Electrochemically Direct Fluorination Functionalization of Styrenes with Different Fluorine Source: Access to Fluoroalkyl Derivatives.

A mild protocol for electrochemically oxidative fluorodifunctionalization of styrenes has been demonstrated. The reaction proceeds under metal, external oxidant, and catalyst free conditions, allowing tunable access to a wide variety of synthetically useful fluoroalkyl derivatives, such as ß-fluorosulfone/fluoromethyl, fluorothiocyanation, and vinylsulfonyl derivatives. Moreover, CsF was shown to be the proper fluorine source for this electrochemical fluorodifunctionalization transformation.

A new 3,4-dinorsteroid from the marine sponge Cliona sp.

A new steroid, 2a-oxa-2-oxo-5ß-hydroxy-3,4-dinor-24-methylcholesta-22E-ene (1), together with 10 known ones (2-11), was isolated from the marine sponge Cliona sp. The structures of these compounds were determined by the spectroscopic methods (UV, IR, MS, and NMR) and X-ray diffraction analysis. Compound 1 was the third example of 3,4-dinorsteroid with a hemiketal at C-5 that was isolated from the natural source. In addition, the antibacterial activities of these compounds were also evaluated. However, none of them exhibited significant inhibition effects.

(+)- and (-)-Tedanine, a pair of new enantiomeric indolone alkaloids from the marine sponge Tedania sp.

(+)- and (-)-Tedanine [(+)-1 and (-)-1], a pair of new enantiomeric indolone alkaloids, along with nine compounds (2-10) were isolated from the marine sponge Tedania sp. The structures of (+)-1 and (-)-1 including absolute configurations were determined by spectroscopic analysis and quantum chemical calculation. Compounds (+)-1 and (-)-1 were the first examples of indolone alkaloids isolated from this genus. In addition, the cytotoxic and antibacterial activities of these compounds were also evaluated.

A highly efficient process to enhance the bioleaching of spent lithium-ion batteries by bifunctional pyrite combined with elemental sulfur.

Bioleaching technologies have been shown to be an environmentally friendly and economically beneficial tool for extracting metals from spent lithium-ion batteries (LIBs). However, conventional bioleaching methods have exhibited low efficiency in recovering metals from spent LIBs. Therefore, relied on the sustainability principle of using waste to treat waste, this study employed pyrite (FeS2) as an energy substance with reducing properties and investigated its effects in combination with elemental sulfur (S0) or FeSO4 on metals bioleaching from spent LIBs. Results demonstrated that the bioleaching efficiency was significantly higher in the leaching system constructed with FeS2 + S0, than in the FeS2 + FeSO4 or FeS2 system. When the pulp densities of FeS2, S0 and spent LIBs were 10 g L-1, 5 g L-1 and 10 g L-1, respectively, the leaching efficiency of Li, Ni, Co and Mn all reached 100%. Mechanistic analysis reveals that in the FeS2 + S0 system, the activity and acid-producing capabilities of iron-sulfur oxidizing bacteria were enhanced, promoting the generation of Fe (Ⅱ) and reducible sulfur compounds. Simultaneously, bio-acids were shown to disrupt the structure of the LIBs, thereby increasing the contact area between Fe (Ⅱ) and sulfur compounds containing high-valence metals. This effectively promoted the reduction of high-valence metals, thereby enhancing their leaching efficiency. Overall, the FeS2 + S0 bioleaching process constructed in this study, improved the leaching efficiency of LIBs while also effectively utilizing waste, providing technical support for the comprehensive and sustainable management of solid waste.

Feasibility of low-intensity ultrasound treatment with hydroxylamine to accelerate the initiation of partial nitrification and allow operation under intermittent aeration.

