Change In Moment Research Articles

Effect of orthopedic insoles on lower limb motion kinematics and kinetics in adults with flat foot: a systematic review.

Flatfoot is characterized by the collapse of the medial longitudinal arch, eversion of the rearfoot and abduction of the loaded forefoot. Orthopedic insoles are the frequently recommended treatment to support the arch of the foot, adjust the structure of the foot, reduce pain, improve stability and new techniques have been applied to the design of orthopedic insoles in recent years. However, the effectiveness of orthopedic insoles in different motions is still debated from the perspective of biomechanics. Therefore, this study aimed to explore the impact of orthopedic insoles on the kinematics and kinetics of lower limb motion, and to verify effectiveness and propose possible future research directions. We conducted a literature search across three databases employing Boolean operations and filtered results based on eligibility criteria. A total of 671 relevant literature were searched in this review, and 19 literature meeting the requirements were finally included. The results showed that: 1) orthopedic insoles were effective when patients walk, run and jump from the perspective of biomechanics; 2) orthopedic insoles had different result on the change of ankle sagittal angle, moment and peak pressure in the metatarsal region; 3) Whether the effect of insoles, which uses new techniques such as different 3D printed technologies and adds various accessories, can be further improved remains to be further studied; 4) Follow-up studies can pay more attention to the differences between diverse populations, increase the breadth of running and jumping and other movements research and long-term intervention.

A global springback compensation method for manufacturing metallic seal ring with complex cross-section and submillimeter precision

The fabrication of complex thin-walled components with irregular cross-sectional geometries often necessitates multi-pass forming processes. The springback phenomena at the microscale level contribute significantly difficulty to the precise control of geometrical accuracy for such components. To achieve submillimeter precision control of micro features in metal seal rings, this research proposed a global springback compensation method to facilitate the attainment of the optimized surfaces of dies. Through the analysis of changes in cross-sectional shape, stress distribution and bending moment in the multiple stages, several partition points were set up to divide the cross-section into four zones. For a partitional control of the manufactured surface, the compensation magnitudes for each segment are determined by iteratively refining the compensation factors using the secant method. The iteration of compensation factors is based on the deviation of dimensions measured by finite element simulation, which greatly saves experimental costs. The experimental results indicate that the predictive dimensional alterations by the global compensation agree with the experimental ones exhibiting a maximum error of less than 3 %. Furthermore, the springback behavior during the unloading and trimming stages coupling caused a dimensional error of 14.9 % for the wave width and 8.3 % for the peak width. Following the application of coupled compensation through two iterations, a distinct decrease in the relative average errors of springback values for both part width and peak width, achieving reductions to 2.4 % and 0.6 %, respectively. Compared to the traditional single springback compensation technique, the global compensation strategy effectively mitigates the out-of-tolerance issues induced by the trimming process.

Study on seismic response of liquefiable soil-pile group considering pile cap and soil contact

In this paper, based on the centrifuge test of liquefied soil-pile foundation system, a numerical model of liquefied soil-pile foundation-structure system is modelled by using OpenSees platform. In the simulation model, the friction effect between liquefied ground and low pile cap is considered, and the method of establishing virtual nodes is used to deal with the non-linear contact between liquefiable soil and low pile cap. The rationality and effectiveness of the numerical simulation method adopted in this paper has been verified and evaluated by comparing with the results of centrifuge experiments. A typical liquefaction soil-pile integrated finite element model is modelled using validated numerical simulation methods. The law of seismic response of the pile foundation system with different embedding depths of pile cap, different contact modes between the pile cap and saturated sand, and the thickness of the overlying saturated loose sand layer are discussed. The results show that the pile cap and pile foundation in the high pile cap system show higher seismic response characteristics than the other three low pile cap system conditions; Under the condition of different contact modes between the pile cap and the surrounding saturated sand, the peak bending moment and residual displacement of the pile foundation calculated by the bond contact are larger than calculated by the friction contact, and the deformation of pile is more significant. By comparing the working conditions of different thicknesses of overlying saturated loose sand layer, it is found that the degree of liquefaction in shallow soils is less affected by thickness of the saturated loose sand. As the thickness of saturated loose sand layer increases, the peak bending moment and residual displacement at the top of the pile also gradually increase. The change of peak bending moment at the soil interface is more obvious.

