Half Cycle Research Articles

Numerical study on the turn maneuvering of a biomimetic robotic fish driven by pectoral fins in labriform mode under self-propulsion

The median and/or paired fin (MPF) swimming mode of fish has extremely strong maneuverability, which is urgently needed for unmanned underwater vehicles. Therefore, determining the mechanism of greater maneuverability of fish in the MPF swimming mode is particularly important. To fill the research gap in the entire turn maneuvering process in MPF swimming mode under self-propulsion, a numerical solution method for three degree-of-freedoms self-propelled swimming of biomimetic robotic fish (BRF) coupled with fluid dynamics and body dynamics were established. Our results revealed that the turning radius of the BRF increases with the increase in the pectoral fin rotation amplitude in both drag-based and lift-based modes. Interestingly, owing to the special streamlined shape of the fish body, it can passively generate thrust during turn maneuvering. According to vortex dynamics, the trailing-edge vortex (TEV) and tip vortex (TV) generated in the power stroke form a vortex ring together with the TEV generated in the recovery stroke during one cycle in drag-based mode. The TEV and TV generated in every half cycle in lift-based mode form a vortex ring, resulting in two vortex rings in one cycle. The vortex ring generation mechanism is the mechanism by which the pectoral fins cannot generate continuous thrust in drag-based mode but can generate continuous thrust in the lift-based mode. The results reveal the BRF labriform mode turning characteristics as well as the relation mechanism between vortex dynamics and thrust, which lays a theoretical foundation for highly maneuverable BRF development.

A Single-Input Multi-Output Resonant Regulating Rectifier Generating Three Outputs in a Half Cycle for Wirelessly Powered Biomedical Devices

A Single-Input Multi-Output Resonant Regulating Rectifier Generating Three Outputs in a Half Cycle for Wirelessly Powered Biomedical Devices

Experimental investigation of scour beneath a pipeline due to tidal currents in a Strait

This study presents an investigation of the impact of tidal currents on scouring beneath pipelines. To elucidate the role of parameters such as current velocity, time period of each cycle, depth of flow, and number of tidal cycles required to attain equilibrium, 38 tests were conducted in a bidirectional flume for a pipeline. The geometry of pipeline and the flow characteristics of the Persian Gulf were scaled down to a ratio of 1:30 based on the Froud law and used for this study. The tests were carried out in clear water conditions. The experimental findings reveal that a significant portion of the scour depth occurs during the mid-range of each half cycle. This is the case regardless of ebb or flood conditions, and when the current velocity is at its maximum value. Also, the scour hole resulting from bidirectional flow exhibits a symmetrical shape with two dunes on either side. Furthermore, the relative scour depths in daily and semi-daily tidal tests are greater by factors of 1.40 and 1.1, respectively, compared to unidirectional tests when the root mean square values from steady current scenarios are considered. Finally, a series of formulae have been developed based on the experimental results.

Plasma and Flow Simulation of the Ion Wind in a Surface Barrier Discharge Used for Gas Conversion Benchmarked by Schlieren Imaging

Surface dielectric barrier discharges (sDBD) are efficient and scalable plasma sources for plasma-based gas conversion. One prominent feature of an sDBD is the generation of an ion wind, which exerts a force on the neutrals, thus leading to an efficient mixing of plasma and a passing gas stream. This becomes apparent by the creation of upstream and downstream vortices in the vicinity of the plasma. In this study, these vortices are generated by high voltage burst pulses consisting of two half cycles of an almost sinusoidal voltage shape. The vortices are monitored by Schlieren imaging diagnostic to benchmark and connect two simulations of the sDBD: a plasma model simulating a streamer for 25 ns starting from the electrode and propagating along a dielectric surface followed by a decay. The streamer is the source of electrical charges accelerated as ion wind by the applied electric field from the sDBD power supply. A second flow simulation models this ion wind as a time-averaged thrust acting on the passing gas stream. The conversion of the time-resolved forces from the nanosecond plasma simulation into the steady state thrust in the flow simulation indicates that the force from the plasma lasts much longer than the actual streamer propagation phase. This is explained by the fact that the charges in the streamer channel remain present for almost 100 ns, and the voltage from the power supply lasts for a few microseconds being applied to the electrode so that ions in the streamer channel are still accelerated even after a streamer stops to propagate after a few ns. The thrust generated during the streamer phase, including the relaxation phase, agrees well with predictions from flow simulation. Additionally, properly converting the time-resolved forces from the plasma simulation into a time-averaged thrust for the flow simulation yields exactly the synthetic Schlieren images as measured in the experiments.