Partial nitrification is a key aspect of efficient nitrogen removal, although practically it suffers from long start-up cycles and unstable long-term operational performance. To address these drawbacks, this study investigated the effect of low intensity ultrasound treatment combined with hydroxylamine (NH2OH) on the performance of partial nitrification. Results show that compared with the control group, low-intensity ultrasound treatment (0.10 W/mL, 15 min) combined with NH2OH (5 mg/L) reduced the time required for partial nitrification initiation by 6 days, increasing the nitrite accumulation rate (NAR) and ammonia nitrogen removal rate (NRR) by 20.4% and 6.7%, respectively, achieving 96.48% NRR. Mechanistic analysis showed that NH2OH enhanced ammonia oxidation, inhibited nitrite-oxidizing bacteria (NOB) activity and shortened the time required for partial nitrification initiation. Furthermore, ultrasonication combined with NH2OH dosing stimulated EPS (extracellular polymeric substances) secretion, increased carbonyl, hydroxyl and amine functional group abundances and enhanced mass transfer. In addition, 16S rRNA gene sequencing results showed that ultrasonication-sensitive Nitrospira disappeared from the ultrasound + NH2OH system, while Nitrosomonas gradually became the dominant group. Collectively, the results of this study provide valuable insight into the enhancement of partial nitrification start-up during the process of wastewater nitrogen removal.

Two New Pairs of Enantiomeric Butenolides from the Marine Sponge Suberties sp.

Two new pairs of enantiomeric butenolides, (+)- and (-)-suberiteslide A, (+)- and (-)-subertieslide B had been obtained from the marine sponge Suberties sp. The structures with absolute configurations of these compounds were unequivocally determined by spectroscopic analyses and ECD (Electronic Circular Dichroism) method. It was the first separation of butenolides from the marine sponges of genus Suberites. Additionally, the anti-inflammatory, antibacterial and cytotoxic activities of these compounds were evaluated. The result indicated that only (-)-subertieslide B showed weak anti-inflammatory activity with the IC50 value of 40.8 µM.

A new chlorobenzoate derivative from the red alga Solieria sp.

A new chlorobenzoate derivative, solieriate (1), together with six known compounds (2-7), were isolated from the red alga Solieria sp. The structures of 1-7 were determined by comprehensive spectroscopic methods and X-ray diffraction analysis. Compound 1 is the first example of halogenated derivative isolated from this genus. In addition, 1 exhibited moderate antibacterial activity on A. baumannii with MIC value of 64 µg/ml.

Spongimides A and B, two new alkaloids from the marine sponge Spongia sp.

Two new alkaloids, spongimides A (1) and B (2), along with five known ones (3-7), were isolated from the marine sponge Spongia sp. The structures of 1 and 2 were determined by the spectroscopic methods (UV, IR, MS, and NMR) and X-ray diffraction analysis. Compounds 1, 3, and 4 were the first examples of 2,4-imidazolidinediones isolated from this genus. In addition, the cytotoxic and antibacterial activities of compounds 1 and 2 were also evaluated.

Two new halogenated metabolites from the red alga Laurencia sp.

Two new halogenated metabolites, laurenhalogens A (1) and B (2), along with four known ones (3-6), were isolated from the red alga Laurencia sp. The structures of 1 and 2 were determined by the means of UV, IR, MS, NMR and X-ray diffraction analysis. In addition, the antibacterial activities of 1-6 were also evaluated.

Synthesis of Marine Cyclopeptide Galaxamide Analogues as Potential Anticancer Agents.

In this paper, eight new galaxamide analogues (Z-1~Z-8) were synthesized and evaluated for their cytotoxic activities against five cancer cell lines, MCF-7, MD-MBA-231, HepG2, Hela, and A549, using MTT assays. The modified analogue Z-6 displayed broad spectrum cytotoxic activity toward each tested cell line with IC50 values of 1.65 ± 0.30 (MCF-7), 2.91 ± 0.17 (HepG2), 4.59 ± 0.27 (MD-MBA-231), 5.69 ± 0.37 (Hela), and 5.96 ± 0.41 (A549) µg/mL, respectively. The galaxamides Z-3 and Z-6 induced concentration-dependent apoptosis of the MCF-7 cells after 72 h as evaluated by the flow cytometry experiment. The results showed that these compounds could induce MCF-7 cell apoptosis by arresting the G0/G1 phase of the cell cycle and finally achieving the effect of inhibiting the proliferation of MCF-7 cells.

