Rapid Synthesis of 3-Methyleneisoindolin-1-ones via Metal-Free Tandem Reactions of Ester-Functionalized Aziridines.

We have disclosed a novel metal-free tandem cyclization reaction for the synthesis of 3-methyleneisoindolin-1-ones starting from ester-functionalized aziridines. This strategy can be effectively promoted by DBU and carboxylic acids. Mechanistically, it involves sequential ring opening of aziridines with carboxylic acids, lactamization, and elimination of carboxylic acids.

Glutathione detection in water and milk using a new probe DCYP based on benzopyranonitrile.

Glutathione (GSH) is a potent antioxidant, fragrance, and anti-browning agent in the field of food chemistry. The accurate GSH evaluation in food and vegetables is critical for instructing the right supplementation of GSH in body. However, most reported GSH fluorescent probes were utilized for the biological imaging. In this study, a new probe DCYP-GSH was developed by coupling of benzopyranonitrile as signal reporter to N-methylpyridine through C = C bond as binding site. Notably, a significant increase in fluorescence intensity and a λmax red-shift of DCYP-GSH in electron spectra were found as a result of the response to GSH. Quantitative detection of GSH in water and milk samples were achieved using probe DCYP-GSH. The development of DCYP-GSH was anticipated to provide an effective toolkit for food safe evaluation.

Two cases report of febuxostat-induced acute liver injury: acute heart failure as a probable risk factor?

Drug induced liver injury, as a sub-type of hepatotoxicity, is rare but practical problem, producing challenges for clinicians. Within the recent two months, two patients with heart failure develop febuxostat-induced acute liver injury during hospital stay. To the best of our knowledge, very few cases of febuxostat-induced hepatotoxicity have been reported up to now. In this paper, two unusual cases of febuxostat-induced acute liver injury are herein described. The medical history, drug treatment, clinical symptoms, liver function tests, diagnosis and prognosis are fully given in this paper. It should be noticed that, two liver injury happen in patients of heart failure with reduced ejection fraction. Whether heart failure is a risk factor of febuxostat related liver injury, deserves further research. This paper reminds the clinicians that more attention should be paid to the acute liver injury caused by febuxostat, and liver function tests are suggested especially for patients of heart failure.

Palladium-catalyzed Heck-carbonylation of alkene-tethered carbamoyl chlorides with aryl formates.

We report a palladium-catalyzed Heck-carbonylation of alkene-tethered carbamoyl chlorides by utilizing aryl formates as convenient CO surrogates. One C-O and two C-C bonds are constructed to give diversiform esterified oxindoles/γ-lactams bearing an all-carbon quaternary stereocenter under gas-free conditions. This transformation features a wide substrate scope and good functional group tolerance and can be easily applied to late-stage functionalization.

Pyrifluquinazon baseline susceptibility and inhibition of Tomato chlorosis virus transmission by Bemisia tabaci.

BACKGROUND: Tomato chlorosis virus (ToCV) is associated with tomato yellow leaf disorder diseases in more than 20 countries. ToCV can be transmitted in a semipersistent manner by whitefly vectors such as Bemisia tabaci. Controlling the vector pests by using chemical insecticides is an efficient and effective approach to reduce and interrupt the virus transmission. Pyrifluquinazon is a new pyridine azomethine derivative, showing insecticidal toxicity to sucking pests by disturbing their feeding behavior. However, limited attention has been paid to the performance of pyrifluquinazon against B. tabaci and ToCV transmission. RESULT: This study showed the lethal concentration of 50% (LC50 ) values of pyrifluquinazon to 22 B. tabaci field populations ranged from 0.54 to 2.44 mg L-1 , and the baseline susceptibility of B. tabaci to pyrifluquinazon was 1.24 mg L-1 with a 95% confidence limit of 0.35-1.85 mg L-1 . Pyrifluquinazon and afidopyropen did not show cross-resistance to dinotefuran and pymetrozine in B. tabaci, which both inhibited the feeding activities of B. tabaci. The antifeedant concentration of 50% (AFC50 ) values at 48 h were 0.70 mg L-1 for pyrifluquinazon and 2.13 mg L-1 for afidopyropen. Foliar application of pyrifluquinazon and afidopyropen reduced the ToCV transmission by 40.91% and 33.33%, respectively and significantly decreased the ToCV loads in tomato plants under laboratory conditions. CONCLUSION: These results provided new information about the effects of modulators of the vanilloid-type transient receptor potential channel on the toxicity to B. tabaci and inhibition of ToCV transmission. © 2023 Society of Chemical Industry.

