Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst.

Mimicking the photosynthesis of green plants to combine water oxidation with CO2 reduction is of great significance for solving energy and environmental crises. In this context, a trinuclear nickel complex, [NiII3(paoH)6(PhPO3)2]·2ClO4 (1), with a novel structure has been constructed with PhPO32- (phenylphosphonate) and paoH (2-pyridine formaldehyde oxime) ligands and possesses a reflection symmetry with a mirror plane revealed by single-crystal X-ray diffraction. Bulk electrocatalysis demonstrates that complex 1 can homogeneously catalyze water oxidation and CO2 reduction simultaneously. It can catalyze water oxidation at a near-neutral condition of pH = 7.45 with a high TOF of 12.2 s-1, and the Faraday efficiency is as high as 95%. Meanwhile, it also exhibits high electrocatalytic activity for CO2 reduction towards CO with a TOF of 7.84 s-1 in DMF solution. The excellent electrocatalytic performance of the water oxidation and CO2 reduction of complex 1 could be attributed to the two unique µ3-PhPO32- bridges as the crucial factor for stabilizing the trinuclear molecule as well as the proton transformation during the catalytic process, while the oxime groups modulate the electronic structure of the metal centers via π back-bonding. Therefore, apart from the cooperation effect of the three Ni centers for catalysis, simultaneously, the two kinds of ligands in complex 1 can also synergistically coordinate the central metal, thereby significantly promoting its catalytic performance. Complex 1 represents the first nickel molecular electrocatalyst for both water oxidation and CO2 reduction. The findings in this work open an avenue for designing efficient molecular electrocatalysts with peculiar ligands.

Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation.

One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear complex [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L = N,N'-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that the Mn(III) ion in 1 has an octahedral coordination structure, whereas the Mn(II) ion in 2 possesses a trigonal bipyramidal configuration and the Cu(II) ion in 2 is four-coordinated with a square-planar geometry. Electrochimerical catalytic investigation demonstrates that the two complexes can electrochemically catalyze water oxidation and CO2 reduction simultaneously. The coordination environments of the Mn(III), Mn(II), and Cu(II) ions in 1 and 2 were provided by the Schiff base ligand (L) and labile solvent molecules. The coordinately unsaturated environment of the Cu(II) center in 2 can perfectly facilitate the catalytic performance of 2. Complexes 1 and 2 display that the over potentials for water oxidation are 728 mV and 216 mV, faradaic efficiencies (FEs) are 88% and 92%, respectively, as well as the turnover frequency (TOF) values for the catalytic reduction of CO2 to CO are 0.38 s-1 at -1.65 V and 15.97 s-1 at -1.60 V, respectively. Complex 2 shows much better catalytic performance for both water oxidation and CO2 reduction than that of complex 1, which could be owing to a structural reason which is attributed to the synergistic catalytic action of the neighboring Mn(III) and Cu(II) active sites in 2. Complexes 1 and 2 are the first two compounds coordinated with Schiff base ligand for both water oxidation and CO2 reduction. The finding in this work can offer significant inspiration for the future development of electrocatalysis in this area.

Is aromatic plants environmental health engineering (APEHE) a leverage point of the earth system?

It is important to note that every ecological niche in an ecosystem is significant. This study aims to assess the importance of medicinal and aromatic plants (MAPs) in the ecosystem from multiple perspectives. A primary model of Aromatic Plants Environmental Health Engineering (APEHE) has been designed and constructed. The APEHE system was used to collect aerosol compounds, and it was experimentally verified that these compounds have the potential to impact human health by binding to AKT1 as the primary target, and MMP9 and TLR4 as secondary targets. These compounds may indirectly affect human immunity by reversing drug resistance in drug-resistant bacteria in the nasal cavity. This is mainly achieved through combined mutations in sdhA, scrA, and PEP. Our findings are based on Network pharmacology and molecular binding, drug-resistance rescue experiments, as well as combined transcriptomics and metabolomics experiments. It is suggested that APEHE may have direct or indirect effects on human health. We demonstrate APEHE's numerous potential benefits, such as attenuation and elimination of airborne microorganisms in the environment, enhancing carbon and nitrogen storage in terrestrial ecosystems, promoting the formation of low-level clouds and strengthening the virtuous cycle of Earth's ecosystems. APEHE also supports the development of transdisciplinary technologies, including terpene energy production. It facilitates the creation of a sustainable circular economy and provides additional economic advantages through urban optimisation, as well as fresh insights into areas such as the habitability of other planets. APEHE has the potential to serve as a leverage point for the Earth system. We have created a new research direction.