A designed moderately thermophilic consortia with a better performance for leaching high grade fine lead-zinc sulfide ore.

Unwieldy fine sulfide ores are produced during mining; without being appropriately disposed of, they can cause environmental pollution and waste resources. This study investigated the leaching performance of a moderately thermophilic consortia (Leptospirillum ferriphilum + Acidithiobacillus caldus + Sulfobacillus benefaciens) for fine lead-zinc sulfide raw ore. The results showed this microbial community created a low pH, high ORP, and high cell concentration environment for mineral leaching, improving bioleaching efficiency. Under the action of this consortia, the zinc leaching rate reached 96.44 in 8 days, and reached 100% after 12 days. EPS analysis indicated that the consortia could mediate the secretion of more polysaccharides to ensure leaching efficiency. EPS levels and amino acids were the main factors affecting bioleaching. An analysis of mineral surface characteristics showed the consortia effectively leached pyrite and sphalerite from the fine sulfide ore, and prevented the mineral surface forming the jarosite that could hinder bioleaching. This study found that bioleaching reduced the potential environmental toxicity of the minerals, providing an important reference for guiding the bioleaching of unwieldy fine sulfide raw ore.

Bioleaching for detoxification of waste flotation tailings: Relationship between EPS substances and bioleaching behavior.

The production of large volumes of waste flotation tailings results in environmental pollution and presents a major ecological and environmental risk. This study investigates bioleaching of waste flotation tailings using Acidithiobacillus ferrooxidans. The experiments were performed with 5.00% solid concentration, pH 2.0 with 100 mL medium for 25 d in the lab. The pH, OPR, metal concentration, dissolved organic matter (DOM) in leachate and extracellular polymeric substances (EPS) were recorded. Bioleaching tailing materials were finally characterized. Results showed that microorganisms, acclimating with mine tailings, effectively accelerated the bioleaching process, achieving maximum Zn and Fe extraction efficiencies of 95.45% and 83.98%, respectively, after 25 days. Compared with raw mine tailings, bioleaching could reduce 96.36% and 95.84% leachable Zn and Pb, and Pb presented a low risk (4.13%), while Zn, Cu, and Cr posed no risk (0.34%, 0.64%, and 0%). Toxicity and environmental risk analysis revealed bioleaching process significantly reduced the environmental risk associated with mine tailings. EPS analysis indicated that the loosely-bound EPS (LB-EPS) and tightly-bound EPS (TB-EPS) fractions contained different organic substances, which played different roles in the bioleaching process. Pearson correlation analysis revealed that EPS was highly correlated with bioleaching behavior (p < 0.05), and EPS was the main factor affecting the bioleaching process, promoting bioleaching in the LB-EPS and TB-EPS fractions.

Ultrasonic coupled bioleaching pretreatment for enhancing sewage sludge dewatering: Simultaneously mitigating antibiotic resistant genes and changing microbial communities.

