Phosphine-Catalyzed Annulations of Azomethine Imines: Allene-Dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] Pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways—the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol—the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates—suggest that it might find extensive applications in heterocycle synthesis

Crowdsourcing geospatial data for Earth and human observations: a review

The transformation from authoritative to user-generated data landscapes has garnered considerable attention, notably with the proliferation of crowdsourced geospatial data. Facilitated by advancements in digital technology and high-speed communication, this paradigm shift has democratized data collection, obliterating traditional barriers between data producers and users. While previous literature has compartmentalized this subject into distinct platforms and application domains, this review offers a holistic examination of crowdsourced geospatial data. Employing a narrative review approach due to the interdisciplinary nature of the topic, we investigate both human and Earth observations through crowdsourced initiatives. This review categorizes the diverse applications of these data and rigorously examines specific platforms and paradigms pertinent to data collection. Furthermore, it addresses salient challenges, encompassing data quality, inherent biases, and ethical dimensions. We contend that this thorough analysis will serve as an invaluable scholarly resource, encapsulating the current state-of-the-art in crowdsourced geospatial data, and offering strategic directions for future interdisciplinary research and applications across various sectors

Efficient Soluble Polymer-Supported Tartrate/Ti Catalyst for Asymmetric Oxidation of Prochiral Sulfides

A group of soluble polymer-supported chiral tartrate ligands was prepared by liquid-phase synthesis with ligand diversity strategy. Moderate to excellent chemical yields and enantiomeric excesses were obtained by using soluble polymer-supported tartrate ester in asymmetric oxidation of prochiral sulfides using Ti(O-i-Pr)4/cumyl hydroperoxide, and the workup was greatly simplified. The influence of substituent in chiral tartrate ligands on the enantioselectivities of the reaction was disclosed

ChemInform Abstract: Efficient Soluble Polymer-Supported Tartrate/Ti Catalyst for Asymmetric Oxidation of Prochiral Sulfides.

A group of soluble polymer-supported chiral tartrate ligands was prepared by liquid-phase synthesis with ligand diversity strategy. Moderate to excellent chemical yields and enantiomeric excesses were obtained by using soluble polymer-supported tartrate ester in asymmetric oxidation of prochiral sulfides using Ti(O-i-Pr)4/cumyl hydroperoxide, and the workup was greatly simplified. The influence of substituent in chiral tartrate ligands on the enantioselectivities of the reaction was disclosed

Endogenous endophthalmitis caused by a multidrug-resistant hypervirulent Klebsiella pneumoniae strain belonging to a novel single locus variant of ST23: first case report in China

Abstract Background Endogenous endophthalmitis caused by hypervirulent Klebsiella pneumoniae (HVKP) is an emerging infectious disease commonly with a devastating visual outcome. Most HVKP strains display a wild-type susceptibility profile to antibiotics. However, reports of antimicrobial-resistant HVKP have increased over time, which poses a serious therapeutic dilemma. Case presentation A 25-year-old man with a liver abscess and poorly controlled diabetes mellitus was admitted for endophthalmitis due to K. pneumoniae. The isolate displayed hypermucoviscosity as determined by a positive string test and exhibited resistance to ceftazidime, piperacillin-tazobactam and amikacin. Whole genome sequencing (WGS) analysis demonstrated the isolate to be a K1-serotype strain and belong to a novel single locus variant of ST23, ST2922. In addition to the virulence genes linked to HVKP, rmpA, magA, iucABCDiutA (aerobactin), ybtAPSTUX (yersiniabactin) and iroBDN (salmochelin), it was found to harbor extended-spectrum β-lactamase (ESBL) gene (bla CTX-M-14), AmpC β-lactamase gene (bla DHA), and 16S rRNA methylase gene (armA). Conclusions This is the first known case of endogenous endophthalmitis caused by a multidrug-resistant HVKP strain ever reported in China. Early diagnosis and treatment with intravenous and intravitreal injection of carbapenem were essential for a favorable visual outcome

Hexarelin suppresses cardiac fibroblast proliferation and collagen synthesis in rat

Abnormal growth of cardiac fibroblasts is critically involved in the pathophysiology of cardiac hypertrophy/remodeling. Hexarelin is a synthetic growth hormone secretagogue (GHS), which possesses a variety of cardiovascular protective activities mediated via the GHS receptor (GHSR), including improving cardiac dysfunction and remodeling. The cellular and molecular mechanisms underlying the effect of GHS on cardiac fibrosis are, however, not clear. In this report, cultured cardiac fibroblasts from 8-day-old rats were stimulated with ANG II or FCS to induce proliferation. The fibroblast proliferation and DNA and collagen synthesis were evaluated utilizing 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, 3H-thymidine incorporation, and 3H-proline incorporation. The level of mRNA of transforming growth factor (TGF)-beta was evaluated by RT-PCR, and the active TGF-beta1 release from cardiac fibroblasts was evaluated by ELISA. The level of cellular cAMP was measured by radioimmunoassay. In addition, the effects of 3,7-dimethyl-l-propargylxanthine (DMPX; a specific adenosine receptor A2R antagonist) and 8-cyclopentyl-1,3-dipropylxanthine (DPCPX; a specific A1R antagonist) were tested. It was found that incubation with 10–7 mol/l hexarelin for 24 h 1) inhibited the ANG II-induced proliferation and collagen synthesis and the 5% FCS- and TGF-beta-induced increase of DNA synthesis in cardiac fibroblast and 2) reduced ANG II-induced upregulation of TGF-beta mRNA expression and active TGF-beta1 release from fibroblasts. Hexarelin increased the cellular level of cAMP in cardiac fibroblasts. DMPX (10–8 mol/l) but not DPCPX abolished the effect of hexarelin on cardiac fibroblast DNA synthesis. It is concluded that hexarelin inhibits DNA and collagen synthesis and proliferation of cardiac fibroblasts through activation of both GHSR and A2R and diminishment of ANG II-induced increase in TGF-beta expression and release

