Dicyanoisophorone-based near-infrared fluorescent probe with large Stokes shift for the monitoring and bioimaging of hypochlorite.

Hypochlorite (ClO-), as one of reactive oxygen species (ROS), is closely linked to various illnesses and is essential for the proper functioning of immune system. Hence, monitoring and assessing ClO- levels in organisms are extremely important for the clinical diagnosis of ClO--related disorders. In this study, a novel ClO--selective fluorescent probe, DCP-ClO, was synthesized with dicyanoisophorone-xanthene unit as parent fluorophore, which displayed excellent selectivity towards ClO-, near-infrared emission (755 nm), large Stokes shift (100 nm), real-time response to ClO-, high sensitivity (LOD = 3.95 × 10-8 M), and low cytotoxicity. The recognition mechanism of DCP-ClO towards ClO- was confirmed to be a typical ICT process by HPLC-MS, HR-MS, 1H NMR and theoretical calculations. Meanwhile, DCP-ClO demonstrated remarkable efficacy in monitoring ClO- levels in water samples and eye-catching ability in imaging endogenous/exogenous ClO- in living organisms, which verified its potential as a powerful tool for the recognition of ClO- in complex biological systems.

Sodium Silicate/Urea/Melamine Ternary Synergistic Waterborne Acrylic Acid Flame-Retardant Coating and Its Flame-Retardant Mechanism.

Waterborne acrylic coatings, the largest market share of predominant environmentally friendly coatings, face limitations in their extensive application due to their flammability. The flame-retardant properties of the coatings could be significantly enhanced by incorporate inorganic flame retardants. However, inorganic flame retardants tend to aggregate and unevenly disperse in waterborne acrylic coatings, causing a substantial decrease in flame retardancy. In this work, sodium silicate was utilized as a flame retardant, with urea and melamine serving as modifiers and synergistic agents. This combination resulted in the preparation of a sodium silicate/urea/melamine ternary synergistic waterborne acrylic flame-retardant coating. This coating was applied to the surface of poplar veneer to create flame-retardant poplar veneer. Subsequently, various instruments, including a scanning electron microscope (SEM), a limiting oxygen index meter (LOI), a thermogravimetric analyzer (TG), and a cone calorimeter (CONE), were employed to investigate the relevant properties and mechanisms of both the flame-retardant coating and poplar veneer. The results demonstrated that the sodium silicate/urea/melamine ternary synergistic flame retardant did not exhibit aggregation and could be uniformly dispersed in waterborne acrylic coatings. The physical and mechanical properties of the ternary synergistic flame-retardant poplar veneer coating were satisfactory. Melamine and urea, acting as modifiers, not only greatly enhanced the dispersibility of sodium silicate in waterborne acrylic coatings, but also assisted in the formation of a silicon-containing char layer through the generation of nitrogen, achieving ternary synergistic flame retardancy. In conclusion, this work explores a novel method to efficiently and uniformly disperse inorganic flame retardants in organic coatings. It significantly improves the dispersibility and uniformity of inorganic flame retardants in organic polymers, thereby substantially enhancing the flame-retardant performance of coatings. This work provides a theoretical basis for the research and application of new flame-retardant coatings in the field of chemistry and materials.

Cyanation with isocyanides: recent advances and perspectives.

Cyanation has attracted considerable attention in organic synthesis because nitriles are key structural motifs in numerous important dyes, agrochemicals, natural products and drug molecules. As the fourth generation of cyanating reagents, isocyanides occupy a prominent place in the synthesis of nitriles due to their favorable stability, easy operability and high reactivity. In recent years, three types of cyanation with isocyanides have been established: the cleavage of the C-NC bond of tertiary alkyl isocyanides (Type I), the rearrangement of aryl isocyanides with azides (Type II), and the reductive cyanation of ketones with α-acidic isocyanides (Type III). This review focuses on advances in cyanation with isocyanides with an emphasis on reaction scope, limitations and mechanisms, which could reveal their remarkable value and superiority for accessing various nitriles. In addition, the future development prospects of this specific field are also introduced. We believe that this feature article will serve as a comprehensive tool to navigate cyanation with isocyanides across the vast area of synthetic chemistry.

Rapid Access to Fused Tetracyclic N-Heterocycles via Amino-to-Alkyl 1,5-Palladium Migration Coupled with Intramolecular C(sp3)-C(sp2) Coupling.

