Synthesis of Benzo[a]carbazoles and Dibenzo[c,g]carbazoles via Sequential Gold Catalysis and Photomediated Cyclization.

Herein, we report a reaction protocol for the construction of benzo[a]carbazole and dibenzo[c,g]carbazole frameworks. The detailed gold catalytic reaction conditions developed for the challenging intermolecular carbon nucleophilic addition to internal alkynes are realized, giving the desired alkyne hydroarylation products in good yields. The resulting trisubstituted alkenes are able to undergo photomediated cyclization, furnishing the desired carbazole molecules with excellent yields and high efficiency.

Palladium-Catalyzed Arylation of C(sp2)-H Bonds and C(sp3)-H Bonds with 4-Amino-benzotriazole as the Bidentate Directing Group.

The arylation of C(sp2)-H and C(sp3)-H bonds in carboxylic acids catalyzed by Pd(II) with 4-aminobentriazole as the directing group was investigated. In addition to activation of the C(sp2)-H bond, selective arylation of alkyl carboxylic acids and amino acids in the ß position can also be achieved. This strategy involved a 5,5-bicyclic Pd intermediate complex whose structure was determined by X-ray single crystal diffraction analysis. Importantly, the DG (directing group) can be easily removed under mild conditions.

CUDM: A Combined UAV Detection Model Based on Video Abnormal Behavior.

The widespread use of unmanned aerial vehicles (UAVs) has brought many benefits, particularly for military and civil applications. For example, UAVs can be used in communication, ecological surveys, agriculture, and logistics to improve efficiency and reduce the required workforce. However, the malicious use of UAVs can significantly endanger public safety and pose many challenges to society. Therefore, detecting malicious UAVs is an important and urgent issue that needs to be addressed. In this study, a combined UAV detection model (CUDM) based on analyzing video abnormal behavior is proposed. CUDM uses abnormal behavior detection models to improve the traditional object detection process. The work of CUDM can be divided into two stages. In the first stage, our model cuts the video into images and uses the abnormal behavior detection model to remove a large number of useless images, improving the efficiency and real-time detection of suspicious targets. In the second stage, CUDM works to identify whether the suspicious target is a UAV or not. Besides, CUDM relies only on ordinary equipment such as surveillance cameras, avoiding the use of expensive equipment such as radars. A self-made UAV dataset was constructed to verify the reliability of CUDM. The results show that CUDM not only maintains the same accuracy as state-of-the-art object detection models but also reduces the workload by 32%. Moreover, it can detect malicious UAVs in real-time.

Construction of Stable Helical Metal-Organic Frameworks with a Conformationally Rigid "Concave Ligand".

A helical metal-organic framework was prepared by using a conformationally rigid tetratopic benzoic acid ligand with binding units pointing toward each other (concave ligand). To avoid the obvious intramolecular interactions between binding units, matching spacing groups were applied to introduce atropic repulsion, thereby allowing the formation of extended frameworks for the first time. With this new ligand design, a helical-shaped MOF with significantly improved air and moisture stability was successfully prepared, thus providing a new strategy for ligand design toward porous material constructions.

Accelerated atrazine degradation and altered metabolic pathways in goat manure assisted soil bioremediation.

The intensive and long-term use of atrazine in agriculture has resulted in serious environmental pollution and consequently endangered ecosystem and human health. Soil microorganisms play an important role in atrazine degradation. However, their degradation efficiencies are relatively low due to their slow growth and low abundance, and manure amendment as a practice to improve soil nutrients and microbial activities can solve these problems. This study investigated the roles of goat manure in atrazine degradation performance, metabolites and bacterial community structure. Our results showed that atrazine degradation efficiencies in un-amended soils were 26.9-35.7% and increased to 60.9-84.3% in goat manure amended treatments. Hydroxyatrazine pathway was not significantly altered, whereas deethylatrazine and deisopropylatrazine pathways were remarkably enhanced in treatments amended with manure by encouraging the N-dealkylation of atrazine side chains. In addition, goat manure significantly increased soil pH and contents of organic matters and humus, explaining the change of atrazine metabolic pathway. Nocardioides, Sphingomonas and Massilia were positively correlated with atrazine degradation efficiency and three metabolites, suggesting their preference in atrazine contaminated soils and potential roles in atrazine degradation. Our findings suggested that goat manure acts as both bacterial inoculum and nutrients to improve soil microenvironment, and its amendment is a potential practice in accelerating atrazine degradation at contaminated sites, offering an efficient, cheap, and eco-friendly strategy for herbicide polluted soil remediation.

"Orthogonal-Twisted-Arm" Ligands for The Construction of Metal-Organic Frameworks (MOFs): New Topology and Catalytic Reactivity.

