On-Off Switching of a Photocatalytic Overall Reaction through Dynamic Spin-State Transition in a Hofmann Clathrate System.

Spin-state transition is a vital factor that dominates catalytic processes, but unveiling its mechanism still faces the great challenge of the lack of catalyst model systems. Herein, we propose that the {Fe-Pt} Hofmann clathrates, whose dynamic spin-state transition of metal centers can be chemically manipulated through iodine treatment, can serve as model systems in the spin-related structural-catalytic relationship study. Taking the photocatalytic synthesis of H2O2 as the basic catalytic reaction, when the spin state of Fe(II) in the clathrate is high spin (HS), sacrificial agents are indispensable to the photosynthesis of H2O2 because only the photocatalytic oxygen reduction reaction (ORR) occurs; when it is low spin (LS), both the ORR and water oxidation reaction (WOR) can take place, enabling a high H2O2 photosynthesis rate of 66 000 µM g-1 h-1 under visible-light irradiation. In situ characterizations combined with density functional theory calculations confirmed that, compared with the HS-state counterpart, the LS state can induce strong charge transfer between the LS Fe(II) and the iodide-coordinating Pt(IV) in the polymer and reduce the energy barriers for both the ORR and WOR processes, dominating the on-off switching upon the photosynthesis of H2O2 in O2-saturated water. What's more, the one-pot tandem reactions were conducted to utilize the synthesized H2O2 for transforming the low-value-added sodium alkenesulfonates into value-added bromohydrin products with decent conversion rates. This work provides a pioneering investigation into on-off switching the photocatalytic overall reaction through manipulating the metallic spin-state transition in spin-crossover systems.

Evaluating the Clinical Efficacy of Teriparatide and Denosumab Combination Therapy in Postmenopausal Osteoporosis: A Systematic Review and Meta-Analysis.

Objective: This meta-analysis aims to assess the clinical effectiveness of the combination therapy involving Teriparatide (TPTD) and Denosumab (DEN) in managing postmenopausal osteoporosis (PMO). The findings provide valuable insights into clinical treatment decisions. Methods: We conducted a comprehensive search of PubMed, the Cochrane Library, Embase, and other relevant databases to gather literature concerning the treatment of PMO with TPTD and DEN. After a thorough screening, we selected and analyzed the final literature set. Information relevant to the study was extracted, and a quality assessment was carried out. The meta-analysis utilized RevMan 5.3 software to evaluate the impact of DEN combined with TPTD on parameters such as bone mineral density (BMD), tartrate-resistant acid phosphatase-5b (TRACP-5b), fracture incidence, and adverse reactions in PMO patients. Results: After the screening process, a total of 513 patients were studied across 8 studies. Among these, 259 patients received treatment involving DEN combined with TPTD (the research group), while 254 patients were subjected to different treatment regimens (the control group). As per the Cochrane Handbook's quality assessment, all included literature exhibited high overall quality. The meta-analysis demonstrated that the research group exhibited significantly higher BMD than the control group, lower TRACP-5b levels and fracture incidence (P < .05). However, the two groups had no evident difference in adverse reaction incidence (P > .05). Conclusions: The combined treatment of DEN and TPTD exhibits notable efficacy in managing PMO, warranting its promotion and use in clinical practice.

Association of osteoporosis risk and polymorphisms of osteoprotegerin gene T950C in postmenopausal Chinese women: A PRISMA-compliant meta-analysis.

BACKGROUND: This study aimed to assess the association between the T950C polymorphism and osteoporosis in postmenopausal Chinese women to further reduce the influence of different genetic backgrounds by meta-analysis and subgroup analysis. METHODS: Through November 2022, a systematic online investigation was performed with the aid of the Cochrane Library, EMBASE, PubMed, Web of Science and the Chinese National Knowledge Infrastructure to find case-control studies looking into the correlation between the osteoprotegerin gene (OPG) T950C polymorphism and postmenopausal osteoporosis susceptibility. RESULTS: This study included 6 studies with a total of 1669 postmenopausal osteoporosis cases and 2992 controls. In the recessive model, postmenopausal women with the CC genotype (mutant homozygote at the T950C locus) had a lower risk of osteoporosis, indicating that the CC genotype of OPG T950C might show a preventive effect on osteoporosis after menopause. In a stratified analysis by geographic area, the population from South China had a significantly higher risk under the dominant model [CC + TC (heterozygote at the T950C locus) vs TT (wild-type homozygotes at the T950C locus): odds ratio = 1.34, 95% confidence interval = 1.17-1.54, P < .01], while the population from South China had a significantly lower risk under the recessive model (CC vs TC + TT: odds ratio = 0.79, 95% confidence interval = 0.69-0.95, P = .02). CONCLUSIONS: Together, the OPG T950C polymorphism may be associated with osteoporosis risk in postmenopausal Chinese women, according to this meta-analysis. Because of the study's limitations, more large-scale research is needed to corroborate these findings.