The effects of flexibility on the formation and evolution of wake vortices behind a heaving plate

The kinematics of vortical structures behind heaving plates with different flexibility has been investigated using particle image velocimetry. The rectangular plates with different thicknesses undergo a trapezoidal velocity profile (acceleration–steady–deceleration). The Reynolds number Rec based on the chord length and the steady velocity is 5330. The formation and evolution processes of the wake vortices are investigated, with the focus on the comparison between the rigid wing and flexible wings. Wake vortices for the rigid wing initiated near the plate edges, while for flexible wings vortices initiated near the quarter-chord from the edges and slid toward the edges as the plates deform and move forward. During the first half cycle (moving forward), both the vortex trajectories and circulation indicate a global two-stage growth of the starting vortices for all the plates, corresponding to the acceleration and steady motion stages, respectively. The flexible plates have larger wake width and attain higher peak circulation initially; however, the circulation for the rigid plate achieves higher peak value during the steady stage. During the second half cycle (moving backward), the vortex trajectories present a two-stage process; however, the circulation is a single growth and decay process. Besides, detailed study reveals that during the acceleration, the circulation grows rapidly and there is a small decay at the end of the acceleration, thus forming the local peak for the first stage. The vortex trajectories for the flexible plates show greater range transversely, as well as the motion reversal in the streamwise direction.

On Rapid Vibration Suppression by Nonlinear Energy Sink during First Half Cycle of Oscillation

On Rapid Vibration Suppression by Nonlinear Energy Sink during First Half Cycle of Oscillation

Dynamical phase transitions in the XY model: A Monte Carlo and mean-field-theory study.

We investigate the dynamical phases and phase transitions arising in a classical two-dimensional anisotropic XY model under the influence of a periodically driven temporal external magnetic field in the form of a symmetric square wave. We use a combination of finite temperature classical Monte Carlo simulation, implemented within a CPU+GPU paradigm, utilizing local dynamics provided by the Glauber algorithm and a phenomenological equation-of-motion approach based on relaxational dynamics governed by the time-dependent free energy within a mean-field approximation to study the model. We investigate several parameter regimes of the variables (magnetic field, anisotropy, and the external drive frequency) that influence the anisotropic XY system. We identify four possible dynamical phases: Ising-SBO, Ising-SRO, XY-SBO, and XY-SRO. Both techniques indicate that only three of them (Ising-SRO, Ising-SBO, and XY-SRO) are stable dynamical phases in the thermodynamic sense. Within the Monte Carlo framework, a finite-size scaling analysis, shows that XY-SBO does not survive in the thermodynamic limit giving way to either an Ising-SBO or a XY-SRO regime. The finite-size scaling analysis further shows that the transitions between the three remaining dynamical phases either belong to the two-dimensional Ising universality class or are first-order in nature. Within the mean-field calculations yield three stable dynamical phases, i.e., Ising-SRO, Ising-SBO and XY-SRO, where the final steady state is independent of the initial condition chosen to evolve the equationsof motion, as well as a region of bistability where the system flows to either Ising-SBO or XY-SRO (Ising-SRO) depending on the initial condition. Unlike the stable dynamical phases, the XY-SBO represents a transient feature that is eventually lost to either Ising-SBO or XY-SRO. Our mean-field analysis highlights the importance of the competition between switching of the stationary point(s) of the free energy after each half cycle of the external field and the two-dimensional nature of the phase space for the equationsof motion.

Enhancing selectivity through forced dynamic operation with intraparticle diffusion limitations: Ethane oxidative dehydrogenation

During steady state operation (SSO) of industrial fixed-bed reactors, diffusion limitations are often present. Well-known impacts include the reduced rate of a positive order reaction and reduced selectivity of the desired intermediate product in a sequential reaction system. This work presents an approach for circumventing diffusion limitations through forced dynamic operation (FDO) of metal oxide catalyzed partial oxidation reactions. Through coupled experiments and modeling, we examine the use of FDO to mitigate selectivity losses of the intermediate product in a parallel-consecutive reaction. With the oxidative dehydrogenation (ODH) of ethane (C2H6) to ethylene (C2H4) over an Al2O3 supported VOx catalyst as the model reaction system, FDO is shown to curtail undesired C2H4 overoxidation to COx that predominates in steady state diffusion-limited pellets, resulting in C2H4 selectivities that are 15 % (absolute) higher compared to SSO in 2.6 mm catalyst pellets. A kinetic model reveals that FDO beneficially alters the distribution of chemisorbed (O*) and lattice (OL) oxygen, which respectively primarily participate in reactions consuming C2H4 and C2H6. FDO is shown to lead to less detrimental impact of diffusion on the ethylene selectivity and yield compared to SSO. During FDO, generated C2H4 reacts with unselective O*, leaving behind selective OL. The reduced bulk phase O2 in the reductive half cycle leads to accumulation of OL, suppressing C2H4 overoxidation. This effect is amplified via C2H4 trapping in the catalyst pellet. Thus, larger catalyst pellets exhibit selectivities that more rapidly increase with reduction time, inducing higher FDO cycle averages compared to SSO. The findings raise the prospect of applying FDO through feed switching or chemical looping as a way to increase intermediate yield in the class of partial oxidation reactions.