Structural Fine-Tuning to Achieve Highly Fluorescent Organic and Water-Soluble Thiazolo[5,4-d]thiazole Chromophores.

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid-state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge-transfer (ICT) in a family of unsymmetrical donor-thiazolo[5,4-d]thiazole-acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution-state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor-π-acceptor systems.

DFT simulations of photovoltaic parameters of dye‐sensitized solar cells with new efficient sensitizer of indolo[3, 2‐b]carbazole complexes

AbstractDeveloping economical and high‐performing sensitizers is crucial in advancing dye‐sensitized solar cells (DSSCs) and optoelectronics. This research paper explores the potential of novel red light‐absorbing organic dyes based on Indolo[3,2‐b]carbazole (ICZ) as the donor applied in co‐sensitizer‐free DSSCs for breakthroughs in photovoltaic (PV) applications. DFT and TD‐DFT based computational methods were employed to calculate the conduction band levels, electron injection capabilities, and power conversion efficiency (PCE) of metal‐free organic dyes (ICZ1–ICZ9) having D‐A‐π‐A architecture. Comprehensive analyses included NBO, DOS, FMO, ICT, MEP, binding energy, and TDM analysis. Quantum chemical calculations of the structural, photochemical, and electrochemical properties, as well as the key parameters, reveals that all the designed dyes could be an excellent candidate for high‐efficiency DSSCs due the small energy gap (2.130–1.947 eV), longer wavelength absorption (759.47–520.63 nm), longer lifetimes (15.65–6.67 ns), a lower ΔGreg (0.29–0.14 eV), a significant dipole moment changes (31.489–16.195D), LHE (0.95‐0.46), the large qCT (0.962–0.689), small DCT (7.657, 4.897 Å), and VOC (1.13–0.86 eV). This quantum simulation showed that, when compared to reference D8, the photovoltaic dyes ICZ8, ICZ2, and ICZ7 are recognized as being eye‐catching. Furthermore, dye@(TiO2)9 cluster model results demonstrate promising prospects for enhancing the photovoltaic (PV) performance of ICZ1–ICZ9 dyes by electron injection and conduction band (CB) engineering. This study will help the experimentalists for developing ICZ‐based PVs as more efficient and sustainable energy solutions.

Determination of dynamic component reactions in support bearings of rotor saws for cutting hot rolled (message 2)

For modern rolling production, the issue of strength and reliability of rotary saw designs, which are designed for cutting hot rolled products, is relevant. One of the factors that reduces the reliability of a rotary saw is the insufficient durability of the bearings of the shaft of the high-speed disk, which perceives the cutting forces. Practice shows that the applied methods of calculating the strength of support bearings do not allow taking into account all possible factors that affect the reliability of bearings in the cutting process. First, as it turned out, during operation, the saw blade has a radial beat, possibly due to an error when cutting the teeth of the blade and the eccentric landing of the blade on the seat when replacing it. Also, due to the fact that the process of cutting with a rotary saw is very short-term, the cutting force is considered to be the impact force. The purpose of this work is to determine the durability of the bearings of the disc shaft of a rotary saw, considering such factors as the radial beating of the disc and the shock load during the cutting process. As you know, during long-term operation of the object, the place for landing the cutting disc on the faceplate wears out, sometimes there is an error in the hole when making a new disc. Therefore, there is an eccentricity of the center of gravity of the disc. The presence of this eccentricity is considered in the work when determining the required forces using D'Alembert's principle of conditional balancing of forces. Given that the duration of cutting is a short-term process (lasts 0.105 sec.), when determining the reactions in the supports of the disk shaft that occur under the action of cutting forces, it is possible to consider the cutting process as an impact phenomenon. Due to the fact that the process of cutting with a circular saw is very short-term, the cutting force is considered the impact force. The magnitudes of the reaction forces in the bearings are determined during cutting using the theorems of impact dynamics: the theorem of impulses and the change of kinetic moment. For the possibility of theoretical determination of the effect of disk beating on the reaction in the bearings of the bearing shaft, experimental studies of disk beating and determined cutting forces were carried out

