An increase of serum CA-125 to two times of nadir level strongly predicts the image-identified relapse of serous ovarian cancer.

Using 70 U/ml or 35 U/ml as CA125 routine abnormal threshold may result in omissions in the relapse detection of Ovarian cancer (OvCa). This study aimed to clarify the association between a biochemical relapse (only the elevation of CA125) and an image-identified relapse to predict the relapsed lesions better. 162 patients who achieved complete clinical response were enrolled from women diagnosed with stage I-IV serous ovarian, tubal, and peritoneal cancers from January 2013 to June 2019 at our center. The CA125 level of 2 × nadir was defined as the indicator of image-identified relapse (P < 0.001). Compared to CA125 level exceeding 35 U/ml, the 2 × nadir of CA125 improve the sensitivity of image-identified relapse (84.9% vs 67.4%, P < 0.001); the 2 × nadir value can act as an earlier warning relapse signal with a longer median time to image-identified relapse (2.7 vs. 0 months, P < 0.001). Of the relapsed population, there was no difference of CA125 changing trend between the neoadjuvant chemotherapy (NACT) and primary debulking surgery (PDS) group after initial treatment. Compared with 35 U/ml, CA125 reaching 2 × nadir during the follow-up process might be a more sensitive and early relapse signal in patients with serous OvCa. This criterion may help guide patients to be recommended for imaging examination to detect potential relapse in time.

Selective C-H Bond Activation in Propane with Molecular Oxygen over Cu(I)-ZSM-5 at Ambient Conditions.

Selective activation of C-H bonds in light alkanes under mild conditions is challenging but holds the promise of efficient upgrading of abundant hydrocarbons. In this work, we report the conversion of propane to propylene with ∼95% selectivity on Cu(I)-ZSM-5 with O2 at room temperature and pressure. The intraporous Cu(I) species was oxidized to Cu(II) during the reaction but could be regenerated with H2 at 220 °C. Diffuse reflectance ultraviolet spectroscopy indicated the presence of both Cu+-O2 and Cu2(µ-O2)2+ species in the zeolite pores during the reaction, and electron paramagnetic resonance results showed that propane activation occurred via a radical-mediated pathway distinct from that with H2O2 as the oxidant. Correlation between spectroscopic and reactivity results on Cu(I)-ZSM-5 with different Cu loadings suggests that the isolated intraporous Cu(I) species is the main active species in propane activation.

Constructing Metal(II)-Sulfate Site Catalysts toward Low Overpotential Carbon Dioxide Electroreduction to Fuel Chemicals.

Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu-NSO4/CN, with highly dispersed Cu(II)-SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (-0.5 V vs. RHE, FEformate=87.4 %). Pure HCOOH is produced with an energy conversion efficiency of 44.3 % at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production.

Prenatal to preimplantation genetic diagnosis of a novel compound heterozygous mutation in HSPA9 associated with Even-Plus syndrome.

BACKGROUND: Heat shock protein family A member 9 (HSPA9) prevents unfolded and dysfunctional protein accumulation, with genetic variants known to be pathogenic. Here, we determined the genetic cause of Even-Plus syndrome (OMIM: 616854) in a Chinese family. METHODS: We collected samples from two affected and two normal individuals. Whole-exome sequencing was performed to identify their genetic profiles. Potential variants were validated using Sanger sequencing. Assisted reproduction with mutation-free embryos successfully blocked the transmission of mutations. RESULTS: We identified novel inherited pathogenic complex heterozygous variations in the HSPA9 gene in the two affected fetuses. Three-dimensional spatial simulation of the HSPA9 protein after prediction of the mutated RNA splicing pattern abolished part of the substrate-binding domain of the protein. According to ACMG guidelines, c. 1822-1G>A and c. 1411-3T>G were classified as pathogenic and likely pathogenic, respectively. Mutation-free embryos were selected for transplantation and reconfirmed to possess no mutations. A healthy daughter was successfully born into the family. CONCLUSIONS: This study is the first to report complex heterozygous variations in the HSPA9 gene that influence alternative splicing in early pregnancy. Our findings expand on the mutational spectrum leading to Even-Plus syndrome and provide a basis for genetic counseling and future embryonic studies.