Extended tetratopic benzoic acid ligands with "orthogonal-twisted-arms" conformations were designed and synthesized for the construction of new MOF structures (OTA-MOF). Upon coordination with Cd2+ and Cu2+ cations, two well-defined new MOFs were prepared. X-ray single crystal structures were successfully obtained, demonstrating the formation of a new topology (4,4,4-c). The OTA2-MOF-Cu gave moderate stability in organic solvents and good gas sorption ability toward CO2 . This new MOF showed superior catalytic reactivity toward the epoxide-CO2 cycloaddition, giving >50 folds yield enhancement over the controlled reaction without MOF. It is expected that this new ligand design, porous structure, and excellent CO2 catalytic reactivity will make OTA-MOF promising new materials for applications in catalysis and separation.

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry.

As an NNN-tridentate ligand, the 2,2':6',2"-terpyridine plays an important role in coordination chemistry. With three coordination sites and low LUMO, terpyridine and its derivatives are one of the typical Pincer ligand and/or non-innocent ligands in transition metal catalysis. Interesting catalytic reactivities have been obtained with these tpy-metal complexes targeting some challenging transformations, such as C-C bond formation and hydrofunctionalization. On the other hand, terpyridine ligands can form "closed-shell" octahedral complexes, which provide a linear and stable linkage in supramolecular chemistry. Numerous supramolecular architectures have been achieved using modified terpyridine ligands including Sierpinski triangles, hexagonal gasket and supramolecular rosettes. This review presents a summary of recent progress regarding transition metal-terpyridine complexes with the focus on their applications in catalysis and supramolecular structure construction. Facile synthesis of terpyridine derivatives is also described. We hope this article can serve to provide some general perspectives of the terpyridine ligand and their applications in coordination chemistry.

Triazole-gold (TAAu) catalyzed three-component coupling (A3 reaction) towards the synthesis of 2, 4-disubstituted quinoline derivatives.

A gold-catalyzed three-component coupling reaction (A3 reaction) was developed as an efficient approach for the synthesis of challenging 2, 4-disubstituted quinoline derivatives. Compared to previously reported Cu/Au bi-catalyst system, this protocol enables achieving A3 reaction only in the presence of triazole-gold catalyst. Notably, 4-alkyl substituted or 2-alkyl substituted quinoline derivatives were obtained with good yields, which highlighted the unique advantage of this new strategy.

Triazole-imidazole (TA-IM) derivatives as ultrafast fluorescent probes for selective Ag+ detection.

1,2,3-Triazole-imidazole derivatives (TA-IM) were prepared as fluorescent probes for silver ion detection. The design principle is the incorporation of an intramolecular H-bond between the imidazole and triazole moiety that enables a co-planar conformation to achieve fluorescence emission in the UV-blue range. Screening of different metal ions revealed excellent binding affinity of this new class of compounds toward silver ions in aqueous solution. The novel probe provided ultrafast detection (<30 s) even for a very low concentration of silver ions (in the nM range) with good linear correlation, making it a practical sensor for detection of silver ions.

Facile synthesis and stereo-resolution of chiral 1,2,3-triazoles.

We describe herein the first facile synthesis of chiral triazoles through side chain functionalization. Readily available C-vinyl triazoles were used as starting materials, followed by sequential epoxidation, rearrangement and reduction to give the corresponding hydroxyl-triazoles. The CalB lipase catalyzed kinetic resolution gave enantiomerically pure (>99% ee) chiral triazoles in excellent yield. These new chiral TAs were also successfully applied as ligands in asymmetric addition of diethylzinc to aldehydes.

Novel Chiral Bifunctional L-Thiazoline-Thiourea Derivatives: Design and Application in Enantioselective Michael Reactions.

Several novel chiral bifunctional L-thiazoline-thiourea derivatives were easily synthesized from commercially available L-cysteine in high yield. These catalysts were subsequently applied to the enantioselective Michael addition of acetylacetone to ß-nitrostyrenes. The products with S configuration were obtained in 98% enantiomeric excess (ee) when the L-thiazoline-thiourea derivatives were used. A plausible transition state model is proposed to explain the observed enantioselectivities.

Finite series expansion of a Gaussian beam for the acoustic radiation force calculation of cylindrical particles in water.

This paper focuses on studying the interaction between an acoustical Gaussian beam and cylindrical particles. Based on the finite series method, the Gaussian beam is expanded as cylindrical functions and the beam coefficient of a Gaussian beam is obtained. An expression for the acoustic radiation force function that is the radiation force per unit energy density and unit cross-sectional surface area for a cylinder in a Gaussian beam is presented. Numerical results for the radiation force function of a Gaussian beam are presented for rigid cylinders, liquid cylinders, elastic cylinders, and viscoelastic cylinders to illustrate the theory. The radiation force function versus the dimensionless frequency ka (where k is the wave number and a is the radius of the cylinder) are discussed for different beam waists. The simulation results show the differences from those of a plane wave when the beam waist w0≤5λ (where λ is the wave length). The beam waist has no effects on the radiation force function when ka<1, while the beam waist has greater effects when ka>1. The radiation force function reaches the plane wave limit when w0>5λ. The acoustic radiation force function is also determined by the parameters of the particles.