In this study, ultrasonic as a pretreatment coupled with bioleaching was used to enhance sludge dewaterability. Changes in microbial diversity and antibiotic resistant genes (ARGs) were studied during the combined treatment process. The results show that under optimal conditions, combined ultrasonic and bioleaching treatment led to decreases in the specific resistance of filtration and bioleaching time by 7.59% and 12.5%, respectively, compared with single bioleaching process. Using high pressure filtration system, the water content of sludge cake treated by the combined treatment was decreased to 58.04%, which was 10.04% lower than bioleaching sludge. After combined treatment, the microbial diversity and the total number of bacteria in the sludge decreased significantly, which caused the decreases in the absolute abundance of sulfonamide and tetracycline ARGs by 1.56-1.58 and 0.34-1.23 log units, respectively. However, the decrease in the total bacterial biomass was greater than the decrease in the number of potential hosts carrying the tetracycline ARG, resulting in an increase in the relative abundance of tetracycline gene. Furthermore, this study proposed a mechanism of the dewatering and ARGs, involving the combined ultrasonic and bioleaching treatment: Firstly, ultrasonic cavitation causes extracellular polymeric substances (EPS) to fall off the surface of sludge; Secondly, this faster and directly makes bacteria cells affected by bio-acidification and bio-oxidation. In this case, the cells could be more easily destroyed by the combined ultrasonic and bioleaching treatment, compared with individual bioleaching treatment; As a result, stronger dewaterability and more removal rates of ARGs were achieved under the combined treatment. The economic analyses showed that the combined ultrasonic and bioleaching treatment is a more practical and economical technique for achieving deep dewatering of sludge.

Three New Butenolides from the Green Alga Caulerpa racemosa var. turbinata.

Three new butenolides, caulerpalide A and a pair of enantiomers, (+)-caulerpalide B and (-)-caulerpalide B, together with seven known compounds, have been isolated from the green alga Caulerpa racemosa var. turbinata. All these structures were determined by spectroscopic techniques. The absolute configurations of caulerpalide A, (+)-caulerpalide B and (-)-caulerpalide B were elucidated by the method of ECD calculation. This is the first separation of butenolides from the algae of genus Caulerpa. Additionally, the antibacterial activities of the nine isolated compounds were also evaluated.

Sinulaspirolactam A, a novel aza-spirocyclic valerenane sesquiterpenoid from soft coral Sinularia sp.

A novel valerenane sesquiterpenoid sinulaspirolactam A (1), together with five known compounds, was isolated from the soft coral Sinularia sp. Their structures were determined by spectroscopic analyses. The absolute configuration of 1 was established by ECD calculation. Compound 1 was the first example of valerenane sesquiterpenoid bearing an aza-spiro[4.5] ring moiety, the plausible biogenetic pathway of which was proposed. Cytotoxic activities of these compounds were also evaluated.

Antineoplastic activity of linear leucine homodipeptides and their potential mechanisms of action.

Galaxamide is a rare cyclic homopentapeptide composed of three leucines and two N-methyl leucines isolated from marine algae Galaxaura filamentosa. The strong antitumor activity of this compound makes it a promising candidate for tumor therapy. The synthesis of galaxamide, however, is a complex process, and it has poor water solubility. On the basis of its special chemical composition, we designed a series of linear leucine homopeptides. Among seven dipeptide derivatives, five compounds with terminal protection groups and methyl substitution of the hydrogen in the amido group showed remarkable inhibitory effects against various cancer cells. N-tertbutyl-D-leucine-N-methyl-D-leucinebenzyl (A7), the only stereomer condensed by two D-leucines, showed the highest antineoplastic activity. A7-treated cells showed cell cycle arrest and morphological changes typical of cells undergoing apoptosis. The population of Annexin-V positive/propidium iodide-negative cells also increased, indicating the induction of early apoptosis. A7 promoted the cleavage of caspase-9 and caspase-3, as well as increased intracellular Ca levels and decreased the mitochondrial membrane potential. Collectively, certain linear leucine dipeptides derived from cyclic pentapeptide are able to inhibit tumor cell proliferation through cell cycle arrest and apoptosis induction. The N-methyl group in the side chain and the D/L conformation of the amino-acid residue are critical for their activity.

Aspergchromones A and B, two new polyketides from the marine sponge-associated fungus Aspergillus sp. SCSIO XWS03F03.

