Activation of MnO6 Units via an Interfacial Electric Field: Electron Injection into Mn t2g for Rapid and Stable Sodium Ion Storage in CeO2 /MnOx.

Manganese-based oxides (MnOx ) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO2 /MnOx is constructed to obtain high electronic/ionic conductivity and structural stability of MnOx . The as-designed CeO2 /MnOx exhibits a remarkable capacity of 397 F g-1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t2g orbitals driven by the formed IEF. Correspondingly, the MnO6 units in MnOx are effectively activated, endowing the CeO2 /MnOx with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO2 /MnOx , which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnOx during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials.

Electronegative Phosphorus-Integrated Co2+ Active Sites for Enhanced Electrocatalytic Nitrogen Reduction.

In the quest for proficient electrocatalysts for ammonia's electrocatalytic nitrogen reduction, cobalt oxides, endowed with a rich d-electron reservoir, have emerged as frontrunners. Despite the previously evidenced prowess of CoO in this realm, its ammonia yield witnesses a pronounced decline as the reaction unfolds, a phenomenon linked to the electron attrition from its Co2+ active sites during electrocatalytic nitrogen reduction reaction (ENRR). To counteract this vulnerability, we harnessed electron-laden phosphorus (P) elements as dopants, aiming to recalibrate the electronic equilibrium of the pivotal Co active site, thereby bolstering both its catalytic performance and stability. Our empirical endeavors showcased the doped P-CoO's superior credentials: it delivered an impressive ammonia yield of 49.6 and, notably, a Faradaic efficiency (FE) of 9.6% at -0.2 V versus RHE, markedly eclipsing its undoped counterpart. Probing deeper, a suite of ex-situ techniques, complemented by rigorous theoretical evaluations, was deployed. This dual-pronged analysis unequivocally revealed CoO's propensity for an electron-driven valence metamorphosis to Co3+ post-ENRR. In stark contrast, P-CoO, fortified by P doping, exhibits a discernibly augmented ammonia yield. Crucially, P's intrinsic ability to staunch electron leakage from the active locus during ENRR ensures the preservation of the valence state, culminating in enhanced catalytic dynamism and fortitude. This investigation not only illuminates the intricacies of active site electronic modulation in ENRR but also charts a navigational beacon for further enhancements in this domain.

Unlocking Spin Gates of Transition Metal Oxides via Strain Stimuli to Augment Potassium Ion Storage.

Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost-effectiveness and a broad potential window. However, their full potential is limited by poor understanding of their slow reaction kinetics and stability issues. This study diverges from conventional complex nano-structuring, concentrating instead on spin-related charge transfer and orbital interactions to enhance the reaction dynamics and stability of TMOs during energy storage processes. We successfully reconfigured the orbital degeneracy and spin-dependent electronic occupancy by disrupting the symmetry of magnetic cobalt (Co) sites through straightforward strain stimuli. The key to this approach lies in the unfilled Co 3d shell, which serves as a spin-dependent regulator for carrier transfer and orbital interactions within the reaction. We observed that the opening of these 'spin gates' occurs during a transition from a symmetric low-spin state to an asymmetric high-spin state, resulting in enhanced reaction kinetics and maintained structural stability. Specifically, the spin-rearranged Al-Co3O4 exhibited a specific capacitance of 1371 F g-1, which is 38 % higher than that of unaltered Co3O4. These results not only shed light on the spin effects in magnetic TMOs but also establish a new paradigm for designing electrochemical energy storage materials with improved efficiency.

High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation.

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO2), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO2 presents an impressive capacitance of 317 F g-1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t2g orbital. Additionally, the charge redistribution from Ni to the t2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.

Local Electric Field Induced by Atomic-Level Donor-Acceptor Couple of O Vacancies and Mn Atoms Enables Efficient Hybrid Capacitive Deionization.

Transition metal oxides suffer from slow salt removal rate (SRR) due to inferior ions diffusion ability in hybrid capacitive deionization (HCDI). Local electric field (LEF) can efficiently improve the ions diffusion kinetics in thin electrodes for electrochemical energy storage. Nevertheless, it is still a challenge to facilitate the ions diffusion in bulk electrodes with high loading mass for HCDI. Herein, this work delicately constructs a LEF via engineering atomic-level donor (O vacancies)-acceptor (Mn atoms) couples, which significantly facilitates the ions diffusion and then enables a high-performance HCDI. The LEF boosts an extended accelerated ions diffusion channel at the particle surface and interparticle space, resulting in both remarkably enhanced SRR and salt removal capacity. Convincingly, the theoretical calculations demonstrate that electron-enriched Mn atoms center coupled with an electron-depleted O vacancies center is formed due to the electron back-donation from O vacancies to adjacent Mn centers. The resulted LEF efficiently reduce the ions diffusion energy barrier. This work sheds light on the effect of atomic-level LEF on improving ions diffusion kinetics at high loading mass application and paves the way for the design of transition metal oxides toward high-performance HCDI applications.

Internal Electric Field Induced by Superexchange Interaction on Mn4+ -O2- -Ni2+ Unit Enables Highly Efficient Hybrid Capacitive Deionization.