Excitation and ionization of a diagnosis gas in front of the flexible μ tube plasma and in a diagnosis tube

The noble gases Helium, Argon, Krypton and even Xeon have been applied as discharge gases for the flexible μ tube plasma (FμTP) with comparable ionization efficiencies. It was assumed that a temporally and spatially limited potential plays a major role in the generation of reactant ions responsible for protonation in the surrounding air. However, the excited and ionized species of ambient air cannot be detected directly by emission spectroscopy because there is no known emission wavelength within the detectable range. In this work, a diagnosis gas was introduced as a substitute for the surrounding air to understand the excitation and ionization outside the discharge capillary. It was found that with Ne, Ar, Kr, Xe as plasma gases the diagnosis gas He can be excited during the positive half cycle. The emission of He 706 nm and N2+ 391 nm propagate with and against diagnosis gas flow directions in case of He and Ne driven plasmas. In case of Ar, Kr, and Xe driven plasmas, the emission of both species mainly develops against the diagnosis gas and the shapes of He 706 nm are wide. Further on, the diagnosis gas He is also excited even though there is a glass wall between the plasma gas flow and diagnosis gas flow. These findings demonstrate that the transient potential is responsible for the excitation of the diagnosis gas, not penning ionization or charge transfer between discharge plasma and diagnosis gas.

Ligand extension of aluminum fumarate metal-organic framework in transferring higher water for adsorption desalination

This article presents the synthesis and characterization of a new microporous metal organic framework (MOF) for adsorption desalination for the first time. The new MOF, designated as “Al-t,t-Ma”, is an analogue of aluminum fumarate (Al-Fum) and is fabricated via ligand extension method. Firstly, the MOF is synthesized, and then characterized by XRD, FTIR spectroscopy, TEM, SEM, TGA and N2 adsorption techniques. Secondly, the water adsorption experiments on the pristine Al-Fum and Al-t,t-Ma are performed for a wide temperature (30 °C ≤ T ≤ 80°C) and pressure (0 < P/Ps ≤ 0.9) ranges. The water adsorption isotherms, kinetics, hydro-thermal stabilities as well as the isosteric heat of adsorption (Qst) are evaluated. Thirdly, based on the experimentally confirmed isotherms, kinetics and isosteric heats data, the adsorption assisted desalination (AD) system is modelled and simulated. Finally, the performances of AD system employing Al-Fum and Al-t,t-Ma MOFs are calculated in terms of the performance ratio (PR) and specific daily water production (SDWP) under various half cycle times (100 s ≤ tcycle ≤ 1000 s) and regeneration temperatures (55°C ≤ Tregen ≤ 80°C). As compared with the pristine Al-Fum, the pore volume of Al-t,t-Ma MOF is found 115 % higher. The proposed Al-t,t-Ma MOF possesses higher water transfer (+57.5 % more) with promising hydro-thermal stability. Employing Al-t,t-Ma MOF as porous adsorbent, the SDWP is achieved 28 m3 per tonne of MOFs per day at the regeneration temperature of 55°C. These results confirm that Al-t,t-Ma MOF is a competent candidate for adsorption desalination.

Experimental study on coal oxidation and temperature rise under different air leakage modes due to atmospheric pressure changes

ABSTRACT The spontaneous combustion of residual coal in enclosed goafs may induce coupled thermodynamic disasters with severe consequences. To study the dynamic characteristics of coal oxidation and temperature increase in an enclosed goaf under varying atmospheric pressure conditions, the air leakage model was analyzed through theoretical derivation. The resistance, temperature, and CO concentration during coal oxidation under different air leakage modes were further studied using a self-built experimental system. The results indicated three air leakage modes of coal oxidation in an enclosed goaf: constant, intermittent, and reciprocating. The resistance of the three modes increased from 5 Pa to 7 Pa with time. Compared to constant air leakage, the time of resistance change was advanced by 1428 s and 1897 s under intermittent and reciprocating air leakage, respectively. Additionally, both intermittent and reciprocating air leakage promote coal oxidation and produce higher CO levels compared to constant air leakage. However, intermittent air leakage is more likely to produce higher temperature points, while reciprocating air leakage is more likely to cause large areas of coal oxidation. The order of the promoting effect of the intermittent and reciprocating half cycle on coal oxidation is 60 s, 300 s, 600 s, and 1200 s. These results are significant for understanding coal spontaneous combustion and efficiently managing enclosed goafs.