A systematic approach to generate polymer library: A search for polymers with high dipole moment

Four machine learning (ML) models are trained using seven molecular descriptors for the prediction of dipole moment. Random forest model has stand out as best model with r-squared values of 0.82 and 0.67 for training and test set, respectively. 10 k polymers are generated using automated process and dipole moment of newly generated polymers is calculated using random forest model. A significant change in dipole moment on structural change is observed. Polymers are screened on the basis on their dipole moment values. Majority of chosen polymers are easy to synthesize. The chosen polymers have revealed resemblances among their structures.

Study on fault-slip process and seismic mechanism under dynamic loading of hard roof fracture disturbance

The dynamic stress disturbance induced by mining is a significant factor triggering fault-slip. To better understand the impact of mining-induced hard roof fracture on fault-slip, combined with the geological conditions of a longwall face in contact with the fault, a dynamic and static numerical model was established using FLAC3D. The influence of dynamic loading from hard roof fracture on fault stability was investigated. The characteristics of changes in fault shear stress, shear displacement, slip area, and seismic moment under dynamic loading were analyzed. Simultaneously, numerical results were compared and analyzed against microseismic (MS) monitoring records in the mining, validating the accuracy of the numerical results. The results indicate that dynamic loading is a critical factor in inducing fault-slip. As a geological weak surface, the fault impedes the transmission of shock waves and causes their attenuation. Under dynamic loading, when the fluctuation of fault shear stress and friction coefficient exceeds the threshold, the fault-slip. During the fault-slip process, accompanied by a sharp increase in shear displacement, the seismic moment increases. Finally, the influence of changes in seismic parameters (e.g. longwall–fault distance, seismic energy, and seismic location) on the fault-slip mechanism was analyzed. This study contributes to a better understanding of the disturbance mechanism of mining-induced dynamic loading on fault-slip and provides a theoretical basis for fault-slip rock bursts.

Computational study of Carreau nanofluid across a stretching cylinder by homogeneous-heterogeneous responses: A frame work of modified Buongiorno's nanofluid model

This paper studies the Carreau nanofluid employed by modified Buongiorno's model to theoretically analyze a homogeneous-heterogeneous process-influenced numerical solution of a Carreau nanofluid flowing through a stretched cylinder. In steady of Carreau nanofluid model proposed by Buongiorno's flow across a linearly extending cylinder influenced by homogeneous/heterogeneous responses are examined and express the changes of moment, energy, and concentration in both graphical and numerical. The following impact factors are consequences of the result, the stretching limiting factor, the curvature limiting factor and other limiting factors. The effects of both convection and heat generation are seen in flow field analysis. In comparison to ambient fluid, the stipulated exterior temperature and concentration are hypothetically increased. For the regulating equations of velocity, energy, and concentration profiles are permuting from a set of partial differential equations stand to ordinary differential equations manipulating an equivalent conversion. The resulting sequence of equations was solved at the boundary value problem in the fifth-order method. The velocity, temperature, concentration, skin friction coefficient, local Nusselt number, and local Sherwood number fields are studied, and then the outputs are illustrated in graphs and tables.

Squatting biomechanics following physiotherapist-led care or hip arthroscopy for femoroacetabular impingement syndrome: a secondary analysis from a randomised controlled trial.

