Homolytic C-O cleavage in phosphates and sulfonates.

The C-O homolytic bond dissociation enthalpies(BDEs) were calculated by high-level ab initio including G4, G3B3, G3, CBS-QB3 and a series of density function theory (DFT) methods. It is found that the wB97 method gave the most reliable C-O BDEs and the root-mean-square deviation (RMSD) is 7.6 kJ/mol. Therefore, the C(sp(2))-O BDE predictions and the substituent effects of alkenyl phosphates/sulfonates and aryl phosphates/sulfonates were investigated in detail by using the wB97 method. Interestingly, there exist different substituent effects in α- and ß-substituted alkenyl phosphates/sulfonates. Excellent linear relationships between the C-O BDEs of ß-substituted alkenyl phosphates/sulfonates with substituent constant σp(+) were found. In addition, the NBO analysis further disclosed the essence of the substituent effects on C-O BDEs.

A naphthalocyanine based near-infrared photosensitizer: synthesis and in vitro photodynamic activities.

A hydrophilic near-infrared (NIR) photosensitizer featuring a naphthalocyanine core and peripheral carboxylate acid groups was synthesized and characterized. Its photophysical and photochemical properties were studied and compared with phthalocyanine. Due to the extended π-conjugation, both the Q band and fluorescence emit of this naphthalocyanine bathochromically shift to NIR region. It also exhibits superior NIR photodynamic efficiency to phthalocyanine as evidenced by high efficiency in generating singlet oxygen (ΦΔ=0.66) and in vitro phototoxicity toward Hela human cervical cancer cells. Therefore, this novel naphthalocyanine could potentially be a NIR photosensitizer for photodynamic therapy.

Effect of ensiled total mixed rations containing sake lees on digestion, nitrogen use, and plasma metabolite concentrations in sheep.

Sake lees are a byproduct of Japanese rice wine and used as ruminant feed with high protein and ethanol contents. This study aimed to explore the effects of ensiled total mixed ration (TMR) containing sake lees on rumen fermentation, digestion, nitrogen (N) use, and plasma metabolites in sheep. Four mature wethers were assigned to a 4 × 4 Latin square design with a factorial arrangement of ensiling treatment (non-ensiled or ensiled TMR) and types of sake lees (traditional or liquefied). Although dietary ethanol consumption was higher in sheep fed ensiled TMR, ruminal and plasma concentrations of methanol and ethanol increased after feeding in all dietary treatments, which was accompanied by the increased plasma concentrations of formate. The intake and digestion of dry matter and N were lower in sheep fed ensiled TMR than in those fed non-ensiled TMR. The plasma concentrations of most amino acids decreased in sheep fed ensiled TMR. Although plasma methionine, serine, and glycine concentrations were not altered by diet, homocysteine concentration was the highest in sheep fed ensiled TMR containing traditional sake lees. The negative impacts of ensiling treatment on N digestion and amino acid utilization should be considered for formulating ensiled TMR containing sake lees.

Association between pulmonary hemorrhage and CPAP failure in very preterm infants.

Background: Pulmonary hemorrhage (PH) in neonates is a life-threatening respiratory complication. We aimed to analyze the perinatal risk factors and morbidity with PH among very preterm infants in a large multicenter study. Methods: This was a multicenter case-control study based on a prospective cohort. Participants included 3,680 in-born infants with a gestational age at 24-32 weeks (birth weight <1,500 g) who were admitted between January 1, 2019, and October 31, 2021. All infants were divided into two groups, namely, the PH and no-PH groups, at a ratio of 1:2 according to the following factors: gestational age (GA), birth weight (BW), and the Score for Neonatal Acute Physiology with Perinatal extension II (SNAPPE II). Perinatal factors and outcomes were compared between the two groups by logistic regression analyses. Results: A total of 3,680 infants were included in the study, and the number of identified cases of PH was 262 (7.1%). The incidence was 16.9% (136/806) for neonates with extremely low BW (BW < 1,000 g) infants. The multivariate analysis showed that CPAP failure (OR 2.83, 95% CI 1.57, 5.08) was significantly associated with PH. PH was associated with a high likelihood of death (OR 3.81, 95% CI 2.67, 5.43) and bronchopulmonary dysplasia (BPD) (≥grade II) (OR 1.58, 95% CI 1.00, 2.48). Conclusions: In this multicenter case-control study based on a prospective cohort, PH to be common among VLBW infants. PH is associated with significant morbidity and mortality, and perinatal management, especially CPAP failure. Respiratory management strategies to decrease the risk of PH should be optimized.

Late Pleistocene-Holocene vegetation history and anthropogenic activities deduced from pollen spectra and archaeological data at Guxu Lake, eastern China.

This study presents high-resolution pollen and charcoal records from Guxu Lake in the Taihu Lake Basin, eastern China, spanning the last 23,000 years. The sedimentary sequences revealed dynamic terrestrial and lacustrine environments during 23.0-11.7 cal ka BP, the climate was relatively cold and dry, and the vegetation was dominated by evergreen-deciduous broadleaf and coniferous mixed forest. During 11.7-4.4 cal ka BP, the Quercus- and Castanopsis-dominated evergreen-deciduous broadleaf mixed forest expanded, while the Poaceae and Artemisia were still the major terrestrial herbs under warmer and more humid conditions. After this period, the climate became relatively cool and dry again, and the vegetation landscape was comparatively stable, as it remains today. Wild rice likely grew before Neolithic humans occupied this area. The variations in Oryza-type Poaceae pollen spectra and distributions of Neolithic archaeological sites indicate rice agriculture may have first appeared and developed with human occupation in ca. 7.0-4.4 ka BP. During the historical period, beginning approximately 4 ka BP, a clear signal of intensified anthropogenic disturbance is evident from the clearing of forests, high charcoal concentrations and the presence of rice pollen in large quantities. These results suggest more intensified rice farming was widespread, with increasing human impact on the environment.

Effect of axial ligands on the molecular configurations, stability, reactivity, and photodynamic activities of silicon phthalocyanines.

To demonstrate the effect of axial ligands on the structure-activity relationship, a series of axially substituted silicon phthalocyanines (SiPcs) have been synthesized with changes to the axial ligands. The reactivity of the axial ligand upon shielding by the phthalocyanine ring current, along with their stability, photophysical, and photodynamic therapy (PDT) activities were compared and evaluated for the first time. As revealed by single-crystal XRD analysis, rotation of the axial -OMe ligands was observed in SiPc 3, which resulted in two molecular configurations coexisting synchronously in both the solid and solution states and causing a split of the phthalocyanine α protons in the (1)H NMR spectra that is significantly different from all SiPcs reported so far. The remarkable photostability, good singlet oxygen quantum yield, and efficient in vitro photodynamic activity synergistically show that compound 3 is one of the most promising photosensitizers for PDT.