Two new polyketides, aspergchromones A (1) and B (2), together with five known compounds, secalonic acid D (3), noreugenin (4), (3S)-5-hydroxymellein (5), (4S)-6-hydroxyisosclerone (6), and (-)-regiolone (7), were isolated from the ethyl acetate extract of marine sponge-derived fungus Aspergillus sp. SCSIO XWS03F03. Their structures were elucidated by means of spectroscopic techniques (1D and 2D NMR, MS, UV, and IR). The absolute configurations of the new compounds were established by ECD calculations. Compound 3 showed moderate antimicrobial activity.

A new α-pyrone from the deep-sea actinomycete Nocardiopsis dassonvillei subsp. dassonvillei DSM 43111(T).

A new α-pyrone, nocapyrone S (1), together with five known compounds (2-6), were isolated from the deep-sea actinomycete Nocardiopsis dassonvillei subsp. dassonvillei DSM 43111(T). Their structures were determined by spectroscopic analyses. The absolute configuration of 1 was established by quantum approaches. Cytotoxic activity of 1 was evaluated against K562, MCF-7, SGC7901, A375, Hela, and HepG2 cell lines.

d-Amino Acid Position Influences the Anticancer Activity of Galaxamide Analogs: An Apoptotic Mechanism Study.

Galaxamide, an extract from Galaxaura filamentosa, is a cyclic pentapeptide containing five l-leucines. Due to the particular cyclic structure and the excellent anticancer activity, synthesis of Galaxamide and its analogs and their subsequent bio-applications have attracted great attention. In the present work, we synthesized six Galaxamide analogs by replacing one of the l-leucines with phenylalanine and varying the d-amino acid position. The anticancer effect of the synthesized Galaxamide analogs was tested against four in vitro human cancer cell lines, human hepatocellular cells (HepG2), human breast cancer cell (MCF-7), human breast adenocarcinoma cells (MDA-MB-435) and a human cervical carcinoma cell line (Hela). Results showed that Galaxamide analogs with different d-amino acid positions displayed distinct anticancer potential. The Galaxamide analog containing d-amino acid at position 5 (Analog-6) presented the strongest anticancer activity. The mechanism study revealed that Analog-6 could cause the early apoptosis of HepG2 cells by inhibiting their growth in the sub-G1 stage of the cell cycle and induce the chromatin condensation and fragmentation, which can be seen as 68% of HepG2 cells inhibited in the sub-G1 stage. Moreover, a mitochondria-mediated pathway was found to be involved in the apoptotic process of Analog-6 on HepG2 cells.

DFT Mechanistic Study of Rh(III)-Catalyzed [3 + 2]/[5 + 2] Annulation of 4-Aryl-1,2,3-triazoles and Alkynes Unveils the Dual C-H Activation Strategy.

Li and co-workers recently developed a dual C-H bond activation strategy, using a Rh(III) catalyst, for [3 + 2]/[5 + 2] annulation of primary 4-aryl-1,2,3-triazoles and alkynes. The Rh(III)-catalyzed dual annulation of 4-aryl-1,2,3-triazoles and alkynes is challenging because only single annulation is achieved using Rh(II) and Ni(0) catalysts. Intrigued by the novel strategy, we performed a density functional theory study to unravel this challenging dual C-H bond activation. A Friedel-Crafts type mechanism proved be more favorable than a concerted metalation-deprotonation (CMD) mechanism for the first C-H bond activation. The second C-H bond activation proceeded via a CMD mechanism. More importantly, the calculation explained why only AgSbF6, among several candidates, performed perfectly, whereas others failed, and why the dual annulation of 4-aryl-1,2,3-triazoles with alkynes was achieved with a Rh(III) catalyst but not with Rh(II) and Ni(0) catalysts. Due to the active catalyst being [Cp*Rh(OAc)]+, AgSbF6, in which SbF6- is a stable anion, among several candidates performed perfectly. The success of the Rh(III)-catalyzed dual C-H bond activation has two origins: (i) the active catalyst [Cp*Rh(OAc)]+ is more stable than Cp*Rh(OAc)2 when the Ag salt is AgSbF6, and this facilitates the first alkyne insertion; and (ii) a rhodium-carbene is easily formed.