Electrochemical oxygen reduction could proceed via either 4e−-pathway toward maximum chemical-to-electric energy conversion or 2e−-pathway toward onsite H2O2 production. Bulk Pt catalysts are known as the best monometallic materials catalyzing O2-to-H2O conversion, however, controversies on the reduction product selectivity are noted for atomic dispersed Pt catalysts. Here, we prepare a series of carbon supported Pt single atom catalyst with varied neighboring dopants and Pt site densities to investigate the local coordination environment effect on branching oxygen reduction pathway. Manipulation of 2e− or 4e− reduction pathways is demonstrated through modification of the Pt coordination environment from Pt-C to Pt-N-C and Pt-S-C, giving rise to a controlled H2O2 selectivity from 23.3% to 81.4% and a turnover frequency ratio of H2O2/H2O from 0.30 to 2.67 at 0.4 V versus reversible hydrogen electrode. Energetic analysis suggests both 2e− and 4e− pathways share a common intermediate of *OOH, Pt-C motif favors its dissociative reduction while Pt-S and Pt-N motifs prefer its direct protonation into H2O2. By taking the Pt-N-C catalyst as a stereotype, we further demonstrate that the maximum H2O2 selectivity can be manipulated from 70 to 20% with increasing Pt site density, providing hints for regulating the stepwise oxygen reduction in different application scenarios.

Herein, two water‐soluble PROXYL‐based magnetic resonance imaging (MRI) macromolecular organic contrast agents (mORCAs) are designed and synthesized: linear and cross‐linked PCE‐mPEG‐Ppa‐PROXYL. They are prepared by conjugating linear and cross‐linked poly(carboxylate ester) (PCE) with poly(ethylene glycol) (mPEG 2000 )‐modified nitroxides (PROXYL), respectively. Both mORCAs form self‐assembled aggregates in an aqueous phase and PROXYL is protected inside a hydrophobic core to achieve great resistance to reduction in the physiological environment, and they have low toxicity. Since cross‐linked PCE‐mPEG‐Ppa‐PROXYL possess a branched architecture, its self‐assembled aggregate is more stable and compact with a greater particle size. Cross‐linked PCE‐mPEG‐Ppa‐PROXYL outperform the linear one in the following aspects: 1) its longitudinal relaxivity ( r 1 = 0.79 m m −1 s −1 ) is higher than that of the linear one ( r 1 = 0.64 m m −1 s −1 ) and both excel the best mORCA reported so far ( r 1 = 0.42 m m −1 s −1 ); 2) its blood retention time (≈48 h) is longer than that of its linear counterpart (≈10 h); 3) cross‐linked PCE‐mPEG‐Ppa‐PROXYL provided better MR imaging contrast resolution in normal organs (liver and kidney) and tumor of mice than the linear one. Overall, cross‐linked PCE‐mPEG‐Ppa‐PROXYL may have great potential to be a novel metal‐free macromolecular contrast agent for MR imaging.

A shared story: Three fawcettimine- and serratinine-type Lycopodium alkaloids are prepared from a common tetracyclic spirodiketone intermediate in concise total syntheses. The intermediate was constructed by a remarkable biosynthesis-inspired transannular N-C bond formation to the spiro-configured carbon center and a hydroxy-directed pinacol coupling promoted by SmI(2).

Background To determine the discrepancy of crown-root morphology of central incisors among different types of skeletal malocclusion using cone-beam computed tomography (CBCT) and to provide guidance for proper torque expression of anterior teeth and prevention of alveolar fenestration and dehiscence. Methods In this retrospective study, a total of 108 CBCT images were obtained (ranging from 18.0 to 30.0 years, mean age 25.8 years). Patients were grouped according to routine sagittal and vertical skeletal malocclusion classification criteria. The patients in sagittal groups were all average vertical patterns, with Class I comprised 24 patients—14 females and 10 males; Class II comprised 20 patients—13 females and 7 males; and Class III comprised 22 subjects—13 females and 9 males. The patients in vertical groups were all skeletal Class I malocclusions, with low angle comprised 21 patients—12 females and 9 males; average angle comprised 24 patients; and high angle comprised 21 patients—11 females and 10 males. All the CBCT data were imported into Invivo 5.4 software to obtain a middle labio-lingual section of right central incisors. Auto CAD 2007 software was applied to measure the crown-root angulation (Collum angle), and the angle formed by a tangent to the central of the labial surface of the crown and the long axis of the crown (labial surface angle). One-way analysis of variance (ANOVA) and Scheffe’s test were used for statistical comparisons at the P < 0.05 level, and the Pearson correlation analysis was applied to investigate the association between the two measurements. Results The values of Collum angle and labial surface angle in maxillary incisor of Class II and mandibular incisor of Class III were significantly greater than other types of sagittal skeletal malocclusions ( P < 0.05); no significant difference was detected among vertical skeletal malocclusions. Notably, there was also a significant positive correlation between the two measurements. Conclusions The maxillary incisor in patients with sagittal skeletal Class II malocclusion and mandibular incisor with Class III malocclusion present remarkable crown-root angulation and correspondingly considerable labial surface curvature. Equivalent deviation during bracket bonding may cause greater torque expression error and increase the risk of alveolar fenestration and dehiscence.