Femoroacetabular impingement syndrome (FAIS) can cause hip pain and chondrolabral damage that may be managed non-operatively or surgically. Squatting motions require large degrees of hip flexion and underpin many daily and sporting tasks but may cause hip impingement and provoke pain. Differential effects of physiotherapist-led care and arthroscopy on biomechanics during squatting have not been examined previously. This study explored differences in 12-month changes in kinematics and moments during squatting between patients with FAIS treated with a physiotherapist-led intervention (Personalised Hip Therapy, PHT) and arthroscopy. A subsample (n = 36) of participants with FAIS enrolled in a multi-centre, pragmatic, two-arm superiority randomised controlled trial underwent three-dimensional motion analysis during squatting at baseline and 12-months following random allocation to PHT (n = 17) or arthroscopy (n = 19). Changes in time-series and peak trunk, pelvis, and hip biomechanics, and squat velocity and maximum depth were explored between treatment groups. No significant differences in 12-month changes were detected between PHT and arthroscopy groups. Compared to baseline, the arthroscopy group squatted slower at follow-up (descent: mean difference -0.04 m∙s-1 (95%CI [-0.09 to 0.01]); ascent: -0.05 m∙s-1 [-0.11 to 0.01]%). No differences in squat depth were detected between or within groups. After adjusting for speed, trunk flexion was greater in both treatment groups at follow-up compared to baseline (descent: PHT 7.50° [-14.02 to -0.98]%; ascent: PHT 7.29° [-14.69 to 0.12]%, arthroscopy 16.32° [-32.95 to 0.30]%). Compared to baseline, both treatment groups exhibited reduced anterior pelvic tilt (descent: PHT 8.30° [0.21-16.39]%, arthroscopy -10.95° [-5.54 to 16.34]%; ascent: PHT -7.98° [-0.38 to 16.35]%, arthroscopy -10.82° [3.82-17.81]%), hip flexion (descent: PHT -11.86° [1.67-22.05]%, arthroscopy -16.78° [8.55-22.01]%; ascent: PHT -12.86° [1.30-24.42]%, arthroscopy -16.53° [6.72-26.35]%), and knee flexion (descent: PHT -6.62° [0.56- 12.67]%; ascent: PHT -8.24° [2.38-14.10]%, arthroscopy -8.00° [-0.02 to 16.03]%). Compared to baseline, the PHT group exhibited more plantarflexion during squat ascent at follow-up (-3.58° [-0.12 to 7.29]%). Compared to baseline, both groups exhibited lower external hip flexion moments at follow-up (descent: PHT -0.55 N∙m/BW∙HT[%] [0.05-1.05]%, arthroscopy -0.84 N∙m/BW∙HT[%] [0.06-1.61]%; ascent: PHT -0.464 N∙m/BW∙HT[%] [-0.002 to 0.93]%, arthroscopy -0.90 N∙m/BW∙HT[%] [0.13-1.67]%). Exploratory data suggest at 12-months follow-up, neither PHT or hip arthroscopy are superior at eliciting changes in trunk, pelvis, or lower-limb biomechanics. Both treatments may induce changes in kinematics and moments, however the implications of these changes are unknown. Australia New Zealand Clinical Trials Registry reference: ACTRN12615001177549. Trial registered 2/11/2015.

Effect of ball positions on trunk, hip, knee, and ankle joint kinematics and kinetics during a spike jump in volleyball

BackgroundAnterior cruciate ligament injuries are serious conditions encountered in volleyball players and occur frequently during spike jump landings. During spike jumps, the lower limb kinematics and kinetics during landing may be altered in relation to the ball position. Research questionDoes the ball position have an effect on lower-limb kinematics and kinetics during spike jumps? MethodsWe measured the lower limb kinematics and kinetics of 20 healthy female college volleyball athletes during a spike jump using a three-dimensional motion analysis system. The ball positions were set to normal, dominant, and non-dominant positions. A repeated analysis of variance was used to compare the lower limb kinematics and kinetics at the initial contact and the maximum knee flexion during jump landing. Additionally, statistical parametric mapping analysis was used to analyze changes over time during the spike jumps. ResultsAt the initial contact of the spike jump landing, the knee valgus angle, trunk lateral bending angle, and maximum knee valgus moment when the ball was set at the non-dominant position increased compared to those at the dominant position. Statistical parametric mapping analysis showed no significant change in knee valgus angle and moment of jump landing. ConclusionKnee valgus angle, trunk lateral bending angle, and maximum knee valgus moment increased with the non-dominant position; furthermore, the risk of ACL injury may also be increased. SignificanceThe posture at ball impact may influence the landing kinematics and kinetics. Therefore, it is necessary to pay close attention to movements during and prior to landing.