Mechanistic Implications of Low CO Coverage on Cu in the Electrochemical CO and CO2 Reduction Reactions.

Electrochemical CO or CO2 reduction reactions (CO(2)RR), powered by renewable energy, represent one of the promising strategies for upgrading CO2 to valuable products. To design efficient and selective catalysts for the CO(2)RR, a comprehensive mechanistic understanding is necessary, including a comprehensive understanding of the reaction network and the identity of kinetically relevant steps. Surface-adsorbed CO (COad) is the most commonly reported reaction intermediate in the CO(2)RR, and its surface coverage (θCO) and binding energy are proposed to be key to the catalytic performance. Recent experimental evidence sugguests that θCO on Cu electrode at electrochemical conditions is quite low (∼0.05 monolayer), while relatively high θCO is often assumed in literature mechanistic discussion. This Perspective briefly summarizes existing efforts in determining θCO on Cu surfaces, analyzes mechanistic impacts of low θCO on the reaction pathway and catalytic performance, and discusses potential fruitful future directions in advancing our understanding of the Cu-catalyzed CO(2)RR.

CO Binding Energy is an Incomplete Descriptor of Cu-Based Catalysts for the Electrochemical CO2 Reduction Reaction.

CO binding energy has been employed as a descriptor in the catalyst design for the electrochemical CO2 reduction reactions (CO2 RR). The reliability of the descriptor has yet been experimentally verified due to the lack of suitable methods to determine CO binding energies. In this work, we determined the standard CO adsorption enthalpies ( Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ ) of undoped and doped oxide-derived Cu (OD-Cu) samples, and for the first time established the correlation of Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ with the Faradaic efficiencies (FE) for C2+ products. A clear volcano shaped dependence of the FE for C2+ products on Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ is observed on OD-Cu catalysts prepared with the same hydrothermal durations, however, the trend becomes less clear when all catalysts investigated are taken into account. The relative abundance of Cu sites active for the CO2 -to-CO conversion and the further reduction of CO is identified as another key descriptor.

NLRP3 participates in the differentiation and apoptosis of PMA­treated leukemia cells.

Acute myeloid leukemia (AML) is a clonal malignant proliferative disease. In recent years, with the use of all­trans retinoic acid to induce cancer cell differentiation in acute promyelocytic leukemia, and its advantages of high efficacy and low toxic side effects, tumor differentiation therapy has become a research hotspot; however, the mechanisms underlying its role remain to be fully established. Nod­like receptor family pyridine domain containing 3 (NLRP3) is the most extensively studied and well­characterized inflammasome, is involved in a variety of inflammation­related diseases, including cancer, and is a very attractive potential target for the study of novel therapeutic agents. Activation of the NLRP3 inflammasome is a double­edged sword in tumor therapy, with evidence of protective anti­tumor and pro­tumor effects in different types of cancer. Whether the NLRP3 inflammasome promotes disease progression or exerts a protective anti­tumor effect in hematological malignancies remains contested. In the present study, the protective anti­tumor effects of NLRP3 on leukemia cells during their differentiation and maturation were investigated. It was found that the upregulation of NLRP3 expression induced using Phorbol 12­Myristate 13­Acetate played a role in promoting the differentiation and maturation of leukemia cells into monocytes/macrophages, and it was directly involved in the apoptosis of leukemia cells and the differentiation and maturation of CD11b+ cells. These results provide novel theoretical evidence for exploring the mechanism of differentiation therapy in leukemia and improves our understanding of the role of NLRP3 in hematologic tumors.

Postpartum stress urinary incontinence: a clinical study of 6,302 cases in Jiangsu Province.