An unprecedented route for the preparation of fused tetracyclic N-heterocycles is presented through the palladium-catalyzed cyclization of isocyanides with alkyne-tethered aryl iodides. In this transformation, a novel amino-to-alkyl 1,5-palladium migration/intramolecular C(sp3)-C(sp2) coupling sequence was observed first. More importantly, isocyanide exhibited three roles, serving simultaneously as a C1 synthon, a C1N1 synthon, and the donor of C(sp3) for C(sp3)-C(sp2) coupling, and the reaction was the sole successful example that achieved C(sp3)-H activation of isocyanide.

Accessing indole-isoindole derivatives via palladium-catalyzed [3+2] cyclization of isocyanides with alkynyl imines.

A facile protocol for the preparation of indole-isoindole derivatives was developed and proceeds via a palladium-catalyzed [3+2] cyclization of isocyanides with alkynyl imines. In this transformation, the palladium catalyst has a triple role, serving simultaneously as a π acid, a transition-metal catalyst and a hydride ion donor, thus enabling the dual function of isocyanide both as a C1 synthon for cyanation and a C1N1 synthon for imidoylation. Significantly, the reaction is the sole successful example for accessing indole-isoindole derivatives, and will open up new avenues to assemble unique N-heterocycle frameworks. Furthermore, the synthetic value of this protocol is demonstrated in the late-stage modification of physiologically active molecules and in the construction of aggregation-induced emission compounds.

Antimildew Effect of Three Phenolic Compounds and the Efficacy of Antimildew Sliced Bamboo Veneer.

The development of the bamboo industry has been hindered by environmental issues caused by the application of bamboo preservatives. Chinese herbal phenolic compounds have been shown to possess broad-spectrum, potent antimildew properties, making them promising candidates for the development of new bamboo mildew inhibitors. In this study, we investigated the antimildew properties of three phenolic compounds, eugenol, carvacrol, and paeonol, against common mildews in bamboo materials using the Oxford cup method and the double-dilution method. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to analyze the antimildew mechanism and its effects on mildew cell morphology. Our results showed that carvacrol exhibited the strongest antimildew activity, with minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) values of 1.56 mg/mL and 1.76 mg/mL, respectively, followed by eugenol and paeonol. At a concentration of 25 mg/mL, eugenol and carvacrol had an inhibitory rate of over 50% against various mildews. Different concentrations of the three compounds significantly disrupted the morphology and structural integrity of mildew hyphae, with the extent of damage increasing with concentration and treatment duration. In the sliced bamboo mildew prevention experiment, carvacrol at a concentration of 29.25 mg/mL was found to be highly effective against all tested mildews. Our study provides new insights and a theoretical basis for the development of eco-friendly bamboo mildew inhibitors based on plant phenolic compounds.

Screening of Ionic Liquids against Bamboo Mildew and Its Inhibition Mechanism.

Ionic liquids are a class of organic molten salts that consist entirely of cations and anions. They are characterized by their low vapor pressure, low viscosity, low toxicity, high thermal stability, and strong antifungal potential. In this study, the inhibitory performance of ionic liquid cations against Penicillium citrinum, Trichoderma viride, and Aspergillus niger was investigated, along with the mechanism of cell membrane disruption. The Oxford cup method, SEM, and TEM were employed to examine the extent of damage and the specific site of action of ionic liquids on the mycelium and cell structure of these fungi. The results showed that 1-decyl-3-methylimidazole had a strong inhibitory effect on TV; benzyldimethyldodecylammonium chloride had a weak inhibitory effect on PC, TV, AN, and a mixed culture; while dodecylpyridinium chloride exhibited significant inhibitory effects on PC, TV, AN, and Mix, with more prominent effects observed on AN and Mix, exhibiting MIC values of 5.37 mg/mL, 5.05 mg/mL, 5.10 mg/mL, and 5.23 mg/mL, respectively. The mycelium of the mildews showed drying, partial loss, distortion, and uneven thickness. The cell structure showed separation of the plasma wall. The absorbance of the extracellular fluid of PC and TV reached the maximum after 30 min, while that of AN reached the maximum after 60 min. The pH of the extracellular fluid decreased initially and then increased within 60 min, followed by a continuous decrease. These findings provide important insights for the application of ionic liquid antifungal agents in bamboo, medicine, and food.

Infantile Cranial Fasciitis: A Clinicopathologic Evaluation.