Causal relationship between circulating cytokines and follicular lymphoma: a two-sample Mendelian randomization study.

Follicular lymphoma (FL), derived from germinal centre (GC) B cells, is a kind of systemic neoplasm. Even though FL is indolent, it remains an incurable haematology Neoplasm. Accumulating evidence has suggested that the circulating cytokine is associated with the development of FL, yet the causal relationship between FL and circulating cytokines remains undetermined. Therefore, we conducted a two-sample Mendelian randomization (MR) to confirm the causal link between FL and levels of circulating cytokines with the use of summary data on circulating cytokines and FL. All these data from genome-wide association study were derived from the Genome-wide pQTL mapping which contains 14,824 individuals. FL data were acquired exclusively from FinnGen, where 218,792 individuals (522 cases vs. 218,270 controls) were involved. Various statistical methods, including the inverse variance weighted method (IVW), weighted median (WME), simple model, weighted model (WM) and MR-Egger, were used to evaluate the potential causal connection between circulating cytokines and FL. Sensitivity analysis, which involves the examination of the heterogeneity, pleiotropy, and leave-one-out method, was also performed to ensure more trustworthy results. A bidirectional MR test was performed to evaluate the direction of causal association between circulating cytokines and FL. Combining all the steps of MR analysis, we revealed four causal cytokines: C-X-C motif chemokine ligand 5 (CXCL5), interleukin-15 receptor A (IL15RA), interleukin-20 (IL20), and neurotrophin-3 (NT-3). The risk of FL may be inversely linked to CXCL5 (OR=0.73, CI: 0.545-0.979, P=0.036), IL-15RA (OR=0.669, CI: 0.451-0.993, P=0.046), and IL-20 (OR=0.565, CI: 0.325-0.981, P=0.043) but positively linked to NT-3 (OR=1.872, CI: 1.063-3.297, P=0.03). In addition, in our study, no causal effect of FL on cytokines was demonstrated and no significant heterogeneity and pleiotropy were found. Our research revealed the causal relationship between cytokines and FL, along with both the anti-protective effect of CXCL5, IL-15RA, and IL-20 and the protective effect of neurotrophin-3 on FL. These findings aim to provide new clues regarding the pathogenesis of FL and to extend the potential of circulating cytokines to therapeutic interventions.

A Prediction Model for Assessing the Efficacy of Thermal Ablation in Treating Benign Thyroid Nodules ≥ 2 cm: A Multi-Center Retrospective Study.

OBJECTIVES: To develop and validate a prediction model utilizing clinical and ultrasound (US) data for preoperative assessment of efficacy following US-guided thermal ablation (TA) in patients with benign thyroid nodules (BTNs) ≥ 2 cm. MATERIALS AND METHODS: We retrospectively assessed 962 patients with 1011 BTNs who underwent TA at four tertiary centers between May 2018 and July 2022. Ablation efficacy was categorized into therapeutic success (volume reduction rate [VRR] > 50%) and non-therapeutic success (VRR ≤ 50%). We identified independent factors influencing the ablation efficacy of BTNs ≥ 2 cm in the training set using multivariate logistic regression. On this basis, a prediction model was established. The performance of model was further evaluated by discrimination (area under the curve [AUC]) in the validation set. RESULTS: Of the 1011 nodules included, 952 (94.2%) achieved therapeutic success at the 12-month follow-up after TA. Independent factors influencing VRR > 50% included sex, nodular composition, calcification, volume, and largest diameter (all p < 0.05). The prediction equation was established as follows: p = 1/1 + Exp∑[8.113 -2.720 × (if predominantly solid) -2.790 × (if solid) -1.275 × (if 10 mL < volume ≤ 30mL) -1.743 × (if volume > 30 mL) -1.268 × (if with calcification) -2.859 × (if largest diameter > 3 cm) +1.143 × (if female)]. This model showed great discrimination, with AUC of 0.908 (95% confidence interval [CI]: 0.868-0.947) and 0.850 (95% CI: 0.748-0.952) in the training and validation sets, respectively. CONCLUSIONS: A clinical prediction model was successfully developed to preoperatively predict the therapeutic success of BTNs larger than 2 cm in size following US-guided TA. This model aids physicians in evaluating treatment efficacy and devising personalized prognostic plans.

