary patients is currently lacking. Objectives of this retrospective, observer agreement, analytical study were to characterize incidental bullae in thoracic CT studies of dogs, assess interobserver variability for characterizing the bullae, and assess anesthesia risks. Inclusion criteria were dogs presenting for non-pneumothorax related reasons that had a thoracic CT at a single specialty and emergency hospital from 2012 to 2021 and had a bulla listed in the CT report. Medical records for dogs meeting inclusion criteria were reviewed to collect data on signalment, weight, total number of general anesthesia procedures 2 years prior and 2 years following the CT scan, and adverse anesthesia events. In addition, the CT images were reviewed by three American College of Veterinary Radiology-certified veterinary radiologists to collect data on the location, size, number of bullae and thickness of the bulla wall. A total of 1119 dogs met initial inclusion criteria and 74 dogs were included in analyses. There was no sex predilection for incidental pulmonary bullae. Bullae were more commonly found in older (median age 11.3 years), large breed dogs (median weight 20.7 kg). A solitary bulla of less than 1 cm was the most common finding with no apparent predilection for a particular lung lobe. There was strong correlation among the three radiologists for bulla location, size, and number, but weak correlations for bulla wall thickness. No adverse anesthesia events were found following CT anesthesia or following repetitive anesthesia procedures.

Continuous Flow Synthesis of N-Sulfonyl-1,2,3-triazoles for Tandem Relay Cu/Rh Dual Catalysis.

The continuous flow synthesis of N-sulfonyl-1,2,3-triazoles, which are convenient reactive azavinyl carbene precursors, for tandem relay Cu/Rh dual catalysis has been developed. Most reactions readily proceeded at 75 °C in a short residence time of 13.09 min in the presence of 2.5 mol % of CuTC. The scope of the reactions was explored by synthesizing diversely functionalized N-sulfonyl and sulfamoyl triazoles in yields ranging from 92 to 98%. To demonstrate the scalability of the process, the reaction was conducted on a 5.4 mmol scale with residence and collection times of 13.09 and 60 min, respectively. Furthermore, a series of controlled experiments were performed to investigate the compatibility of Cu and Rh in a batch or a continuous flow system. Finally, the first integrated flow system using the azavinyl carbene intermediate under the tandem relay Cu/Rh dual catalysis was developed for the synthesis of various cis-diamino enones from alkynes and sulfonyl azides.

A Review on Fucoidan Structure, Extraction Techniques, and Its Role as an Immunomodulatory Agent.

Functional ingredients for human health have recently become the focus of research. One such potentially versatile therapeutic component is fucose-containing sulfated polysaccharides (FCSPs), referred to as fucoidans. The exploitation of marine brown algae provides a rich source of FCSPs because of their role as a structural component of the cell wall. Fucoidans are characterized by a sulfated fucose backbone. However, the structural characterization of FCSPs is impeded by their structural diversity, molecular weight, and complexity. The extraction and purification conditions significantly influence the yield and structural alterations. Inflammation is the preliminary response to potentially injurious inducements, and it is of the utmost importance for modulation in the proper direction. Improper manipulation and/or continuous stimuli could have detrimental effects in the long run. The web of immune responses mediated through multiple modulatory/cell signaling components can be addressed through functional ingredients, benefiting patients with no side effects. In this review, we attempted to address the involvement of FCSPs in the stimulation/downregulation of immune response cell signaling. The structural complexity and its foremost influential factor, extraction techniques, have also attracted attention, with concise details on the structural implications of bioactivity.

Optimal Distributed MQTT Broker and Services Placement for SDN-Edge Based Smart City Architecture.

A smart city is an urban area that collects data from various devices to effectively manage urban resources. The smart city IoT infrastructure connects numerous devices to an Internet-protocol-based low-power wireless network, shares massive amounts of data, and facilitates the development of new services. Message queuing telemetry transport (MQTT), a lightweight exchange protocol for the IoT environment, uses a publish and subscribe structure via a centralized broker to share data. The extent of edge computing provides distributed and closer resources to the data source while maintaining low transmission costs. However, a centralized MQTT data broker is unsuitable for distributed edge resources and could result in high latency, traffic, and bottleneck risk. Therefore, we proposed a distributed MQTT broker optimized architecture. A distributed MQTT broker for edge resources could reduce network traffic and data delivery latency by only managing consumed topics in the network. We formulate an integer non-linear program to optimize container placement and avoid wasting edge computing resources. We compared our proposed architecture to the existing distributed MQTT middleware architecture with greedy and random container placement through extensive simulation. Our methods show better performance in lowering deployment failure ratio, power consumption, network usage, and synchronization overhead.