One-Pot Synthesis of Polycyclic Sultams Enabled by Gold-Catalyzed Hydroamination of o-Alkynylbenzenesulfonamides and Subsequent Iodine(III)-Mediated Counteranion-Assisted Intramolecular Annulation.

Herein we present a facile and efficient one-pot synthetic protocol for the construction of polycyclic sultams. This protocol involves gold-catalyzed intramolecular hydroamination of o-alkynylbenzenesulfonamides followed by HTIB-mediated counteranion-assisted intramolecular annulation. The transformation tolerates a wide range of functional groups, resulting in the formation of highly functionalized and valuable polycyclic sultam skeletons in moderate to excellent yields. These polycyclic sultams are widely used as key building blocks in organic science.

A novel dual-function fluorescent probe for the detection of cysteine and its applications in vitro.

A fluorescent probe of both colorimetric and ratiometric type for highly selective and sensitive detection of Cys (cysteine) is very important in biological analysis. In this work, a new colorimetric and ratiometric fluorescent probe ((E)-2-(2-(5-(4-(acryloyloxy)phenyl)furan-2-yl)vinyl)-3-methylbenzo[d]thiazol-3-ium iodide, LP-1) was designed and synthesized for the detection of Cys. The reaction mechanism of LP-1 toward Cys involves a conjugate addition reaction between Cys and the α,ß-unsaturated carbonyl group, leading to the formation of an intermediate thioether, followed by intramolecular cyclization to produce the desired compounds LP-1-OH. At this point, the ICT process is activated, significantly increasing the fluorescence intensity of the molecules. Meanwhile, LP-1 is highly selective and sensitive to Cys identification under optimized experimental conditions. LP-1 shows a good linear relationship in the range of Cys concentration from 0.40 µM to 40 µM (R2 = 0.9942) and the limit of detection (LOD) of Cys is 0.19 µM. In addition, we have developed a simple, portable and low-cost smartphone-based high-sensitivity Cys detection method based on naked eye obvious color detection. LP-1 also has low cell toxicity and can be successfully used for biological imaging of Cys, suggesting that it is a promising biological application tool for Cys detection.

A new ratiometric fluorescent probe for rapid and highly selective detection of Cysteine in bovine serum.

As one of the most fundamental thiol compounds in the human body, cysteine (Cys) is involved in maintaining redox balance. Abnormal Cys levels can lead to various diseases. In this work, we successfully synthesized a fluorescent probe (CTBA) that can specifically detect Cys using acrylate as the reaction site, and CTBA has met the selectivity and anti-interference for Cys detection under optimized conditions. The linear range for Cys detection is between 0.05 and 100 µM and the detection limit is 0.0381 µM. Finally, this probe is used to detect the Cys content in three bovine serum samples and the test results are satisfactory.

A new FRET-based fluorescent probe: Colorimetric and ratiometric detection of hypochlorite and anti-counterfeiting applications.

Hypochlorite (ClO-), as the main component of widely used disinfectants in daily life, comes into closer contact with the human body, which can lead to a number of diseases. The high-performance method is increasingly needed to detect ClO- in our daily life. In this report, we successfully synthesized a FRET ratiometric fluorescent probe (NDAC) containing benzoxadiazole moieties and coumarin moieties bound via ethylenediamine. As expected, NDAC has excellent selectivity and anti-interference ability toward ClO-, and the ratio of fluorescence intensity (I471 nm/I533 nm) has a very good linear relationship with the concentration of ClO-, with a wide linear range (2.5-1750 µM) and low detection limit (0.887 µM). Furthermore, we have successfully applied it for the quantitative detection of ClO- in water samples in daily life. At the same time, there is a very clear change in the fluorescence color after the reaction of the NDAC with ClO-. The blue/green value (B/G) of this color change also shows a very good linear relationship to ClO- (5.0-1000 µM). Therefore, the NDAC has also been successfully used for test strip detection and quantitative detection of ClO- in actual samples through smartphone-based fluorescence image analysis, and this method can provide faster, more convenient and more accessible detection. In addition, NDAC sensors also have potential applications in the field of information anti-counterfeiting.

Natural and anthropogenic controls on environmental change during the Holocene based on a multi-proxy record obtained from subalpine peatland in southern China.