OBJECTIVE: To investigate the clinicopathologic features, immunophenotype, molecular genetic changes, and differential diagnosis of cranial fasciitis (CF). METHODS: The clinical manifestations, imaging, surgical technique, pathologic characteristics, special staining, and immunophenotype, as well as break-apart fluorescence in situ hybridization assay for USP6 of 19 CF cases were analyzed, retrospectively. RESULTS: The patients were 11 boys and 8 girls, aged 5 to 144 months, with a median age of 29 months. There were 5 cases (26.31%) in the temporal bone, 4 cases (21.05%) in the parietal bone, 3 cases (15.78%) in the occipital bone, 3 cases (15.78%) in the frontotemporal bone, 2 cases (10.52%) in the frontal bone, 1 case (5.26%) in the mastoid of middle ear, and 1 case (5.26%) in the external auditory canal. The main clinical manifestations were painless, with the presentation of masses that grew rapidly and frequently eroded the skull. There was no recurrence and no metastasis after the operation. Histologically, the lesion consists of spindle fibroblasts/myofibroblasts arranged in bundles, braided or atypical spokes. Mitotic figures could be seen, but not atypical forms. Immunohistochemical studies showed diffuse strong positive SMA and Vimentin in all CFs. These cells were negative for Calponin, Desmin, ß-catenin, S-100, and CD34. The ki-67 proliferation index was 5% to 10%. Ocin blue-PH2.5 staining showed blue-stained mucinous features in the stroma. The positive rate of USP6 gene rearrangement detected by fluorescence in situ hybridization assay was about 10.52%, and the positive rate was not related to age. All patients were observed for 2 to 124 months and showed no signs of recurrence or metastasis. CONCLUSIONS: In summary, CF was a benign pseudosarcomatous fasciitis that occurs in the skull of infants. Preoperative diagnosis and differential diagnosis were difficult. Computed tomography typing might be beneficial for imaging diagnosis, and pathologic examination might be the most reliable way to diagnose CF.

Halogen cation-promoted and solvent-regulated electrophilic cyclization for the regioselective synthesis of 3-haloquinolines and 3-halospirocyclohexadienones.

A novel approach for the production of halogen cations through the reaction of halogens with silver ions is described in this paper. On this basis, the regioselective synthesis of 3-haloquinolines and 3-halospirocyclohexadienones is realized through solvent regulation. The gram-scale reaction and the compatibility of complex substrates demonstrate the synthetic potential of this protocol, which will be an appealing strategy in organic synthesis.

Clinicopathological Analysis of Sturge-Weber Syndrome with Focal Cortical Dysplasia FCD IIIc.

Objective: To investigate the clinicopathological features of children with Sturge-Weber syndrome and to analyze the correlation between the distribution area of leptomeningeal angiomatosis, the degree of cerebral cortical calcification, and the degree of cerebral atrophy associated with epileptic seizures. Methods: 10 children were diagnosed with SWS with FCD IIIc by histopathology and immunohistochemistry. Spearman correlation analysis was used to calculate the association of SWS with FCD IIIc and seizures in children. Results: The leptomeningeal angiomatosis area was markedly positively correlated with the degree of brain atrophy in 10 children with SWS (r = 0.783, p = 0.007). The distribution of leptomeningeal hemangiomatosis, the degree of cortical calcification, and brain atrophy were not significantly correlated with epilepsy. Conclusion: SWS may be accompanied by FCD IIIc. The more extensive the cerebral lobes of leptomeningeal angiomatosis in SWS, the more pronounced the brain atrophy.

Process and Anti-Mildew Properties of Tea Polyphenol-Modified Citral-Treated Bamboo.

In order to reduce the oxidative degradation of citral, our research group modified citral with the natural antioxidant from tea polyphenols and applied it to bamboo processing to enhance the anti-mold effect of bamboo, but its application to the bamboo treatment process and the anti-mold effect is still not clear. For this reason, in this paper, the tea polyphenol-modified citral anti-mildew treatment of bamboo as well as the anti-mildew properties of bamboo were explored using the orthogonal testing method and a UV-vis spectrophotometer. The results showed that when the concentration of tea polyphenol-modified citral reached 175 mg mL-1 and above, the efficacy of the anti-mildew treated bamboo against common molds reached 100%; the improved anti-mildew treatment process parameters for bamboo were as follows: impregnation pressure 0.6 MPa, impregnation time 150 min, and tea polyphenol-modified citral concentration 200 mg mL-1. Following the tea polyphenol-modified citral anti-mildew treatment of bamboo, not only did it improve the anti-mildew properties of the bamboo materials, but it also added a fresh lemon fragrance without altering the original colour, microstructure, and chemical properties of the bamboo materials.