Advances in the development of phosphodiesterase 7 inhibitors.

Phosphodiesterase 7 (PDE7) specifically hydrolyzes cyclic adenosine monophosphate (cAMP), a second messenger that plays essential roles in cell signaling and physiological processes. Many PDE7 inhibitors used to investigate the role of PDE7 have displayed efficacy in the treatment of a wide range of diseases, such as asthma and central nervous system (CNS) disorders. Although PDE7 inhibitors are developed more slowly than PDE4 inhibitors, there is increasing recognition of PDE7 inhibitors as potential therapeutics for no nausea and vomiting secondary. Herein, we summarized the advances in PDE7 inhibitors over the past decade, focusing on their crystal structures, key pharmacophores, subfamily selectivity, and therapeutic potential. Hopefully, this summary will lead to a better understanding of PDE7 inhibitors and provide strategies for developing novel therapies targeting PDE7.

Introducing melatonin to the horticultural industry: physiological roles, potential applications, and challenges.

Melatonin (N-acetyl-5-methoxytryptamine) is an emerging biomolecule that influences horticultural crop growth, flowering, fruit ripening, postharvest preservation, and stress protection. It functions as a plant growth regulator, preservative and antimicrobial agent to promote seed germination, regulate root system architecture, influence flowering and pollen germination, promote fruit production, ensure postharvest preservation, and increase resistance to abiotic and biotic stresses. Here, we highlight the potential applications of melatonin in multiple aspects of horticulture, including molecular breeding, vegetative reproduction, production of virus-free plants, food safety, and horticultural crop processing. We also discuss its effects on parthenocarpy, autophagy, and arbuscular mycorrhizal symbiosis. Together, these many features contribute to the promise of melatonin for improving horticultural crop production and food safety. Effective translation of melatonin to the horticultural industry requires an understanding of the challenges associated with its uses, including the development of economically viable sources.

Construction of Bridged Aza- and Oxa-[n.2.1] Skeletons via an Intramolecular Formal [3+2] Cycloaddition of Aziridines and Epoxides with Electron-Deficient Alkenes.

An intramolecular formal [3+2] cycloaddition of activated aziridines and epoxides with electron-deficient alkene has been developed for the general and efficient construction of bridged aza- and oxa-[n.2.1] (n = 3 or 4) skeletons. This strategy can be efficiently promoted by lithium iodide. To demonstrate its potential, the intramolecular formal [3+2] cycloaddition was used to access the important intermediate of homoepiboxidine.

pH-Triggered Transition from Micellar Aggregation to a Host-Guest Complex Accompanied by a Color Change.

A pH-triggered transition from micellar aggregation to a host-guest complex was achieved based on the supramolecular interactions between calixpyridinium and pyrroloquinoline quinone disodium salt (PQQ-2Na) accompanied by a color change. Our design has the following three advantages: (1) a regular spherical micellar assembly is fabricated by the supramolecular interactions between calixpyridinium and PQQ-2Na at pH 6 in an aqueous solution, (2) increasing the pH can lead to a transition from micellar aggregation to a host-guest complex due to the deprotonation of calixpyridinium, and at the same time (3) increasing the pH can lead to a color change owing to the deprotonation of calixpyridinium and the complexation of deprotonated calixpyridinium with PQQ-2Na. Benefitting from the low toxicity of calixpyridinium and PQQ-2Na, this pH-induced transition from micellar aggregation to a host-guest complex was further studied as a controllable-release model.