In this article, we present an improved artificial potential field method of trajectory planning and obstacle avoidance for redundant manipulators. Specifically, we not only focused on the position for the manipulator end-effectors but also considered their posture in the course of trajectory planning and obstacle avoidance. We introduced boundaries for Cartesian space components to optimize the attractive field function. Moreover, the manipulator achieved a reasonable speed to move to the target pose, regardless of the difference between the initial pose and target pose. We proved the stability using Lyapunov stability theory by introducing velocity feedforward, when the manipulator moved along a continuous trajectory. Considering the shape of the manipulator joints and obstacles, we set up the collision detection model by projecting the obstacles to link coordinates. In this case, establishing the repulsive field between the nearest points on every joint and obstacles with the closest distance was sufficient for achieving obstacle avoidance for redundant manipulators. The simulation results based on a nine-degree-of-freedom hyper-redundant manipulator, which was designed and made in our laboratory, fully substantiated the efficacy and superiority of the proposed method.

There are three abnormally high porosity zones developed in buried Paleogene nearshore subaqueous fan and sublacustrine fan clastic reservoirs at 2,800-3,200 m, 3,250-3,700 m and 3,900-4,400 m, respectively, within the Shengtuo area of the Dongying Sag. Here the porosity of reservoirs buried deeper than 4,000 m can still be greater than 20%. Investigation of these three abnormally high porosity (AHP) zones in the 3 rd to 4 th analysis, core physical property testing and other technical methods. The results show that, the AHP primary intergranular pores (more than 50% of the total porosity), while secondary pores and micropores in authigenic clays may develop in some reservoirs. AHP reservoirs in the AHP zone of 3,900-4,400 m are dominated by micropores in matrix, visible pores are mainly grain dissolution pores but with low absolute content (< 1%), so this zone belongs to the micropores primary AHP zone. The genesis of the three AHP zones was studied to distinguish between porosity enhancement and porosity preservation. Our research shows that, in deeply buried clastic reservoirs in the Shengtuo area, mineral dissolution occurred in a relatively closed diagenetic system with high temperature and high salinity. Reservoir rocks underwent extensive feldspar dissolution, while detrital carbonate grains and carbonate cements show dissolution enhanced porosity only a little due to the precipitation of almost isovolumetric dissolution products in the nearby primary intergranular pores in forms of authigenic clays and quartz cements. Net enhanced porosity originating from feldspar dissolution is generally less than 0.25%. Thus, the subsurface dissolution has little impact on the mid-deep buried high porosity reservoirs. Reservoirs in braided channels of middle fans in sublacustrine fans and reservoirs in the middle-front of fan bodies of nearshore overpressure and early hydrocarbon emplacement have effectively retarded compaction and carbonate are the main controlling factors in the development of AHP zones.unexpectedly high porosity and permeability at substantial burial depth. Studies on the origin and distribution of these high-quality abnormally high porosity (AHP) reservoirs are of great importance for oil-gas exploration and production. is statistically higher than the porosity values occurring in typical sandstone reservoirs of a given lithology (composition and texture), age and burial/temperature history. In sandstones containing abnormally high porosities, such porosities

Although dirhodium-catalyzed multicomponent reactions of diazo compounds, nucleophiles and electrophiles have achieved great advance in organic synthesis, the introduction of allylic moiety as the third component via allylic metal intermediate remains a formidable challenge in this area. Herein, an attractive three-component reaction of readily accessible amines, diazo compounds, and allylic compounds enabled by a novel dirhodium­(II)/Xantphos catalysis is disclosed, affording various architecturally complex and functionally diverse α-quaternary α-amino acid derivatives in good yields with high atom and step economy. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium­(II)-catalyzed carbene insertion and allylic alkylation process, in which the catalytic properties of dirhodium are effectively modified by the coordination with Xantphos, leading to good activity in the catalytic allylic alkylation process.

Graded UMR recession for 15-35 PD of esodeviation was as effective as graded BMR recession for 30-70 PD of esodeviation. There was no statistical difference in changes in deviation per millimetre of recession between equivalent amounts of unilateral and bilateral recession.