Local buckling of the bottom flange in steel-concrete composite beams with trapezoidal corrugated webs subjected to end restraint at high temperatures

Steel-concrete composite beams with trapezoidal corrugated webs (SCBCW) are prone to rapid failure at high temperatures due to local instability of the bottom flange. The failure mechanism of SCBCW, which is an integral part of the holistic structure and subject to axial and rotational restraints from adjacent members at elevated temperatures, differs from conventionally simply supported steel-concrete composite beams with straight webs. To investigate the evolution of local buckling in the compressed flange of SCBCW under high temperature conditions, a composite beam model with frame restraints was developed using ABAQUS finite element software. In this model, the composite beam is connected to restraint frame columns through high-strength bolts. The changes in axial stress, bending moment, and deflection of the compressed flange of SCBCW were analyzed as temperature increased. Results indicate that at elevated temperatures, additional bending moments occur in the flange plane due to axial restraints, section temperature gradients, section negative bending moments and accordion effect caused by corrugated web on compressed bottom flange of SCBCW. This leads to a gradual increase in axial compressive stress before local buckling occurs followed by a decrease due to internal force redistribution upon onset of buckling. Studies show that initial buckling of bottom flange occurs on one side of flat section of web where axial compressive stress is relatively high while restraint effect on web is low; Subsequent local buckling of the beam then appears on opposite side adjacent flat section of web after initial buckle occure on one side. After local buckling appears on both sides of web tension bands appear on both sides where bottom flange experiences localized bucking. The setting of longitudinal stiffeners (LS) can effectively improve the local stability of the bottom flange of the composite beam, while the setting of transverse stiffeners (TS) has no significant impact.

Dynamic Dipole Moment of Luminescent Liquid Crystals Enabled Highly Efficient Active Waveguide Materials Design and Synthesis

AbstractOrganic optical waveguide materials have attracted considerable attention for their promising applications in photonic and optoelectronic devices. However, for most materials, excellent light‐loss properties at high temperature cannot be obtained due to many factors. Consequently, realizing efficient optical waveguide materials that perform well at elevated temperatures remains a significant challenge. In this study, relying on the luminescent properties and self‐assembly properties of luminescent liquid crystals (LLCs), successfully fabricated materials are present for highly efficient active optical waveguides. A systematically synthesized set of LLCs with different structures is named according to the substituent type and the position of the cyano group, namely α‐DECN, α‐DEEOCN, β‐DECN, and β‐DEEOCN. Notably, α‐DECN and β‐DECN reveal hexagonal columnar phase, while α‐DEEOCN and β‐DEEOCN exhibit smectic phase. Optical waveguide experiments have revealed that the obtained LLCs showed highly efficient optical waveguide behavior, where the lowest light loss reached 0.15 dB mm−1 at room temperature. Remarkably, these LLCs show even lower light loss at high temperatures, with the light loss reaching 0.11 dB mm−1 as the lowest point. Further experimental results indicate that this phenomenon is attributed to the change in the dipole moment of these molecules. This research forms a significant groundwork for advanced exploration in optical waveguide material.

Changes in Lower-Extremity Gait Biomechanics Following High-Cadence Cycling.