OBJECTIVES: To investigate the prevalence and influencing factors of stress urinary incontinence (SUI) within 6-8 weeks postpartum in Jiangsu Province. MATERIAL AND METHODS: We designed a multi-center cross-sectional study involving seven hospitals in Jiangsu province, and enrolled women who underwent postpartum examination at 6-8 weeks in these hospitals between July 2019 and June 2021. According to the presence or absence of SUI, the enrolled patients were divided into two groups: the SUI group and the non-SUI group, respectively. We assessed the general health status, noted the details of delivery, and checked the pelvic floor electromyographic parameters of the postpartum women in both groups. RESULTS: Among 6,302 cases of postpartum women in Jiangsu province, there were 1,579 cases of SUI, with a prevalence of 25.06%. The prevalence of SUI increased significantly with age, BMI, increasing parity, coexisting constipation, organ prolapse, and diastasis recti abdominis. Compared to the non-SUI group, the SUI group had a lower mean value of the pre-baseline rest phase, shorter rise and fall times of fast muscle contractions, and a lower mean value of the endurance contraction phase. Multiple regression analysis revealed associations with weight (especially overweight and obesity), coexisting organ prolapse, constipation, parity, gestational week of delivery, mode of delivery, and mean value of endurance contraction phase. CONCLUSIONS: The prevalence of postpartum stress urinary incontinence in Jiangsu Province was 25.06%, and was linked to being overweight, parity > 2, coexisting organ prolapse, constipation, and a decrease in the mean value of the endurance contraction phase of the electromyograph. In this report, we offer a theoretical basis for the effective prevention of postpartum SUI clinically.

Interface synergism and engineering of Pd/Co@N-C for direct ethanol fuel cells.

Direct ethanol fuel cells have been widely investigated as nontoxic and low-corrosive energy conversion devices with high energy and power densities. It is still challenging to develop high-activity and durable catalysts for a complete ethanol oxidation reaction on the anode and accelerated oxygen reduction reaction on the cathode. The materials' physics and chemistry at the catalytic interface play a vital role in determining the overall performance of the catalysts. Herein, we propose a Pd/Co@N-C catalyst that can be used as a model system to study the synergism and engineering at the solid-solid interface. Particularly, the transformation of amorphous carbon to highly graphitic carbon promoted by cobalt nanoparticles helps achieve the spatial confinement effect, which prevents structural degradation of the catalysts. The strong catalyst-support and electronic effects at the interface between palladium and Co@N-C endow the electron-deficient state of palladium, which enhances the electron transfer and improved activity/durability. The Pd/Co@N-C delivers a maximum power density of 438 mW cm-2 in direct ethanol fuel cells and can be operated stably for more than 1000 hours. This work presents a strategy for the ingenious catalyst structural design that will promote the development of fuel cells and other sustainable energy-related technologies.

Metal-Organic Frameworks-Based Optical Nanosensors for Analytical and Bioanalytical Applications.

Metal-organic frameworks (MOFs)-based optical nanoprobes for luminescence and surface-enhanced Raman spectroscopy (SERS) applications have been receiving tremendous attention. Every element in the MOF structure, including the metal nodes, the organic linkers, and the guest molecules, can be used as a source to build single/multi-emission signals for the intended analytical purposes. For SERS applications, the MOF can not only be used directly as a SERS substrate, but can also improve the stability and reproducibility of the metal-based substrates. Additionally, the porosity and large specific surface area give MOF a sieving effect and target molecule enrichment ability, both of which are helpful for improving detection selectivity and sensitivity. This mini-review summarizes the advances of MOF-based optical detection methods, including luminescence and SERS, and also provides perspectives on future efforts.

Correlating the Experimentally Determined CO Adsorption Enthalpy with the Electrochemical CO Reduction Performance on Cu Surfaces.

CO binding energy has been widely employed as a descriptor for effective catalysts in the electrochemical CO2 and CO reduction reactions (CO(2) RR), however, it has yet to be determined experimentally at electrochemical interfaces due to the lack of suitable techniques. In this work, we developed a method to determine the standard adsorption enthalpy of CO on Cu surfaces with quantitative surface enhanced infrared absorption spectroscopy. On dendritic Cu at -0.75 V vs. SHE, the standard adsorption enthalpy, entropy and Gibbs free energy were determined to 1.5±0.5 kJ mol-1 , ≈37.9±13.4 J/(mol K), and ≈-9.8±4.0 kJ mol-1 , respectively. Comparison of the standard adsorption enthalpy of oxide-derived Cu and dendritic Cu, as well as their CORR activities, suggests the presence of stronger binding sites on OD Cu, which could favor multicarbon products. The method developed in this work will help establish the correlation between the CO binding energy and the CO(2) RR activity.