Comparative Review of Malignant Melanoma and Histologically Well-Differentiated Melanocytic Neoplasm in the Oral Cavity of Dogs.

Oral malignant melanoma (OMM) is the most common neoplasm of the canine oral cavity. It is characterized by its aggressive local disease as well as its high rate of lymphatic invasion and distant metastasis. OMM carries a poor prognosis, with most patients succumbing to the disease due to progression of the neoplasm. Histopathologically, OMM is characterized by significant nuclear atypia, a mitotic index of greater than 4/10 hpf, and evidence of vascular invasion or metastasis. Clinically, these lesions can become locally invasive, causing lysis of bones and severe inflammation of the surrounding soft tissue. With time, these lesions can spread to the regional lymph node and to the lungs and other organs. Prognosis can vary depending on the size of the primary tumor, regional node involvement, and distant metastatic disease; however, multiple studies report a relatively short median survival time ranging from less than 4 months to 8 months. Histologically well- differentiated melanocytic neoplasms (HWDMN) are a variant of OMM and sometimes referred to as canine oral melanocytic neoplasms of low malignant potential. Unlike OMM, patients with HWDMN have longer survival times. Histopathologically, HWDMNs have well-differentiated melanocytes with a low mitotic index of 3 or less per 10 hpf and minimal nuclear atypia. HWDMNs have better prognosis with a mean survival time of up to 34 months. This article is a comparative review of OMM and its less aggressive counterpart.

1,3-Aza-Brook Rearrangement of Aniline Derivatives: In Situ Generation of 3-Aminoaryne via 1,3-C-(sp2)-to-N Silyl Migration.

The design, synthesis, and validation of 3-aminobenzyne precursors induced by C-(sp2)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30%.

Progressive Traffic-Oriented Resource Management for Reducing Network Congestion in Edge Computing.

Edge computing can deliver network services with low latency and real-time processing by providing cloud services at the network edge. Edge computing has a number of advantages such as low latency, locality, and network traffic distribution, but the associated resource management has become a significant challenge because of its inherent hierarchical, distributed, and heterogeneous nature. Various cloud-based network services such as crowd sensing, hierarchical deep learning systems, and cloud gaming each have their own traffic patterns and computing requirements. To provide a satisfactory user experience for these services, resource management that comprehensively considers service diversity, client usage patterns, and network performance indicators is required. In this study, an algorithm that simultaneously considers computing resources and network traffic load when deploying servers that provide edge services is proposed. The proposed algorithm generates candidate deployments based on factors that affect traffic load, such as the number of servers, server location, and client mapping according to service characteristics and usage. A final deployment plan is then established using a partial vector bin packing scheme that considers both the generated traffic and computing resources in the network. The proposed algorithm is evaluated using several simulations that consider actual network service and device characteristics.

Ligand Architecture Perturbation Influences the Reactivity of Nonheme Iron(V)-Oxo Tetraamido Macrocyclic Ligand Complexes: A Combined Experimental and Theoretical Study.