We sought to investigate the lower-extremity biomechanics underlying increased gait velocity following high-cadence cycling. Ground reaction forces (GRF) and lower-extremity kinematics and kinetics were recorded as 15 healthy adults walked at a self-selected pace prior to and immediately following a 15 min bout of cycling at a cadence of 75 rotations per minute. Propulsive GRF and stance-phase peak dorsiflexion and knee extension angles increased, while peak plantarflexion and hip extension angles decreased. Swing-phase peak dorsiflexion, plantarflexion, knee flexion, and hip flexion angles increased, while peak knee extension angle decreased. Peak dorsiflexion, knee extension, and hip extension angular velocity also increased during swing. No changes in peak joint moments were observed; however, peak positive ankle, knee, and hip joint power generation increased following cycling. Completing high-cadence cycling improves gait velocity by increasing propulsive GRF; increasing joint angular velocity during the swing phase of gait for the ankle, knee, and hip; and increasing positive power production by the ankle, knee, and hip during the stance phase. Increased gait velocity post cycling exercise did not increase lower-extremity joint moments. Cycling may be a viable exercise-based modality for increasing gait velocity, especially in populations where gait ability or joint loading is of particular concern.

Spinal joint moment prediction following simulated breast surgery using a female whole-body musculoskeletal model

This study aimed to use a musculoskeletal model to predict changes in spinal moments following simulated breast surgery. A female full body musculoskeletal model with a fully articulated thoracolumbar spine and independent moveable breast segments was customised for this study. Key findings suggest that the simulated removal of breast tissue (750 g to 1501 g) can reduce the magnitude of lumbar spine extensor moments by >0.05 Nm/kg during walking and jogging. A customised female whole-body musculoskeletal model is capable of providing a first approximation of changes in spinal loading following simulated breast surgery.

Scalable Analysis of Dipole Moment Fluctuations for Characterizing Intermolecular Interactions and Structural Stability.

Accurately predicting protein-ligand interactions is essential in computational molecular biochemistry and in silico drug development. Monitoring changes in molecular dipole moments through molecular dynamics simulations provides valuable insights into dipole-dipole interactions, which are critical for understanding protein structure stability and predicting protein-ligand binding affinity. In this study, we propose a novel method to monitor changes in the interangle between dipole vectors of residue molecules within proteins and ligand molecules, aiming to evaluate the strength and consistency of interactions within the complex. Additionally, we extend the concept of positional root-mean-square fluctuation (RMSF), commonly used for protein structure stability analysis, to dipole moments, thus defining dipole moment RMSF. This enables us to analyze the stability of dipole moments for each residue within the protein and compare them across residues and between binding and non-binding complexes. Using the CRBP1-retinoic acid complex as our model system, we observed a significant difference in the interangle change of dipole moments for the key residue at the residue-level between the non-binding and binding complexes. Furthermore, we found that the dipole moment RMSF value of the non-binding complex was substantially larger than that of the binding complex, indicating greater dipole moment instability in the non-binding complex. Leveraging the concept of scalability inherent in the calculation of dipole moment vectors, we systematically expanded the residues within the protein's primary secondary structure. Our dipole moment analysis approach can provide valuable predictive insights into complex candidates, especially in situations where experimental comparisons are challenging.

Impact of plantar flexion resistive moment of dynamic ankle foot orthosis on measures of center of pressure and clinical gait outcomes in individuals with post-stroke hemiparesis

BackgroundAn ankle-foot orthosis (AFO) with plantar flexion resistance (PFR) can improve the first rocker function during gait, but the incremental changes in the resistive moment on balance and gait have not been well identified. ObjectivesTo investigate the effect of changing the PFR moment of dynamic AFO (DAFO) on measures of the center of pressure (COP) and clinical gait outcomes in individuals with post-stroke hemiparesis. MethodIn this randomized repeated measure study of 36 stroke individuals, the customized DAFO using foot drop ankle units set in three PFR situations (low, medium, and high) was evaluated. The balance parameters for COP measures were investigated by HUMAC® Balance & Tilt System. Gait parameters and ankle kinematics were recorded using the 3D motion analysis through force platform and optoelectronic system. The comparison was made using a parametric ANOVA test and the P value was set at 0.05 for statistical significance. ResultsSignificant differences were observed for COP average velocity (1.30 ± 0.64, 1.10 ± 0.05, and 1.37 ± 0.43), COP path length (43.3 ± 4.6, 33.4 ± 4.3, and 36.3 ± 5.4), walking velocity (11.0 ± 3.1, 13.2 ± 4.4, and 9.9 ± 3.5), and cadence (31.5 ± 2.0, 33.0 ± 3.1, and 29.0 ± 1.6) respectively for low, medium and high PFR settings (P < 0.05). Except for the COP path length and cadence, posthoc multiple comparisons revealed significant differences between low and medium (P < 0.05) and medium and high (P < 0.05) PFR grades. PFR with medium resistance demonstrated near-normal maximal peak ankle dorsiflexion (mean deviation of 8 degrees, P < 0.05). ConclusionMedium PFR grade should be encouraged since it can enhance balance parameters like path length and average velocity of COP, increase cadence and average velocity during gait, and improve maximal peak ankle dorsiflexion.