Tandem utilization of CO2 photoreduction products for the carbonylation of aryl iodides.

Photocatalytic CO2 reduction reaction has been developed as an effective strategy to convert CO2 into reusable chemicals. However, the reduction products of this reaction are often of low utilization value. Herein, we effectively connect photocatalytic CO2 reduction and amino carbonylation reactions in series to reconvert inexpensive photoreduction product CO into value-added and easily isolated fine chemicals. In this tandem transformation system, we synthesize an efficient photocatalyst, NNU-55-Ni, which is transformed into nanosheets (NNU-55-Ni-NS) in situ to improve the photocatalytic CO2-to-CO activity significantly. After that, CO serving as reactant is further reconverted into organic molecules through the coupled carbonylation reactions. Especially in the carbonylation reaction of diethyltoluamide synthesis, CO conversion reaches up to 85%. Meanwhile, this tandem transformation also provides a simple and low-cost method for the 13C isotopically labeled organic molecules. This work represents an important and feasible pathway for the subsequent separation and application of CO2 photoreduction product.

Enhanced Cuprophilic Interactions in Crystalline Catalysts Facilitate the Highly Selective Electroreduction of CO2 to CH4.

Cu(I)-based catalysts have proven to play an important role in the formation of specific hydrocarbon products from electrochemical carbon dioxide reduction reaction (CO2RR). However, it is difficult to understand the effect of intrinsic cuprophilic interactions inside the Cu(I) catalysts on the electrocatalytic mechanism and performance. Herein, two stable copper(I)-based coordination polymer (NNU-32 and NNU-33(S)) catalysts are synthesized and integrated into a CO2 flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO2-to-CH4 conversion due to clearly inherent intramolecular cuprophilic interactions. Substitution of hydroxyl radicals for sulfate radicals during the electrocatalytic process results in an in situ dynamic crystal structure transition from NNU-33(S) to NNU-33(H), which further strengthens the cuprophilic interactions inside the catalyst structure. Consequently, NNU-33(H) with enhanced cuprophilic interactions shows an outstanding product (CH4) selectivity of 82% at -0.9 V (vs reversible hydrogen electrode, j = 391 mA cm-2), which represents the best crystalline catalyst for electrocatalytic CO2-to-CH4 conversion to date. Moreover, the detailed DFT calculations also prove that the cuprophilic interactions can effectively facilitate the electroreduction of CO2 to CH4 by decreasing the Gibbs free energy change of potential determining step (*H2COOH → *OCH2). Significantly, this work first explored the effect of intrinsic cuprophilic interactions of Cu(I)-based catalysts on the electrocatalytic performance of CO2RR and provides an important case study for designing more stable and efficient crystalline catalysts to reduce CO2 to high-value carbon products.

Identification of plasma microRNA-22 as a marker for the diagnosis, prognosis, and chemosensitivity prediction of osteosarcoma.

OBJECTIVE: MicroRNA (miR)-22 plays crucial roles in malignant tumors and is involved in regulation of chemosensitivity. Additionally, altered expression of circulating miR-22 has been reported in various cancers. This study was designed to investigate plasma miR-22 expression in patients with osteosarcoma (OS) and determine its diagnostic, prognostic, and chemosensitivity prediction value. METHODS: Plasma miR-22 levels in 120 patients with OS and 120 healthy controls were detected by real-time quantitative reverse transcription PCR. Associations of plasma miR-22 expression with the patients' clinicopathological features and prognosis were then assessed. RESULTS: Plasma miR-22 levels in patients with OS were significantly lower than those in healthy controls. Low plasma miR-22 levels were correlated with large tumor size, advanced clinical stages, positive distant metastasis, and poor tumor response to preoperative chemotherapy. Plasma miR-22 could discriminate OS patients from controls and distinguish patients with a good response to therapy from those with a poor response to therapy. Multivariate analysis revealed that low plasma miR-22 expression was a significant independent predictor of unfavorable prognosis. CONCLUSIONS: Altered plasma levels of miR-22 might serve as a novel, noninvasive biomarker for OS diagnosis, prognosis, and chemosensitivity prediction.