Internal electric field (IEF) construction is an innovative strategy to regulate the electronic structure of electrode materials to promote charge transfer processes. Despite the wide use of IEF in various applications, the underlying mechanism of its formation in an asymmetric TM-O-TM unit still remains poorly understood. Herein, the essential principles for the IEF construction at electron occupancy state level and explore its effect on hybrid capacitive deionization (HCDI) performance is systematically investigated. By triggering a charge separation in Ni-MnO2 via superexchange interactions in a coordination structure unit of Mn4+ -O2- -Ni2+ , the formation of an IEF that can enhance charge transfer during the HCDI process is demonstrated. Experimental and theoretical results confirm the electrons transfer from O 2p orbital to TM (Ni2+ and Mn4+ ) eg orbital via superexchange interactions in the basic Mn4+ -O2- -Ni2+ coordination unit. As a result of the charge redistribution, the IEF endows Ni-MnO2 with superior electron and ion transfer property. This work presents a unique material design strategy that activates the electrochemical performance, and provides insights into the formation mechanism of IEF in an asymmetric TM-O-TM unit, which has potential applications in the construction of other innovative materials.

Interfacial Push-Pull Dynamics Enable Rapid Had Desorption for Enhanced Formate Electrooxidation.

The electrocatalytic conversion of formate in alkaline solutions is of paramount significance in the realm of fuel cell applications. Nonetheless, the adsorptive affinity of adsorbed hydrogen (Had) on the catalyst surface has traditionally impeded the catalytic efficiency of formate in such alkaline environments. To circumvent this challenge, our approach introduces an interfacial push-pull effect on the catalyst surface. This mechanism involves two primary actions: First, the anchoring of palladium (Pd) nanoparticles on a phosphorus-doped TiO2 substrate (Pd/TiO2-P) promotes the formation of electron-rich Pd with a downshifted d band center, thereby "pushing" the desorption of Had from the Pd active sites. Second, the TiO2-P support diminishes the energy barrier for Had transfer from the Pd sites to the support itself, "pulling" Had to effectively relocate from the Pd active sites to the support. The resultant Pd/TiO2-P catalyst showcases a remarkable mass activity of 4.38 A mgPd-1 and outperforms the Pd/TiO2 catalyst (2.39 A mgPd-1) by a factor of 1.83. This advancement not only surmounts a critical barrier in catalysis but also delineates a scalable pathway to bolster the efficacy of Pd-based catalysts in alkaline media.

[Evaluation of shensongyangxin capsules in the treatment of paroxysmal atrial fibrillation: a randomized, double-blind and controlled multicenter trial].

OBJECTIVE: To evaluate the efficacy and safety of Chinese medicinal shensongyangxin capsules in the treatment of paroxysmal atrial fibrillation. METHODS: From August 2007 to July 2008, Beijing Chaoyang Hospital conducted a multicenter study, select the eleven hospital's outpatient subjects, aged 18 to 75 years old, male or female, paroxysmal atrial fibrillation (at least one electrocardiogram diagnosis) seizure frequency ≥ 2 times/month, according to the ratio 1:1:1, subjects were randomly divided into three groups: a. shensongyangxin group, taking shensongyangxin capsule 4 + propafenone analogues 150 mg, 3 times a day; b. propafenone group, taking propafenone tablets 150 mg + 4 shensongyangxin analogues, 3 times a day; shensongyangxin capsule + propafenone group, taking shensongyangxin capsule 4 + propafenone 150 mg, 3 times a day. The treatment course is 8 weeks, with 3 times of follow-up. RESULTS: Total of 349 cases of paroxysmal atrial fibrillation, which 117 cases in shensongyangxin group, 115 cases in propafenone group; 117 cases in shensongyangxin + propafenone group. The baseline data analysis showed that there were no significantly difference (P > 0.05) among the three groups of atrial fibrillation seizure frequency, vital signs, general condition, medical history, 24-hour ambulatory ECG, 12-lead normal electrocardiogram, cardiac ultrasound and symptoms. The comparison before and after (8 weeks) treatment showed that the frequency (from 6 times/m to 2 times/m in each group, P < 0.01), number of cases [from 46 (43.3%) to 22 (20.8%), 43 (43.4%) to 25 (25.3%), and 40 (40.6%) to 31 (29.2%), respectively P < 0.01] and duration time of attack of atrial fibrillation (from 4 h to 0.5 h, 4 h to 0.5 h, and 4.25 h to 0.5 h, respectively P < 0.01) all decreased in three groups. No significant difference among the three groups comparing the overall effect (62.3%, 58.6%, and 58.5%, respectively, P > 0.05), while the efficacy of TCM symptoms in shensongyangxin group (80.2%) was better than that of propafenone group (67.7%) (P < 0.05). Safety evaluation showed that adverse reaction rate was 1.8% in shensongyangxin group, and 8.2% and 5.4% in propafenone group and shensongyangxin + propafenone group. CONCLUSION: Shensongyangxin capsules and propafenone have comparable efficacies in the treatment of PAF. The efficacy of TCM symptoms is better than propafenone. Shensongyangxin capsules have an excellent profile of safety.