Antioxidant-Mediated Modification of Citral and Its Control Effect on Mildewy Bamboo.

To reduce the oxidative degradation of citral and improve its antimildew performance, citral was modified with natural antioxidants such as tea polyphenols, ascorbic acid, and theaflavin in the present study. Additionally, the effects of these natural antioxidants on the citral degradation rate and DPPH radical-scavenging rate, as well as the effectiveness of antioxidant-modified citral in the antimildew treatment of bamboo were investigated. Ascorbic acid, theaflavin, and tea polyphenols improved the antioxidant performance of citral to some extent, and the tea polyphenols exhibited the best antioxidant performance. When the amount of tea polyphenols added to citral reached 1.0%, the oxidative degradation of citral was effectively prevented. Compared with citral, tea-polyphenol-modified citral could reduce the efficacy of the bamboo antimildew treatment against all four mildews and the effectiveness of the antimildew treatment reached 100%. Citral modification with antioxidants reduced the amount of citral required in the treatment, thereby reducing the treatment cost for bamboo mildew.

Preparation of Citral Compound and Its Bamboo Antimildew Properties.

To reduce the amount of citral used without reducing the antimildew performance of bamboo, the citral compound preparation process, the distribution of the compound in bamboo, and its antimildew performance were investigated using the Oxford cup method, Fourier-transform infrared spectroscopy, and ultraviolet spectrophotometry. The results revealed that the combination of citral with cinnamaldehyde or thymol may lead to partial chemical reactions, which may change the chemical structure of citral and affect its bacteriostatic properties. The bacteriostatic properties of the citraldehyde thymol compound against common molds of bamboo were considerably superior to those of the citral cinnamaldehyde compound. The limonaldehyde thymol compound showed a low distribution trend outside and vice versa inside in the treated bamboo. The citral thymol compound exhibited good antimildew performance at a concentration of 200 mg/mL. The citral thymol compound could reduce the amount of citral by approximately 67 mg/mL without reducing the antimildew performance of bamboo.

Candida albicans Multilocus Sequence Typing Clade I Contributes to the Clinical Phenotype of Vulvovaginal Candidiasis Patients.

Candida albicans is the most frequent fungal species responsible for vulvovaginal candidiasis (VVC), which exhibits distinct genetic diversity that is linked with the clinical phenotype. This study aimed to assess the genotypes and clinical characteristics of different C. albicans isolates from VVC patients. Based on multilocus sequence typing (MLST), clade 1 was identified as the largest C. albicans group, which appeared most frequently in recurrent VVC and treatment failure cases. Further study of antifungal susceptibility demonstrated that MLST clade 1 strains presented significantly higher drug resistance ability than non-clade 1 strains, which result from the overexpression of MDR1. The mRNA and protein expression levels of virulence-related genes were also significantly higher in clade 1 isolates than in non-clade 1 isolates. Proteomic analysis indicated that the protein stabilization pathway was significantly enriched in clade 1 strains and that RPS4 was a central regulator of proteins involved in stress resistance, adherence, and DNA repair, which all contribute to the resistance and virulence of MLST clade 1 strains. This study was the first attempt to compare the correlation mechanisms between C. albicans MLST clade 1 and non-clade 1 strains and the clinical phenotype, which is of great significance for VVC classification and treatment.

Preparation and Flame Retardant Properties of Calcium-Aluminium Hydrotalcite with Root Cutting Silicate Layers as Bamboo Flame Retardants.

Bamboo has been widely used in architecture, decoration and other fields because of its advantages of short growth period, high strength and degradability. However, bamboo, as a combustible material like wood, are easy to burn and cause building fires. However, the existing bamboo water-based flame retardants have some shortcomings, such as strong hygroscopicity and easy loss, which limits the application of bamboo products. In order to improve the flame retardant performance of bamboo, CaAl-SiO2 layered double hydroxide (LDH) as bamboo flame retardant was synthesised by coprecipitation method. The influence of preparation technology on CaAl-SiO3-LDH structures and properties as well as the flame retardant and smoke suppression characteristics of flame retardant-treated bamboo was discussed. The results revealed that the crystallisation temperature, crystallisation time and crystallisation concentration of CaAl-SiO3-LDHs considerably affected its structure and properties. The optimum technological parameters for preparing CaAl-SiO3-LDHs by using the coprecipitation method are as follows: crystallisation temperature of 100 °C, crystallisation time of 9 h and Ca2+ solution molar concentration of 0.33 mol/L. Compared with nonflame-retardant wood, CaAl-SiO3-LDH flame retardant treatment delayed the peak time of the heat release rate by 20 s and the ignition time by 77.78% and increased the carbon residue rate by 9.54%. This study can provide reference for the research of new flame retardant for bamboo products.