Conduit Route Selection for Total Cavopulmonary Connection in Patients With Apicocaval Juxtaposition.

Apicocaval juxtaposition (ACJ) may complicate the selection of conduit route in patients with single ventricles when total cavopulmonary connection (TCPC) is performed. We reviewed our experience of pathway selection and evaluated the clinical results. Of 128 patients who underwent TCPC at our hospital between January 2009 and April 2016, 31 with ACJ were included in this study. In 24 patients, the conduit was placed between the inferior vena cava (IVC) and the ipsilateral pulmonary artery. To avoid compression of the conduit and pulmonary veins in 5 patients, the conduit was placed between the IVC and the contralateral pulmonary artery. In 2 patients, the tube graft was anastomosed with the IVC orifice within the atrium, then guided through the atrial free wall and anastomosed with the contralateral pulmonary artery outside the heart (intra/extracardiac Fontan). Patient demographics were compared with those of patients without ACJ. The mean age and body weight at surgery were 58.5 ±â€¯32.4 months and 16.2 ±â€¯6.0 kg, respectively. The mean postoperative pulmonary artery pressure was 15 ±â€¯3 mm Hg. The postoperative data did not differ significantly from that of patients without ACJ who underwent extracardiac TCPC. One patient died of overwhelming infection. The mean follow-up was 17.5 ±â€¯15.4 months (range, 1-65 months). There were no conduit-related early or late complications. TCPC in patients with ACJ can be performed with excellent early and midterm results. The route between the IVC and the ipsilateral pulmonary artery is our preference.

Early- and mid-term outcomes of surgical repair of persistent truncus arteriosus in children / 中国胸心血管外科临床杂志

@#Objective To evaluate the early- and mid-term outcomes of surgical repair of persistent truncus arteriosus in children in a single institution of China. Methods The clinical data of 27 consecutive patients with persistent truncus arteriosus undergoing surgical repair in Guangzhou Women and Children’s Medical Center from November 2009 to May 2018 were retrospectively reviewed. There were 14 males and 13 females. Median age was 3.0 months (range: 13 days -11 years), of whom 10 (37.0%) were older than 6 months. Results There were three early deaths with a mortality of 11.1%. The main complications included VSD partial repair in 2 patients, complete atrioventricular block in one patient. The mean follow-up time was 24.5±19.3 months (range: 1–76 months). There were three late deaths, and two patients lost follow. Echocardiology showed seven patients of right heart outflow tract obstruction, including three in pulmonary artery trunk, and four of pulmonary artery branches. One patient showed moderate aortic valve regurgitation. None required re-intervention during the follow-up. Survival estimates for the entire cohort following surgery were both 76.1% (95%CI 59.2% to 92.9%) at 1 year and 5 years. Conclusion The surgical repair of persistent truncus arteriosus (PTA) remains challenges. The early- and mid-term outcomes of surgical repair of persistent truncus arteriosus are acceptable. For older children with severe pulmonary artery hypertension and/or trunk valve regurgitation, the risk of death is still higher. Some children have the higher risk of late right heart obstructive lesions.

[Surgical treatment of total anomalous pulmonary venous connection under 6 months of age].