Synthesis, Properties, and Regioselective Functionalization of 9,9a-BN Anthracene.

A novel 9,9a-BN anthracene 5 has been synthesized by the Ru-catalyzed electrocyclization of BN-aromatic enynes. The photophysical properties of 5 are different from those of all-carbon anthracene and other reported BN-anthracenes. The reactivity of 5 has been investigated by treating 5 with organolithium compounds, Br2, or N-iodosuccinimide. The resulting halogenated compounds can be easily functionalized via cross-coupling reactions. UV-vis and fluorescence spectroscopy of 5 have been investigated to explore the photophysical properties of these BN-anthracenes.

A novel rosamine-based fluorescent probe for the rapid and selective detection of cysteine in BSA, water, milk, cabbage, radish, apple, and pear.

A novel fluorescent probe (RA), based on the rosamine skeleton bearing acrylate group, has been reasonably designed and prepared, which employed an addition-cyclization-elimination sequence reaction mechanism to detect cysteine. RA displayed rapid response to cysteine within 1.5 min, and exhibited satisfactory selectivity for cysteine over H2S, glutathione (Glu), and homocysteine (Hcy), due to the formation of seven-membered lactam favored kinetically. Fluorescence ratio was utilized to detect cysteine from 6.0 to 20.0 µM with a detection limit of 0.29 µM. More, RA was used to monitor cysteine in BSA, water, milk, milk powder, cabbage, radish, apple, and pear.

Rhodium(iii)-catalyzed switchable C-H acylmethylation and annulation of 2,2'-bipyridine derivatives with sulfoxonium ylides.

A novel protocol for Rh(iii)-catalyzed switchable C-H acylmethylation and annulation of 2,2'-bipyridine derivatives with sulfoxonium ylides is reported. This protocol provides a facile approach to synthesize structurally diverse acylmethylated 2,2'-bipyridine derivatives and acyl pyrido[2,3-a]indolizines with a broad range of functional group tolerance.

The effect of secondary capping on the control of phosphorus release from sediment by activated thin-layer capping with Al-PIA.

It is well-known that the activated thin-layer capping covering by secondary capping of contaminated sediment poses a threat to the inactivation of activated material. In this study, the static simulation experiment was conducted to study the effect of secondary capping thickness by sediment on the control of TP release from the sediment by aluminum-based P-inactivation agent (Al-PIA), and to propose the phosphorus adsorption pathway of Al-PIA. The results showed that Al-PIA could effectively reduce the release of phosphorus pollutants from the sediment at the capping intensity of 2 kg/m2. When the secondary capping thickness of sediment were 0, 2, 4, 7, 10, and 15 mm, the average removal rates of TP were 87.57%, 76.39%, 61.22%, 51.32%, 41.93%, and 32.11%, respectively, indicating that the removal efficiency of phosphorus decreased with the increase of the secondary capping thickness of the sediment. The adsorbed phosphorus by Al-PIA was mainly non-apatite inorganic phosphorus (NAIP) in inorganic phosphorus. With the increase of the secondary capping thickness of sediment, the NAIP proportion of phosphorus adsorbed by Al-PIA increased. Meanwhile, the removal rate of phosphorus in the activated capping system showed a first increase and then decrease trend, and the removal rates of total phosphorus (TP), inorganic phosphorus (IP), and organic phosphorus (OP) were obvious except for that of organic phosphorus (OP).

UV Accelerated Assemblies Constructed Using Calixpyridinium in Aqueous Solution.