Correlating CO Coverage and CO Electroreduction on Cu via High-Pressure in Situ Spectroscopic and Reactivity Investigations.

The absolute coverage of CO has been a missing piece in the mechanistic puzzle of the CO reduction reaction (CORR) on Cu. For the first time, we revealed the upper bound of the CO coverage under electrocatalytic conditions to be 0.05 monolayer at atmospheric pressure and the saturation CO coverage to be ∼0.25 monolayer by conducting surface enhanced infrared spectroscopy at CO pressures up to 60 barg in a custom-designed spectroelectrochemical cell. CORR activities on Cu were also determined in the same pressure range. Calculated reaction orders of C2+ products with respect to adsorbed CO are substantially less than unity, clearly indicating that the coupling of adsorbed CO is not the rate-determining step leading to multicarbon products. The increase in CO coverage can reduce the C affinity on the Cu surface and favor the selectivity towards oxygenates, especially acetate, over ethylene. Uncommon products, including ethane, glycolaldehyde, and ethylene glycol, were detected in appreciable amounts, likely due to a new C-C coupling mechanism taking place at elevated CO pressures.

Intercepting Elusive Intermediates in Cu-Mediated CO Electrochemical Reduction with Alkyl Species.

Understanding of the reaction network of Cu-catalyzed CO2/CO electroreduction reaction [CO(2)RR] remains incomplete despite intense research efforts. This is in part because the rate-determining step occurs early in the reaction network, leading to short lifetimes of subsequent surface-bound intermediates, the knowledge of which is key to selectivity control. In this work, we demonstrate that alkyl groups can effectively couple with surface intermediates in the Cu-catalyzed CORR and, for the first time, intercept elusive C1 and C2 intermediates. Combined reactivity data and in situ spectroscopic results demonstrated that surface-bound alkyl groups derived from the corresponding alkyl iodides are able to couple with adsorbed CO to form carboxylates and ketones via one and two successive nucleophilic attacks, respectively. Leveraging this new chemistry, CHx (x ≤ 3) and C2Hx (x ≤ 4) are intercepted and identified as precursors for methane and n-propanol in the CORR, respectively. Importantly, reaction pathways leading to methane and C2+ products are not intrinsically orthogonal, but their connection is mainly impeded by low coverages of energetic intermediates. This study shows that perturbing the reaction of interest by introducing a slightly interacting probe reaction network could be an effective and general strategy in mechanistic studies of catalytic reactions.

Enhancing Hydrogen Oxidation and Evolution Kinetics by Tuning the Interfacial Hydrogen-Bonding Environment on Functionalized Platinum Surfaces.

Developing efficient catalytic systems for the hydrogen oxidation and evolution reactions (HOR/HER) is essential in the world's transition to renewable energy. There is a growing recognition that the HOR/HER activity depends on properties of the electrochemical interface, rather than just the composition and structure of the catalyst. Herein, we demonstrate that specifically adsorbed organic additives (theophylline derivatives) could enhance the intrinsic HOR/HER activity in base on polycrystalline Pt by up to a factor of 3 via introducing weakly hydrogen-bonded water, as confirmed by in situ surface enhanced infrared and Raman spectroscopies. Optimal HOR/HER activity is achieved on a 7-n-butyltheophylline decorated Pt surface, which sufficiently disrupts the hydrogen bonding network in the double layer without depleting the interfacial water. This work demonstrates the promise of electrochemical interfacial engineering as a strategy to boost electrocatalytic performance.

Understanding the complementarities of surface-enhanced infrared and Raman spectroscopies in CO adsorption and electrochemical reduction.