Investigation of the Release Mechanism and Mould Resistance of Citral-Loaded Bamboo Strips.

In the present study, the sustained-release system loading citral was synthesised by using PNIPAm nanohydrogel as a carrier and analysed its drug-release kinetics and mechanism. Four release models, namely zero-order, first-order, Higuchi, and Peppas, were employed to fit the experimental data, and the underlying action mechanism was analysed. The optimised system was applied to treat a bamboo mould, followed by assessment of the mould-proof performance. Our experimental results revealed that the release kinetics equation of the system conformed to the first order; the higher the external temperature, the better the match was. In the release process, PNIPAm demonstrated a good protection and sustained-release effect on citral. Under the pressure of 0.5 MPa, immersion time of 120 min, and the system concentration ratio of 1, the optimal drug-loading parameters were obtained using the slow-release system with the best release parameters. Compared to the other conditions, bamboos treated with pressure impregnation demonstrated a better control effect on bamboo mould, while the control effect on Penicillium citrinum, Trichoderma viride, Aspergillus niger, and mixed mould was 100% after 28 days. Moreover, the structure and colour of bamboo remained unchanged during the entire process of mould control.

circ0093740 Promotes Tumor Growth and Metastasis by Sponging miR-136/145 and Upregulating DNMT3A in Wilms Tumor.

As a research hotspot, circular RNAs (circRNAs) is one type of non-coding RNAs which have many different functions in biological processes. However, there is lack of study investigating the underlying molecular mechanism and the potential roles of circRNAs in Wilms tumor. We conducted a high-throughput microarray sequencing to screen differentially expressed circRNAs in Wilms tumor. A novel circRNA (circ0093740) was identified as a frequently upregulated circRNA in Wilms tumor cells and tissues. Suppression of circ0093740 remarkably inhibited the proliferation and migration ability in Wilms tumor, validated by several experiments. The molecular mechanism of circ0093740 was investigated by luciferase assays and RNA immunoprecipitation assays. The results revealed that circ0093740 promotes the growth and migration ability by sponging miR-136/145 and upregulating DNMT3A. In conclusion, our study discovered the biological role of the circ0093740-miR-136/145-DNMT3A axis in Wilms tumor growth and metastasis which is important for developing new treatment strategy.

Microscopic analysis of overglaze green pigment on Chinese famille rose porcelain from the Imperial Palace.

Famille rose porcelain made in the imperial workshop was one of the symbols of the highest manufacturing techniques in ancient China. It was very precious and only owned by the royals for a long time. Because of its complex making technology, overglaze green pigment painted on famille rose porcelain shows many variations. In this work, selected porcelain shards that were excavated at the Forbidden City were analyzed by using microscopy observation, micro-Raman spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectrometer to obtain a deep understanding of overglaze green pigment technique on famille rose porcelain. The results revealed that four types of green pigment are used in the selected samples. With different recipes and combinative ways on green pigment and opaque white pigment, craftsmen can choose the using method of pigment to get the effect they want.

Accelerating Sequential Minimal Optimization via Stochastic Subgradient Descent.

Sequential minimal optimization (SMO) is one of the most popular methods for solving a variety of support vector machines (SVMs). The shrinking and caching techniques are commonly used to accelerate SMO. An interesting phenomenon of SMO is that most of the computational time is wasted on the first half of iterations for building a good solution closing to the optimal. However, as we all know, the stochastic subgradient descent (SSGD) method is extremely fast for building a good solution. In this paper, we propose a generalized framework of accelerating SMO through SSGD for a variety of SVMs of binary classification, regression, ordinal regression, and so on. We also provide a deep insight about why SSGD can accelerate SMO. Experimental results on a variety of datasets and learning applications confirm that our method can effectively speed up SMO.