Iron(V)-oxo complexes bearing negatively charged tetraamido macrocyclic ligands (TAMLs) have provided excellent opportunities to investigate the chemical properties and the mechanisms of oxidation reactions of mononuclear nonheme iron(V)-oxo intermediates. Herein, we report the differences in chemical properties and reactivities of two iron(V)-oxo TAML complexes differing by modification on the "Head" part of the TAML framework; one has a phenyl group at the "Head" part (1), whereas the other has four methyl groups replacing the phenyl ring (2). The reactivities of 1 and 2 in both C-H bond activation reactions, such as hydrogen atom transfer (HAT) of 1,4-cyclohexadiene, and oxygen atom transfer (OAT) reactions, such as the oxidation of thioanisole and its derivatives, were compared experimentally. Under identical reaction conditions, 1 showed much greater reactivity than 2, such as a 102-fold decrease in HAT and a 105-fold decrease in OAT by replacing the phenyl group (i.e., 1) with four methyl groups (i.e., 2). Then, density functional theory calculations were performed to rationalize the reactivity differences between 1 and 2. Computations reproduced the experimental findings well and revealed that the replacement of the phenyl group in 1 with four methyl groups in 2 not only increased the steric hindrance but also enlarged the energy gap between the electron-donating orbital and the electron-accepting orbital. These two factors, steric hindrance and the orbital energy gap, resulted in differences in the reduction potentials of 1 and 2 and their reactivities in oxidation reactions.

Alginic Acid from Padina boryana Abate Particulate Matter-Induced Inflammatory Responses in Keratinocytes and Dermal Fibroblasts.

Particulate matter (PM) is a significant participant in air pollution and is hence an inducer of serious health issues. This study aimed to evaluate the dust protective effects of alginate from Padina boryana (PBA) via inflammatory-associated pathways to develop anti-fine dust skincare products. In between the external and internal environments, the skin is considered to be more than a physical barrier. It was observed that PM stimulates inflammation in the skin via activating NF-κB and MAPK pathways. The potential of PBA to inhibit the studied pathways were evident. The metal ion content of PM was considerably reduced by PBA and thus attributed to its chelation ability. Current research demonstrated the potential of P. boryana alginates to be implemented as a protective barrier against inflammation imposed with heavy metal and bacterial-derived endotoxin bound to the surface of the PM. Concisely, the results suggest that the bioactive components derived from the brown algae Padina boryana increased the cellular resistance to PM-stimulated inflammation-driven skin damage.

Impact of acidity regulator and excipient nutrients on digestive solubility and intestinal transport of calcium from calcium phosphate and carbonate.

The aim of the current study was to investigate the effect of an acidity regulator (SPORIX®), lactose, and vitamin D3 as excipient ingredients on digestive solubility and intestinal transport of calcium from four different calcium materials (tricalcium phosphate (TCP), fish bone (FB), nano-fish bone (NFB), and algae calcium (AC)) through an in vitro digestion model system combined with Caco-2 cells. The concentration of ionized calcium (Ca2+) in an aqueous fraction after in vitro digestion increased with the addition of SPORIX®, and it was further enhanced by adding SPORIX® + lactose + vitamin D3 into TCP, FB, NFB, and AC, respectively. In particular, FB with SPORIX® + lactose + vitamin D3 enhanced calcium ionization to 33.89 ± 0.69 mg g-1, which was about 11.76 times higher than that of FB only. In the case of intestinal cellular uptake of calcium, there was no significant difference in all the tested calcium materials with SPORIX® + lactose + vitamin D3. However, the absolute amount of intestinal transport of calcium in FB (43.95 ± 3.29 µg) was significantly higher than other calcium materials with the addition of SPORIX® + lactose + vitamin D3 (p < 0.05). This study suggests that the co-consumption of SPORIX®, lactose, and vitamin D3 with FB could enhance the calcium bioavailability by lowering pH as well as improving calcium intestinal transport by modulating the paracellular and transcellular uptake mechanism.

Enhanced Redox Reactivity of a Nonheme Iron(V)-Oxo Complex Binding Proton.