In this work, an irregular calixpyridinium-suramin sodium supramolecular assembly was constructed by the strong host-guest electrostatic interactions. More interestingly, a novel regular spherical supramolecular assembly was also fabricated by the hydrogen bonding interactions between suramin sodium and the UV accelerated addition product of deprotonated calixpyridinium in water. The same principle was also applied to construct a UV accelerated regular spherical self-assembly by the addition product of deprotonated calixpyridinium in water. Compared with the complicated and irreversible covalent connection of the light-responsive groups to the building block, which is one of the common means of obtaining light-responsive supramolecular systems, this finding not only provides a smart, facile, and universally applicable method to construct deprotonated calixpyridinium-based light-responsive host-guest systems but also provides a new idea for the development of other novel light-responsive building blocks.

Palladium-Catalyzed C-2 and C-3 Dual C-H Functionalization of Indoles: Synthesis of Fluorinated Isocryptolepine Analogues.

Here we report a protocol to synthesize diversiform fluorinated isocryptolepine analogues with potential biological activities in one step via directed C-2 and C-3 dual C-H functionalization of indoles. We also attempted to take into account fluorinated imidoyl chlorides as a novel kind of synthons in the directed C-H functionalization reactions. As a result, a variety of fluorinated isocryptolepine analogues were obtained in up to 96% yield. Moreover, we conducted control experiments to disclose the reaction mechanism.

A novel approach for rhodium(iii)-catalyzed C-H functionalization of 2,2'-bipyridine derivatives with alkynes: a significant substituent effect.

We described a novel approach for the C-H functionalization of 2,2'-bipyridine derivatives with alkynes. DFT calculations and experimental data showed a significant substituent effect at the 6-position of 2,2'-bipyridine, which weakened the adjacent N-Rh bond and provided the possibility of subsequent rollover cyclometalation, C-H activation, and functionalization.

Synthesis of bis-BN-Naphthalene-Fused Oxepins and Their Photoluminescence Including White-Light Emission.

A series of novel bis-BN-naphthalene-fused oxepin derivatives were synthesized via a Pd-catalyzed tandem reaction from brominated 2,1-borazaronaphthalenes and cis-bis(boryl)alkenes. X-ray crystallographic analysis revealed that bis-BN-naphthalene-fused oxepins feature a planar framework. The electronic and photophysical properties of the novel BN-naphthalene-fused oxepins were investigated by UV-vis and fluorescence spectroscopies and density functional theory (DFT) calculations, which disclosed the distinct electronic and photophysical properties of the analogous hydrocarbon system. Interestingly, dual-fluorescent emissions were observed upon dissolving N-substituted derivatives 10-14 in dimethyl sulfoxide. Tunable emission colors especially for white-light emissions can be achieved by controlling the ratio of solvents, concentration, or temperature using only a single-molecule compound.

Silver-promoted cascade radical cyclization of γ,δ-unsaturated oxime esters with P(O)H compounds: synthesis of phosphorylated pyrrolines.

A cascade radical cyclization was realized for the first silver-promoted imino-phosphorylation of γ,δ-unsaturated oxime esters, which provided a step-economical and redox-neutral route to access a variety of phosphorylated pyrrolines in good to excellent yields. Moreover, a new bulky trivalent phosphine ligand with a pyrroline motif was obtained through a deoxidation process.

Photolysis of a calixpyridinium-based supramolecular amphiphilic assembly and its selective turn-on fluorescence recognition of lysine in water.

A new calixpyridinium-based light-responsive host-guest recognition motif was found in this work. This host-guest recognition motif was further discovered to be applied as a selective turn-on fluorescent sensor for lysine over other natural amino acids.

Rhodium(iii)-catalyzed unreactive C(sp3)-H alkenylation of N-alkyl-1H-pyrazoles with alkynes.

The first example of pyrazole-directed rhodium(iii)-catalyzed unreactive C(sp3)-H alkenylation with alkynes has been described, which showed a relatively broad substrate scope with good functional group compatibility. Moreover, we demonstrated that the transitive coordinating center pyrazole could be easily removed under mild conditions.