In situ/operando surface enhanced infrared and Raman spectroscopies are widely employed in electrocatalysis research to extract mechanistic information and establish structure-activity relations. However, these two spectroscopic techniques are more frequently employed in isolation than in combination, owing to the assumption that they provide largely overlapping information regarding reaction intermediates. Here we show that surface enhanced infrared and Raman spectroscopies tend to probe different subpopulations of adsorbates on weakly adsorbing surfaces while providing similar information on strongly binding surfaces by conducting both techniques on the same electrode surfaces, i.e., platinum, palladium, gold and oxide-derived copper, in tandem. Complementary density functional theory computations confirm that the infrared and Raman intensities do not necessarily track each other when carbon monoxide is adsorbed on different sites, given the lack of scaling between the derivatives of the dipole moment and the polarizability. Through a comparison of adsorbed carbon monoxide and water adsorption energies, we suggest that differences in the infrared vs. Raman responses amongst metal surfaces could stem from the competitive adsorption of water on weak binding metals. We further determined that only copper sites capable of adsorbing carbon monoxide in an atop configuration visible to the surface enhanced infrared spectroscopy are active in the electrochemical carbon monoxide reduction reaction.

Application of Da Vinci robotic surgery system in cervical cancer: A single institution experience of 557 cases.

OBJECTIVE: Conflicting data have been published regarding the oncologic appropriateness of minimally invasive surgery (MIS) in the treatment of cervical cancer. The purpose of the present study was to investigate whether our experience in the treatment of early cervical cancer using a robotic surgical approach was safe and oncologically effective. METHODS: The data of 557 patients with cervical cancer treated by robotic surgery were retrospectively collected, including the perioperative and survival outcomes. Tumor stage was based on the International Federation of Gynecology and Obstetrics (FIGO 2009). The disease-free survival (DFS) and overall survival (OS) were calculated by the Kaplan-Meier method. RESULTS: Of the 557 patients, 196 (35.2%) patients were stage IA1 to IB1, and 304 (54.6%) patients were stage IB2 to I1A2. Also included were 57 (10.2%) patients with either recurrent or persistent disease following concurrent chemoradiotherapy. Two patients (0.4%) experienced severe intraoperative complications and 11 patients (2.0%) developed postoperative complications. A stratified analysis of survival was conducted in 91 patients who met a follow-up time of 3-year or more. The median follow-up time was 49 (range, 6-57) months. Both the 3-year DFS and OS of early-stage (stage IA1 to IB1) cervical cancer were 97.6%. For patients with locally advanced (stage IB2 to IIA2) disease, DFS and OS were 88.1% and 90.5%, respectively. The patients with recurrent or persistent disease had DFS and OS of 62.5%. CONCLUSION: Our study results demonstrated that the robotic surgical approach could achieve satisfying therapeutic outcomes in patients with early-stage cervical cancer, with a low complication rate. For advanced cervical cancer patients with recurrent or persistent disease following concurrent chemoradiotherapy, robotic surgery undertaken as supplementary therapy may improve prognosis. However, there remains a need for additional prospective data reporting long-term survival of cervical cancer patients treated with a robotic surgical approach.

Survival outcomes of minimally invasive surgery for early-staged cervical cancer: A retrospective study from a single surgeon in a single center.

OBJECTIVE: Recent studies have shown that minimally invasive surgery (MIS) is associated with a higher recurrence rate in patients with early-stage cervical cancer. In this study, we aim to report the survival outcomes of patients with early-stage cervical cancer who received MIS, performed in a single center by the same surgeon. METHODS: Eligible participants included patients with early-stage cervical cancer in stage IA1 with lymphovascular space invasion (LVSI+), IA2, and IB1. The surgeries were carried out by a single surgeon and survival outcomes of the 137 patients were evaluated retrospectively. RESULTS: The median follow-up time for the 137 patients was 53 (25-94) months, with the five-year disease-free survival (DFS) rate of 96.4% and the five-year overall survival (OS) rate of 96.8%. Among them, six (4.38%) patients relapsed and four (2.92%) of whom died. The five-year DFS rate was significantly higher in patients with tumor≤2 cm in size than in those with tumor >2 cm (P = 0.013), however, with no significant difference in the five-year OS rate (P = 0.219). CONCLUSION: According to the existing literature and the results of this study, for MIS, the proficiency levels of a surgeon may be associated with survival outcomes of cancer patients. Tumor size may also be an important factor affecting survival outcomes of cervical cancer patients.