Analysis of clinical features of primary empty sella.

OBJECTIVE: A retrospective analysis of clinical data of 60 patients with primary empty sella (PES) was conducted to further improve the understanding of the disease. METHODS: The clinical data of 60 patients diagnosed with PES admitted to the Department of Endocrinology of Wuhan Union Hospital for different reasons from January 2000 to September 2018 were analyzed. RESULTS: The 60 cases comprised 22 (36.67%) male and 38 (63.33%) female patients, for a male-to-female ratio of 1:1.73. There was predominance of 50-59 year-olds and women with multiple pregnancies. Of the 60 patients, 41.67% showed fatigue, 26.67% dizziness and headache, 21.67% nausea and vomiting, 18.33% anorexia, and 6.67% visual impairment and other symptoms. Twenty-seven patients (45.0%) had normal pituitary function, and 33 (55.0%) had hypopituitarism. Complete PES was more prone to result in hypopituitarism than partial PES. Men with PES were more likely to have hypopituitarism than women. CONCLUSION: The incidence of PES was significantly higher in women than in men; PES was common in middle-aged and older women with multiple pregnancies. Symptoms were diverse and clinical manifestations may lack specificity compared to other diseases and need to be differentiated. About half of PES patients may develop hypopituitarism. Therefore, for patients with empty sella detected on magnetic resonance imaging (MRI) with or without clinical symptoms, the pituitary function should be thoroughly and promptly evaluated.

A Facile Synthetic Method for Anhydride from Carboxylic Acid with the Promotion of Triphenylphosphine Oxide and Oxaloyl Chloride.

A highly efficient synthesis reaction of carboxylic anhydrides catalyzed by triphenylphosphine oxide is described for the quick synthesis of a range of symmetric carboxylic anhydrides and cyclic anhydrides under mild and neutral conditions with a high yield. The system adopts the strong reactive intermediate Ph3PCl2 as the catalyst of carboxylic acid salt; driven by catalytic reaction, the synthesis takes a relatively short time to complete.

Reduced incidence of interstitial pneumonitis after allogeneic hematopoietic stem cell transplantation using a modified technique of total body irradiation.

Allogeneic hematopoietic stem cell transplantation is a curative-intent treatment for patients with high-risk hematologic diseases. However, interstitial pneumonitis (IP) and other toxicities remain major concerns after total body irradiation (TBI). We have proposed using linear accelerators with rice-bag compensators for intensity modulation (IM-TBI), as an alternative to the traditional cobalt-60 teletherapy with lung-shielding technique (Co-TBI). Patients who received a TBI-based myeloablative conditioning regimen between 1995 and 2014 were recruited consecutively. Before March 2007, TBI was delivered using Co-TBI (n = 181); afterward, TBI was administered using IM-TBI (n = 126). Forty-four patients developed IP; of these cases, 19 were idiopathic. The IP-related mortality rate was 50% in the total IP cohort and 63% in the idiopathic subgroup. The 1-year cumulative incidences of IP and idiopathic IP were 16.5% and 7.4%, respectively; both rates were significantly higher in the Co-TBI group than in the IM-TBI group. Multivariate analysis revealed that Co-TBI was an independent prognostic factor for both total and idiopathic IP. In the acute myeloid leukemia subgroup, patients with different TBI techniques had similar outcomes for both overall and relapse-free survival. In conclusion, IM-TBI is an easy and effective TBI technique that could substantially reduce the complication rate of IP without compromising treatment efficacy.