A Hybrid Method to Incrementally Extract Road Networks Using Spatio-Temporal Trajectory Data

With the rapid development of urban traffic, accurate and up-to-date road maps are in crucial demand for daily human life and urban traffic control. Recently, with the emergence of crowdsourced mapping, a surge in academic attention has been paid to generating road networks from spatio-temporal trajectory data. However, most existing methods do not explore changing road patterns contained in multi-temporal trajectory data and it is still difficult to satisfy the precision and efficiency demands of road information extraction. Hence, in this paper, we propose a hybrid method to incrementally extract urban road networks from spatio-temporal trajectory data. First, raw trajectory data were partitioned into K time slices and were used to initialize K-temporal road networks by a mathematical morphology method. Then, the K-temporal road networks were adjusted according to a gravitation force model so as to amend their geometric inconsistencies. Finally, road networks were geometrically delineated using the k-segment fitting algorithm, and the associated road attributes (e.g., road width and driving rule) were inferred. Several case studies were examined to demonstrate that our method can effectively improve the efficiency and precision of road extraction and can make a significant attempt to mine the incremental change patterns in road networks from spatio-temporal trajectory data to help with road map renewal

Integrated near-infrared fiber-optic photoacoustic sensing demodulator for ultra-high sensitivity gas detection

An integrated near-infrared fiber-optic photoacoustic sensing demodulator was established for ultra-high sensitivity gas detection. The demodulator has capacities of interference spectrum acquisition and calculation, laser modulation control as well as digital lock-in amplification. FPGA was utilized to realize all the control and signal processing functions, which immensely improved the integration and stability of the system. The photoacoustic signal detection based on fiber-optic Fabry–Perot (F-P) acoustic sensor was realized by applying ultra-high resolution spectral demodulation technique. The detectable frequency of photoacoustic signal achieved 10 kHz. The system integrated lock-in amplification technology, which made the noise sound pressure and dynamic response range of sound pressure detection reached 3.7 μPa/√Hz @1 kHz and 142 dB, respectively. The trace C2H2 gas was tested with a multi-pass resonant photoacoustic cell. Ultra-high sensitivity gas detection was accomplished, which was based on high acoustic detection sensitivity and the matching digital lock-in amplification. The system detection limit and normalized noise equivalent absorption (NNEA) coefficient were reached 3.5 ppb and 6.7 × 10−10 cm−1WHz−1/2, respectively. The devised demodulator can be applied for long-distance gas measurement, which depends on the fact that both the near-infrared photoacoustic excitation light and the probe light employ optical fiber as transmission medium

Construction and characterization of thymidine auxotrophic (ΔthyA) recombinant Lactobacillus casei expressing bovine lactoferricin

Abstract Background Lactobacillus casei (L. casei) is well known for its probiotic property in human and animals. Lactoferricin (Lfcin) polypeptide can effectively modulate host immune responses and have antimicrobial activity in vivo and in vitro. In order to develop a food-grade L. casei system constitutively expressing bovine Lfcin, this study constructed a thymidine auxotrophy (ΔthyA) recombinant L. casei. Results Based on the thymidylate synthase gene (thyA) insert site, LFEC(Lfcin expression cassette)was inserted into L. casei genome through homologous recombination, successfully expressed and could be stably inherited. The recombinant L. casei, ΔthyA L. casei-LFEC, is sensitive to chloramphenicol and limited when cultured without thymine. Meanwhile, ΔthyA L. casei-LFEC has both good antibacterial activity against Escherichia coli and Staphylococcus aureus and antiviral activity against porcine epidemic diarrhea virus (PEDV). Conclusions We successfully constructed a recombinant L. casei strain expressing Lfcin, ΔthyA L. casei-LFEC, which could only survive in the presence of thymine, and had excellent antimicrobial and antiviral activity with good genetic stability and sensitivity. This research provides a cost-effective alternative to the antibiotics with additional biological functions and wider applicability prospect. Using ΔthyA as the selectable mark instead of antibiotic to construct genetic engineering L.casei provides a safe and effective approach of feed additives in livestock raising

Chitosan and chitosan‑based composites as beneficial compounds for animal health: Impact on gastrointestinal functions and biocarrier application

Chitosan and chitosan-based composites are increasingly gaining attention as feed additives in animal production. However, few studies have summarized their multifunctional roles and applications in animals. This review presents an extensive overview of chitosan and chitosan-based composites in animal nutrition, with emphasis on their roles in gastrointestinal function and substance delivery. It is surmised that the supplementation of chitosan and its derivatives to animals improves the growth performance, productivity, nutrient digestibility, antioxidant capacity, gut health, immunity, and health status of animals. Additionally, the encapsulation of chitosan-based composites as bioactive agents for nutrient, drug, and vaccine delivery enhances the nutritional qualities of animal feeds and boosts animal health. Therefore, a comprehensive understanding of the potentials of chitosan and chitosan-based composites as feed additives, their actions on gastrointestinal health and bio-delivery, and the challenges underlying their applications would promote their effective and efficient utilization for animal production and foster research progress in this field