Efficacy and safety of Shexiang Baoxin pill (MUSKARDIA) in patients with stable coronary artery disease: a multicenter, double-blind, placebo-controlled phase IV randomized clinical trial.

BACKGROUND: The Shexiang Baoxin Pill (MUSKARDIA) has been used for treating coronary artery disease (CAD) and angina for more than 30 years in China. Nevertheless, methodologically sound trials on the use of MUSKARDIA in CAD patients are scarce. The aim of the study is to determine the effects of MUSKARDIA as an add-on to optimal medical therapy (OMT) in patients with stable CAD. METHODS: A total of 2674 participants with stable CAD from 97 hospitals in China were randomized 1:1 to a MUSKARDIA or placebo group for 24 months. Both groups received OMT according to local tertiary hospital protocols. The primary outcome was the occurrence of a major adverse cardiovascular event (MACE), defined as a composite of cardiovascular death, non-fatal myocardial infarction (MI), or non-fatal stroke. Secondary outcomes included all-cause mortality, non-fatal MI, non-fatal stroke, hospitalization for unstable angina or heart failure, peripheral revascularization, angina stability and angina frequency. RESULTS: In all, 99.7% of the patients were treated with aspirin and 93.0% with statin. After 2 years of treatment, the occurrence of MACEs was reduced by 26.9% in the MUSKARDIA group (MUSKARDIA: 1.9% vs. placebo: 2.6%; odds ratio = 0.80; 95% confidence interval: 0.45-1.07; P  = 0.2869). Angina frequency was significantly reduced in the MUSKARDIA group at 18 months (P = 0.0362). Other secondary endpoints were similar between the two groups. The rates of adverse events were also similar between the two groups (MUSKARDIA: 17.7% vs. placebo: 17.4%, P = 0.8785). CONCLUSIONS: As an add-on to OMT, MUSKARDIA is safe and significantly reduces angina frequency in patients with stable CAD. Moreover, the use of MUSKARDIA is associated with a trend toward reduced MACEs in patients with stable CAD. The results suggest that MUSKARDIA can be used to manage patients with CAD. TRIAL REGISTRATION: chictr.org.cn, No. ChiCTR-TRC-12003513.

[Long-term outcome of percutaneous balloon mitral valvuloplasty in patients with rheumatic mitral valve stenosis].

OBJECTIVE: To observe the outcome of percutaneous balloon mitral valvuloplasty (PBMV) in patients with rheumatic mitral valve stenosis. METHODS: From April 1992 to November 2008, 1768 patients underwent PBMV in our hospital.Clinical and echocardiographic follow up data were analyzed in 426 patients from April 1992 to August 1998. Left atrial pressure and the mitral valve gradient (MVG) were measured before and immediately after PBMV in all patients. RESULTS: PBMV was successful in 1748 out of 1768 patients (98.86%). Left atrial pressure decreased from (38 +/- 7) mm Hg (1 mm Hg = 0.133 kPa) to (12 +/- 4) mm Hg (P < 0.001), MVG decreased from (28 +/- 6) mm Hg to (8 +/- 3) mm Hg (P < 0.001) and the area of the mitral valve increased from (0.98 +/- 0.26) cm(2) to (1.97 +/- 0.39) cm(2) (P < 0.001) post PBMV. The main complications included death (n = 2), acute pericardial effusion (n = 1), severe mitral regurgitation (n = 12), cerebral embolism (n = 2) and pulmonary edema (n = 1). Ten years follow up was finished in 426 patients and 288 patients (67.6%) were still in NYHA class Ior II without mitral valve replace operation or repeated PBMV, restenosis was evidenced in 140 patients (33.3%) and 31 patients dead (7.5%). CONCLUSION: PBMV was an effective therapy option for patients with rheumatic mitral valve stenosis.

Genetic factors contribute to patient-specific warfarin dose for Han Chinese.

BACKGROUND: Warfarin is a commonly prescribed anticoagulant drug for the prevention of thromboses. To address the association of genetic factors and warfarin dosage for ethnic Han Chinese, we genotyped six candidate genes involved in the warfarin interactive pathway with focus on SNPs with reported association with warfarin dose. METHODS: We recruited a study population consisted of 318 patients receiving warfarin treatment and 995 healthy controls. PCR and direct sequencing were used to identify the sequence polymorphisms. RESULTS: In our study population, SNP rs1799853 of CYP2C9, rs1687390 of ORM1-2, and rs2069919 of PROC showed no variation. SNPs rs12714145 of GGCX and rs1799809 of PROC showed no significant correlation with warfarin dose. The associations of SNPs rs9934438 and rs9923231 of VKORC1, the 3 (rs1057910) and C(-65) (rs9332127) alleles of CYP2C9, and SNP rs4653436 of EPHXI with the dose of warfarin were significant. CONCLUSION: A multiple regression model based on the genetic polymorphisms of VKORC1, CYP2C9, EPHX1 and the non-genetic factors of age and body weight can explain 40.2% of the variance in warfarin dose in Han Chinese patients. Translation of this knowledge into clinical guidelines for warfarin prescription may improve the safety and efficacy of warfarin treatment among Han Chinese.