Defect-Induced Dipole Moment Change of Passivators for Improving the Performance of Perovskite Photovoltaics

Defect-Induced Dipole Moment Change of Passivators for Improving the Performance of Perovskite Photovoltaics

Excellent catalytic activity for NO decomposition on Rhn supported on grain-boundary terminations of the MgO (0 0 1) surface

In the present study, we first propose the grain-boundary termination of the MgO (001) surface (referred as GB@MgO(001)) as the substrate to support a series of Rhn clusters to trap and dissociate NO. Using van der Waals density functional theory calculations, we have studied the interaction between the Rhn (n = 1 ∼ 8) cluster and the MgOΣ5(210)GB@MgO(001) and the properties of the adsorption and dissociation of NO on Rhn/GB@MgO(001) systems. The Rhn clusters can tightly bond to the GB@MgO(001), with interfacial interactions comparable to those at the Rhn/MgO-nanotube interface. Stable quasi-two-dimensional Rhn clusters provide more active sites to NO. Moreover, NO dissociation is activated, with all the complete reaction paths occur below the reference state, indicating the possibility of the NO decomposition. An extremely small energy barrier of 0.037 eV was obtained for NO dissociating on the square-Rh4/GB@MgO(001) system. Molecular dynamic (MD) calculations reveal that NO can be completely decomposed at 527 K without obvious structure distortions of the complex. The adsorption of NO yields a change in the total magnetic moment of the Rhn/GB@MgO(001) system, but it has a minimal impact on the adsorption energy of NO. Our results also show that the optimal Rhn clusters that are good at trapping and dissociating NO are not the most stable structures, but rather clusters of relatively low dimension that are bound to the substrate with a moderate strength. As a result, the modification and tuning of the substrate structure can effectively enrich the structure of Rh cluster catalyst and improve its physical properties so that it can potentially play a greater role in other redox reactions, which motivates us to continue designing various types of GB@MgO(001) for different purposes.

Synthesis of 1,3-Dibromopyrene as Precursor of 1-, 3-, 6-, and 8-Substituted Long-Axially Symmetric Pyrene Derivatives.

Pyrene derivatives bearing substituents at positions 1, 3, 6, and 8 find numerous applications, as exemplified by their use in lasers, sensors, and bioimaging probes. However, these derivatives typically have point-symmetric or short-axially symmetric structures, whereas long-axially symmetric derivatives remain underexplored because of the difficulty in obtaining their precursor, 1,3-dibromopyrene. To address this problem, we herein synthesized 1,3-dibromopyrene from 1-methoxypyrene in an overall yield (71 % over four steps) considerably exceeding those of existing methods. 1,3-Dibromopyrene was converted into 13OPA, a long-axially symmetric pyrene dye with electron-donor (alkoxy) groups at positions 1 and 3 and electron-acceptor (formyl) groups at positions 6 and 8. 13OPA exhibited photophysical properties distinct from those of its point-symmetric and short-axially symmetric isomers, featuring a broad and strongly redshifted absorption, strong fluorescence with reduced sensitivity to protic solvents, and small dipole moment change upon photoexcitation. The derivatization of 13OPA into a Schiff base and its functionalization via Lewis acid-base pairing were also demonstrated. Thus, our work expands the design scope of pyrene-based molecules, particularly those used as emitters.