Acid effects on the chemical properties of metal-oxygen intermediates have attracted much attention recently, such as the enhanced reactivity of high-valent metal(IV)-oxo species by binding proton(s) or Lewis acidic metal ion(s) in redox reactions. Herein, we report for the first time the proton effects of an iron(V)-oxo complex bearing a negatively charged tetraamido macrocyclic ligand (TAML) in oxygen atom transfer (OAT) and electron-transfer (ET) reactions. First, we synthesized and characterized a mononuclear nonheme Fe(V)-oxo TAML complex (1) and its protonated iron(V)-oxo complexes binding two and three protons, which are denoted as 2 and 3, respectively. The protons were found to bind to the TAML ligand of the Fe(V)-oxo species based on spectroscopic characterization, such as resonance Raman, extended X-ray absorption fine structure (EXAFS), and electron paramagnetic resonance (EPR) measurements, along with density functional theory (DFT) calculations. The two-protons binding constant of 1 to produce 2 and the third protonation constant of 2 to produce 3 were determined to be 8.0(7) × 108 M-2 and 10(1) M-1, respectively. The reactivities of the proton-bound iron(V)-oxo complexes were investigated in OAT and ET reactions, showing a dramatic increase in the rate of sulfoxidation of thioanisole derivatives, such as 107 times increase in reactivity when the oxidation of p-CN-thioanisole by 1 was performed in the presence of HOTf (i.e., 200 mM). The one-electron reduction potential of 2 (Ered vs SCE = 0.97 V) was significantly shifted to the positive direction, compared to that of 1 (Ered vs SCE = 0.33 V). Upon further addition of a proton to a solution of 2, a more positive shift of the Ered value was observed with a slope of 47 mV/log([HOTf]). The sulfoxidation of thioanisole derivatives by 2 was shown to proceed via ET from thioanisoles to 2 or direct OAT from 2 to thioanisoles, depending on the ET driving force.

Highly Selective Room-Temperature Suzuki-Miyaura Coupling of Bromo-2-sulfonyloxypyridines for Unsymmetrical Diarylpyridines.

A new and mild synthetic approach has been developed for the synthesis of pharmaceutically important unsymmetrical diarylpyridines via chemoselective Suzuki-Miyaura coupling reactions of bromo-2-sulfonyloxypyridines. Most reactions allow for facile access to aryl-2-sulfonyloxypyridines at room temperature in yields of 5-99% with excellent chemoselectivity in the presence of Pd(OAc)2 (2.0 mol %) and Ad2BnP (2.4 mol %). The second arylation of the remaining tosyl or triflyl group in the monoarylpyridine derivatives obtained was successfully accomplished for the synthesis of unsymmetrical 2,3-, 2,4-, 2,5-, and 2,6-diarylpyridine derivatives. Furthermore, a one-pot synthesis of unsymmetrical diarylpyridines starting from bromo-2-sulfonyloxypyridine was accomplished to demonstrate the practical convenience. Finally, with this method, an antibacterial agent, a topoisomerase inhibitor, and etoricoxib, a nonsteroidal anti-inflammatory drug, were successfully synthesized from the corresponding bromo-2-hydroxypyridines in overall yields of 80, 86, and 49%, respectively.

A High-Valent Manganese(IV)-Oxo-Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity.

A mononuclear nonheme manganese(IV)-oxo complex binding the Ce4+ ion, [(dpaq)MnIV (O)]+ -Ce4+ (1-Ce4+ ), was synthesized by reacting [(dpaq)MnIII (OH)]+ (2) with cerium ammonium nitrate (CAN). 1-Ce4+ was characterized using various spectroscopic techniques, such as UV/Vis, EPR, CSI-MS, resonance Raman, XANES, and EXAFS, showing an Mn-O bond distance of 1.69 Šwith a resonance Raman band at 675 cm-1 . Electron-transfer and oxygen atom transfer reactivities of 1-Ce4+ were found to be greater than those of MnIV (O) intermediates binding redox-inactive metal ions (1-Mn+ ). This study reports the first example of a redox-active Ce4+ ion-bound MnIV -oxo complex and its spectroscopic characterization and chemical properties.

Chan-Lam coupling reaction of sulfamoyl azides with arylboronic acids for synthesis of unsymmetrical N-arylsulfamides.

An efficient method was developed for the synthesis of unsymmetrical N-arylsulfamides using sulfamoyl azides and arylboronic acids in the presence of 10 mol% of copper chloride as the catalyst. The reaction was facilitated in MeOH in an open flask at room temperature. Unlike the coupling of sulfamides and boronic acids, the use of sulfamoyl azides was found to be beneficial with respect to the yield and reaction time.

Mn(III)-Iodosylarene Porphyrins as an Active Oxidant in Oxidation Reactions: Synthesis, Characterization, and Reactivity Studies.