OBJECTIVE: To discuss the experience of surgical treatment of total anomalous pulmonary venous connection (TAPVC) in infants. METHODS: The clinic data of 84 cases with TAPVC under 6 months of age underwent surgical treatment at Department of Cardiac Surgery, Guangzhou Women and Children's Medical Center from January 2012 to October 2015 were analyzed retrospectively. There were 58 male and 26 female patients. The patients were aged 1 days to 6 months with a mean of (2.4±2.2) months at surgery, including 22 newborns. Body weight was 1.8 to 6.8 kg with a mean of (4.3±1.2) kg. There were 24 cases of intracardiac type, 46 cases of supracardiac type, 10 cases of infracardiac type and 4 cases of mixed type. There were 26 cases received emergent operation. There were 14 cases used Sutureless technique in operations and 46 cases used conventional methods in the no-intracardiac type cases, and 2 cases enlarged the anastomsis with autologous pericardium. According to the condition, corrective surgeries of other anomalies were performed in the meantime, including 3 Warden operations (right side), 3 bilateral bidirectional Gleen operation, 2 correction of unroofed coronary sinus syndrome, 1 coarctation of aorta correction with deep hypothermic circulation arrest, and 1 repair of ventricular septal defect. RESULTS: The ratio of newborn was higher in Sutureless technique group than in conventional methods group (7/14 vs. 32.6%, χ(2)=4.927, P=0.043), and mean age was less ((1.8±0.4) months vs. (2.4±2.2) months, F=4.257, P=0.042), but there were no difference in body weight, cardiopulmonary bypass time and aorta clamped time between the two groups. Followed up for 1 to 46 months, 10 cases (11.9%) died overall and the mortality of intracardiac (3/10) and mixed (2/4) type were much higher than in intracardiac (4.2%) and supracardiac (13.0%) type. The mortality were no difference between newborn and infants, or whether emergent operation, or Sutureless technique and conventional methods. The maximal pulmonary venous flow velocity was abnormal speed-up >1.8 m/s at 1 week and 1 to 3 months post-operation mostly. CONCLUSIONS: The mortality of TAPVC was differed by different types. Intrinsic pulmonary vein stenosis maybe the main cause of mortality. The high quality of anastomsis could reduce the operative mortality.

Outcomes of total cavopulmonary connection for single ventricle palliation.

BACKGROUND: The aim of this study was to review the early and mid-term outcomes of the total cavopulmonary connection (TCPC) procedure and evaluate risk factors for prolonged pleural effusions. METHODS: The clinical records of 82 consecutive patients, who underwent a TCPC operation between January 2008 and December 2013, were reviewed for incidence of prolonged pleural effusions, duration of ventilation time and pleural drainage, length of intensive care unit (ICU) stay, and early and mid-term morbidity and mortality. RESULTS: The median age at surgery was 3.0 years. The main single ventricle diagnoses included 18 cases of a double-inlet single ventricle, 17 cases of heterotaxy, 16 cases of tricuspid atresia, 4 cases of mitral atresia, 12 cases of unbalanced complete atrioventricular canal (CAVC), 5 cases of double-outlet right ventricle (DORV) combined with ventricular septal defect (VSD) and pulmonary stenosis (PS), 4 cases of transposition of the great arteries (TGA) combined with VSD and PS, 4 cases of corrected transposition of great arteries (cTGA) combined VSD and PS, and 2 cases of criss-cross heart. Preoperative mean pulmonary artery pressure (mPAP) was 13.66±2.21 mmHg with 23.2% (n=19) higher than 15 mmHg. A total of 61 (74.4%) patients underwent a fenestration. The perioperative mortality was 4.9%. The median duration of pleural effusion was 10 days (range, 3-80 days), and prolonged pleural effusions occurred in 16 (19.5%) patients. Multivariable analysis revealed that mPAP >15 mmHg was independently associated with prolonged pleural effusions (OR, 8.33; 95% CI, 2.33-29.74; P=0.001), and creation of a fenestration was associated with decreased odds of effusion (OR, 0.21; 95% CI, 0.06-0.74; P=0.015). Five-year estimated Kaplan-Meier survival of two-stage TCPC was significantly higher than that of one-stage group(96.7% vs. 79.7%, P=0.023). Patients with heterotaxy or obstructed totally anomalous pulmonary venous connection (TAPVC) had significantly worse mid-term survival. CONCLUSIONS: Staged TCPC improved the early and mid-term survival of patients with a single ventricle. mPAP >15 mmHg was independently associated with prolonged pleural effusions and a fenestration significantly associated with a lower odds of effusion.

Early- and Middle-Term Surgical Outcomes in Patients with Heterotaxy Syndrome.

OBJECTIVES: Heterotaxy syndrome is a recognized risk factor for surgical cardiac interventions. We evaluated the early- and middle-term results of a surgical intervention for patients with heterotaxy syndrome. METHODS: A total of 42 patients with heterotaxy syndrome were enrolled (September 2008 to March 2015). Left and right atrial isomerism were identified in 26% (11 out of 42) and 74% of patients (31 out of 42), respectively. The median age of the patients at the time of surgery was 6.8 months (range: 5 days to 22.3 years). Biventricular repair was completed in 3 patients with left atrial isomerism. Seventeen out of 39 patients who were scheduled for single ventricular repair completed a modified Fontan procedure. RESULTS: The hospital mortality rate was 4.7% (2 out of 42). Another 5 deaths occurred in the remaining survivors following hospital discharge with a follow-up duration of 45.8 ± 23.6 months (range: 13-111 months). The 1-year and 5-year survival rates were 88.1% (37/42) and 83.3% (35/42), respectively. Univariate analysis and multivariate analysis identified pulmonary venous obstruction and atrioventricular valve replacement as additional risk factors for mortality. CONCLUSIONS: Right ventricular bypass surgery remains the preferred palliative procedure for patients with heterotaxy syndrome. Based on the current results, the early- and middle-term outcomes are satisfactory.