The interactions between past climate, human activity and environmental change in subtropical mountainous areas are poorly understood due to the lack of reliable records in South China. In this study, the evolution of the East Asian summer monsoon (EASM) during the Holocene, and the interactions between regional human activity and environmental change, were studied using multi-proxy records from a subalpine peat core recovered from South China. The chronology of this peat core has been well-constrained by 10 AMS 14C dates of peat stems. A series of proxy indicators, including carbon isotopes (δ13C), loss on ignition (LOI), magnetic susceptibility (MS), the chemical index of alteration (CIA), and geochemical elements from the Shiwangutian (SWGT) peatland were used to reconstruct the palaeohydrological changes during the Holocene. Regional moisture levels showed a generally arid-wet-arid pattern, and three phases of climatic change were detected as follows. 1) Between 11,600 and 9000 cal yr BP, the EASM was weak and a relatively dry climate developed. 2) Between 9000 and 4000 cal yr BP, the prevalence of humid climatic conditions was associated with a strong summer monsoon. 3) After 4000 cal yr BP, the climate shifted to relatively dry conditions. Further comparisons and analysis suggested that solar insolation, migration of the Intertropical Convergence Zone (ITCZ), and El Niño-Southern Oscillation (ENSO) activity played an important role in determining the variations in Holocene EASM intensity. In addition, the increase in both MS and heavy metal concentrations over the last 1000 years is consistent with an increase in the population of Hunan Province. Therefore, it can be inferred that population growth and the associated expansion of cropland and mining led to an increase in soil erosion and metal tool use. These findings suggest that the impact of human activity generally outweighed the natural climatic controls on the environment and landscape in the mountainous region of southern China over the last 1000 years.

Haplotype-resolved chromosomal-level genome assembly reveals regulatory variations in mulberry fruit anthocyanin content.

Understanding the intricate regulatory mechanisms underlying the anthocyanin content (AC) in fruits and vegetables is crucial for advanced biotechnological customization. In this study, we generated high-quality haplotype-resolved genome assemblies for two mulberry cultivars: the high-AC 'Zhongsang5801' (ZS5801) and the low-AC 'Zhenzhubai' (ZZB). Additionally, we conducted a comprehensive analysis of genes associated with AC production. Through genome-wide association studies (GWAS) on 112 mulberry fruits, we identified MaVHAG3, which encodes a vacuolar-type H+-ATPase G3 subunit, as a key gene linked to purple pigmentation. To gain deeper insights into the genetic and molecular processes underlying high AC, we compared the genomes of ZS5801 and ZZB, along with fruit transcriptome data across five developmental stages, and quantified the accumulation of metabolic substances. Compared to ZZB, ZS5801 exhibited significantly more differentially expressed genes (DEGs) related to anthocyanin metabolism and higher levels of anthocyanins and flavonoids. Comparative analyses revealed expansions and contractions in the flavonol synthase (FLS) and dihydroflavonol 4-reductase (DFR) genes, resulting in altered carbon flow. Co-expression analysis demonstrated that ZS5801 displayed more significant alterations in genes involved in late-stage AC regulation compared to ZZB, particularly during the phase stage. In summary, our findings provide valuable insights into the regulation of mulberry fruit AC, offering genetic resources to enhance cultivars with higher AC traits.

Apoptosis is induced in cancer cells via the mitochondrial pathway by the novel xylocydine-derived compound JRS-15.

The novel compound JRS-15 was obtained through the chemical modification of xylocydine. JRS-15 exhibited much stronger cytotoxic and pro-apoptotic activity than its parent compound in various cancer cell lines, with IC(50) values in HeLa, HepG2, SK-HEP-1, PC-3M and A549 cells ranging from 12.42 to 28.25 µM. In addition, it is more potent for killing cancer than non-cancerous cells. Mechanistic studies showed that JRS-15 treatment arrested cell cycle at the G1/S phase, which further triggered the translocation of Bax and Bak to the mitochondria, resulting in mitochondrial membrane potential (MMP) depolarization and the subsequent release of cytochrome c and the second mitochondria-derived activator of caspase (Smac). The sequential activation of caspase-9 and caspase-3/7 and the cleavage of poly (ADP-ribose) polymerase (PARP) were observed following these mitochondrial events. Caspase-8, an initiator caspase that is required to activate the membrane receptor-mediated extrinsic apoptosis pathway was not activated in JRS-15-treated cells. Further analysis showed that the levels of the anti-apoptotic proteins Bcl-xL and XIAP were significantly reduced upon JRS-15 treatment. Furthermore, the caspase-9 inhibitor z-LEHD-fmk, the pan-caspase inhibitor z-VAD-fmk, and Bcl-xL or XIAP overexpression all effectively prevented JRS-15-induced apoptosis. Taken together, these results indicate that JRS-15 induces cancer cell apoptosis by regulating multiple apoptosis-related proteins, and this compound may therefore be a good candidate reagent for anticancer therapy.