C-C Coupling Is Unlikely to Be the Rate-Determining Step in the Formation of C2+ Products in the Copper-Catalyzed Electrochemical Reduction of CO.

The identity of the rate-determining step (RDS) in the electrochemical CO reduction reaction (CORR) on Cu catalysts remains unresolved because: 1) the presence of mass transport limitation of CO; and 2) the absence of quantitative correlation between CO partial pressure (pCO ) and surface CO coverage. In this work, we determined CO adsorption isotherms on Cu in a broad pH range of 7.2-12.9. Together with electrokinetic data, we demonstrate that the reaction orders of adsorbed CO at pCO <0.4 and >0.6 atm are 1st and 0th , respectively, for multi-carbon (C2+ ) products on three Cu catalysts. These results indicate that the C-C coupling is unlikely to be the RDS in the formation of C2+ products in the CORR. We propose that the hydrogenation of CO with adsorbed water is the RDS, and the site competition between CO and water leads to the observed transition of the CO reaction order.

Preoperative Conization May Have a Positive Impact on Survival in Early-Stage Cervical Cancer: A Propensity-Matched Study.

INTRODUCTION: A recent prospective randomized study demonstrated that minimally invasive surgery (MIS) was inferior to open surgery in disease survival in early-stage cervical cancer. Our aim was to investigate whether there were survival benefits of preoperative conization prior to MIS for early-stage cervical cancer. METHODS: We retrospectively analyzed patients who eventually underwent definitive MIS with stage IA2 to IB1 (no >2 cm) squamous cell carcinoma, adenocarcinoma, and adenosquamous carcinoma. Preoperatively, the patients were separated into 2 groups: one managed with conization and the other undergoing biopsy without conization. Propensity scoring weight and matching were used to reduce the influence of possible allocation biases. The Cox regression model was used for univariate and multivariate analyses of disease recurrence and survival. RESULTS: 227 patients were contained in this study (99 patients in the conization group and 128 patients in the nonconization group). The 5-year DFS of the conization group was statistically better than that of the nonconization group (98.4% vs. 91.8%, p = 0.011). By univariate analysis, conization (HR = 0.11, 95% CI = 0.01-0.87, p = 0.03) and histologic cell type (p = 0.01) were considered as risk factors for recurrence. Multivariate analysis further confirmed conization (HR = 0.04, 95% CI = 0.01-0.51, p = 0.01) and histologic cell type (p < 0.01) correlated with DFS. After propensity score matching (1:1), 84 patients were included in the conization and nonconization groups, respectively, with 5-year DFS still higher in the conization group (98.3% vs. 92.9%, p = 0.037). The results after univariate and multivariate analyses were consistent with those prior to propensity score matching. CONCLUSION: Preoperative conization in conjunction with MIS seemed to be a safe and feasible approach, with results that may have implications for the reduction of recurrence. Histologic cell type also impacted survival. Therefore, more future prospective studies are warranted.

Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper.

Rigorous electrokinetic results are key to understanding the reaction mechanisms in the electrochemical CO reduction reaction (CORR), however, most reported results are compromised by the CO mass transport limitation. In this work, we determined mass transport-free CORR kinetics by employing a gas-diffusion type electrode and identified dependence of catalyst surface speciation on the electrolyte pH using in-situ surface enhanced vibrational spectroscopies. Based on the measured Tafel slopes and reaction orders, we demonstrate that the formation rates of C2+ products are most likely limited by the dimerization of CO adsorbate. CH4 production is limited by the CO hydrogenation step via a proton coupled electron transfer and a chemical hydrogenation step of CO by adsorbed hydrogen atom in weakly (7 < pH < 11) and strongly (pH > 11) alkaline electrolytes, respectively. Further, CH4 and C2+ products are likely formed on distinct types of active sites.