Mn(III)-iodosylarene porphyrin adducts, [Mn(III)(ArIO)(Porp)]+, were synthesized by reacting electron-deficient Mn(III) porphyrin complexes with iodosylarene (ArIO) at -60 °C and characterized using various spectroscopic methods. The [Mn(III)(ArIO)(Porp)]+ species were then investigated in the epoxidation of olefins under stoichiometric conditions. In the epoxidation of olefins by the Mn(III)-iodosylarene porphyrin species, epoxide was formed as the sole product with high chemoselectivities and stereoselectivities. For example, cyclohexene oxide was formed exclusively with trace amounts of allylic oxidation products; cis- and trans-stilbenes were oxidized to the corresponding cis- and trans-stilbene oxides, respectively. In the catalytic epoxidation of cyclohexene by an electron-deficient Mn(III) porphyrin complex and sPhIO at low temperature (e.g., -60 °C), the Mn(III)-iodosylarene porphyrin species was evidenced as the active oxidant that effects the olefin epoxidation to give epoxide as the product. However, at high temperature (e.g., 0 °C) or in the case of using an electron-rich manganese(III) porphyrin catalyst, allylic oxidation products, along with cyclohexene oxide, were yielded, indicating that the active oxidant(s) was not the Mn(III)-iodosylarene adduct but probably high-valent Mn-oxo species in the catalytic reactions. We also report the conversion of the Mn(III)-iodosylarene porphyrins to high-valent Mn-oxo porphyrins under various conditions, such as at high temperature, with electron-rich porphyrin ligand, and in the presence of base (OH-). The present study reports the first example of spectroscopically well-characterized Mn(III)-iodosylarene porphyrin species being an active oxidant in the stoichiometric and catalytic oxidation reactions. Other aspects, such as one oxidant versus multiple oxidants debate, also were discussed.

3-Hydroxy-2-(trialkylsilyl)phenyl Triflate: A Benzyne Precursor Triggered via 1,3-C-sp2-to-O Silyl Migration.

3-Hydroxy-2-(trialkylsilyl)phenyl triflates are presented as new versatile hydroxyaryne precursors. These are base-activated aryne precursors induced via a C-sp2-to-O 1,3-Brook rearrangement. The reaction of various arynophiles and 3-trialkylsiloxybenzyne generated from 3-hydroxy-2-(trialkylsilyl)phenyl triflate efficiently afforded highly regioselective phenol derivatives. Furthermore, through crossover experiments, the intramolecular mechanism of silyl migration was demonstrated.

Taurine Attenuates Doxorubicin-Induced Toxicity on B16F10 Cells.

This study aimed to investigate the effect of doxorubicin co-treatment with taurine on B16F10 melanoma cells. Frequently, Doxorubicin is used in the treatments of many different kinds of cancers, some of which are soft tissue sarcomas, hematological malignancies and carcinomas. However, the clinical application of doxorubicin is compromised by its severe adverse effects, including cardiotoxicity. In the present study, the efficacy of doxorubicin co-treatment with taurine was investigated. B16F10 cell viability was evaluated using MTT assays, trypan blue dye exclusion assays, and fluorescent staining technique. Apoptotic cells were detected by flow cytometry and the proteins associated with apoptosis and cellular differentiations were assessed by immunoblotting. Doxorubicin inhibited cell growth and induced cell death in B16F10 cells. Interestingly, doxorubicin co-treatment with taurine inhibited apoptosis in B16F10 cells. These results indicate that doxorubicin co-treatment with taurine attenuates doxorubicin-induced cytotoxicity and reduces ROS production in B16F10 cells.

4-hydroxybenzaldehyde-chitooligomers suppresses H2O2-induced oxidative damage in microglia BV-2 cells.

Positive charges of chitooligomer (COS) enable COS to interact with negatively charged anionic groups on the cell surface resulting in an improvement in the biological activity of COS and its derivatives. In this study, 4-hydroxybenzaldehyde-COS (HB-COS) was synthesized and investigated for its abilities against H2O2-induced oxidative stress in microglia BV-2 cells. Under oxidative stress, HB-COS significantly attenuated reactive oxygen species (ROS) generation and DNA oxidation, and upregulated the protein levels of antioxidative enzymes. HB-COS is therefore proposed as a potential protective agent against neuronal damage.