Early and mid-term results of the arterial switch operation in patients with intramural coronary artery.

Intramural coronary artery is known to be a risk factor for early death after an arterial switch operation (ASO). We evaluated the early and mid-term results of ASO for patients with intramural coronary artery. From September 2008 to March 2012, seven patients with an intramural coronary artery underwent ASO at our hospital. The mean age at operation was 2.4 months (2 days-1 year), and the mean body weight was 4.3 ± 2.2 kg. The mean follow-up was 35.3 ± 16.5 months (22-63 months). The individual coronary button technique was used in seven patients. The intramural segment was unroofed in one patient; in one patient with myocardial ischemia, the intramural segment was unroofed and enlarged using a patch of autologous pericardium. There was one operative death because of low cardiac output syndrome (14.2% mortality). In the same time period at our hospital, three deaths were reported in 68 ASO patients (4.4% mortality) without an intramural coronary artery. There was no statistical difference between the two groups (P > 0.05). There were no late deaths, and no patients required a coronary intervention. Intramural coronary artery is a well-known risk factor for early death after ASO. To optimize results, the coronary transfer technique should be tailored to each patient's particular anatomy. Intraoperative or postoperative myocardial ischemia should be addressed aggressively by immediately reimplanting the coronary artery. Unroofing the intramural segment, even the distal portion, should restore normal coronary blood flow.

[Surgical treatment of congenital vascular ring].

OBJECTIVE: To discuss the diagnosis and surgical treatment of congenital vascular ring and prognostic factors. METHODS: The clinic data of 42 cases of congenital vascular from January 2010 to December 2013 was analyzed retrospectively (accounting for 1.04% congenital heart operations over the same period ). There were 26 male and 16 female patients, aged at surgery 24 days to 6 years (average 10.7 months). The diagnosis including pulmonary artery sling in 26 cases, double aortic arch in 10 cases, right aortic arch with aberrant left subclavian artery in 3 cases, pulmonary artery sling and right aortic arch with vagus left subclavian artery in 2 cases, pulmonary artery sling and left aortic arch with vagus right subclavian artery in 1 case. In addition to 4 cases the remaining 38 patients were still combined with other cardiovascular malformations. Thirty-six cases of children underwent spiral CT airway remodeling, 23 children underwent fiber- bronchoscopy. In addition to 2 cases of airway abnormalities not seen, the rest of the children were present in varying degrees in different parts of tracheal stenosis or tracheomalacia. All patients underwent surgical correction of congenital vascular ring, concomitant heart deformity correction surgery according to the situation (7 cases of atrial septal defect repair, 3 of ventricular septal defect repair, 1 of mitral valvuloplasty, 1 of bi-Glenn, 1 of coarctation of the aorta correction with ventricular septal defect repair, 1 of trilogy of Fallot correction). One case suffered resection of tracheal stenosis and Slide tracheoplasty simultaneously, another case was implanted tracheal stenting postoperatively after pulmonary artery sling correction. RESULTS: Three patients died in hospital (7.1%), the cause of death were recurrent granuloma formation postoperatively. Remaining 39 patients were successfully discharged. The median time of overall survival of children with mechanical ventilation was 14 h (22 h) (M (Q(R))), median ICU residence time was 5 d (8 d), and the median in-hospital time was 19 d (9 d). Tracheal intubation time and postoperative ICU duration time in children with pulmonary artery sling children were much more than in children with double aortic arch (23 h (123 h) vs. 9 h(9 h), 7 d (13 d) vs. 4 d (2 d)), but the difference were not statistically significant. There was significant difference in the duration of hospitalization between the patient with the pulmonary artery sling and double aortic arch (23 d (9 d) vs. 16 d(6 d)) (χ(2) = 10.157, P = 0.006). CONCLUSIONS: The recent results of surgical treatment of congenital vascular ring is safe and effective. The extent and scope of tracheal stenosis and tracheomalacia is a critical influence prognosis.