Comparison of different elastic strain definitions for largely deformed SEI of chemo-mechanically coupled silicon battery particles

Amorphous silicon is a highly promising anode material for next-generation lithium-ion batteries. Large volume changes of the silicon particle have a critical effect on the surrounding solid-electrolyte interphase (SEI) due to repeated fracture and healing during cycling. Based on a thermodynamically consistent chemo-elasto-plastic continuum model we investigate the stress development inside the particle and the SEI. Using the example of a particle with SEI, we apply a higher order finite element method together with a variable-step, variable-order time integration scheme on a nonlinear system of partial differential equations. Starting from a single silicon particle setting, the surrounding SEI is added in a first step with the typically used elastic Green–St-Venant (GSV) strain definition for a purely elastic deformation. For this type of deformation, the definition of the elastic strain is crucial to get reasonable simulation results. In case of the elastic GSV strain, the simulation aborts. We overcome the simulation failure by using the definition of the logarithmic Hencky strain. However, the particle remains unaffected by the elastic strain definitions in the particle domain. Compared to GSV, plastic deformation with the Hencky strain is straightforward to take into account. For the plastic SEI deformation, a rate-independent and a rate-dependent plastic deformation are newly introduced and numerically compared for three half cycles for the example of a radial symmetric particle.

A planar plume array emanating from an atmospheric pressure argon plasma jet employing floating electrodes

Large-scale plasma plumes downstream of plasma jets are in urgent need from a practical viewpoint. In this Letter, an argon plasma jet with floating electrodes is proposed to produce a large-scale planar plume array. Results indicate that with increasing peak voltage (Vp), the planar plume array elongates gradually and scales up in the lateral direction to an optimal value of 90.0 mm. There is only one discharge pulse per voltage half cycle, whose intensity and duration increase with increasing Vp. Moreover, there is a time lag between the initiations of individual plumes. Fast photography reveals that the planar plume array originates from the repeated process of some micro-discharge filaments stretching along the argon stream. By optical emission spectroscopy, the spatial distribution of plasma parameters is obtained, such as electron density, electron temperature, and gas temperature. At last, the planar plume array is employed to test the surface modification of polyethylene terephthalate, for which a uniform modification has been realized with a scan velocity of 1.0 cm/min. These results are of great significance for the development of large-scale atmospheric pressure plasma sources.

Ultra-Nonlinear Subcycle Photoemission of Few-Electron States from Sharp Gold Nanotapers.

The generation of ultrashort electron wavepackets is crucial for the development of ultrafast electron microscopes. Recent studies on Coulomb-correlated few-electron number states, photoemitted from sharp metallic tapers, have shown emission nonlinearities in the multiphoton photoemission regime which scale with the electron number. Here, we study few-electron photoemission from gold nanotapers triggered by few-cycle near-infrared pulses, demonstrating extreme 20th-order nonlinearities for electron triplets. We report interferometric autocorrelation traces of the electron yield that are quenched to a single emission peak with subfemtosecond duration due to these high nonlinearities. The modulation of the emission yield by the carrier-envelope phase suggests that electron emission predominantly occurs during a single half cycle of the driving laser field. When applying a bias voltage to the tip, recollisions in the electron trajectories are suppressed and coherent subcycle electron beams are generated with promising prospects for ultrafast electron microscopy with subcycle time resolution.

The Rôle of Iron in Zeolite Beta for deNOx Catalysis

Selective catalytic reduction with ammonia (NH3-SCR) is a widely used deNOx process, employing zeolitic catalysts. Here, we examine framework substituted and extra-framework exchanged transition metal zeolite catalysts, in the extensively studied Fe – zeolite Beta focusing on the influence of the transition metal cation on the NH3-SCR reaction, and aiming to unravel the underlying mechanisms and their impact on catalytic performance. We use hybrid multiscale density functional theory (DFT)/molecular mechanics to investigate the NH3-SCR at various Fe-BEA active sites including systems with both framework and extra-framework Fe cations. The catalytically active sites under investigation include Fe-FeF-BEA, Fe-AlF-BEA, and Cu-FeF-BEA, (where the subscript F indicates framework species) on which the formation and consumption of key intermediates of both oxidation and reduction half cycles species are analysed. We show the distinctive ability of framework Fe sites to promote the formation of key nitrate and nitrosamine intermediates. Furthermore, we find a strong binding affinity of NH3 with framework Fe systems including Cu(II)-FeF-BEA, Fe(III)-FeF-BEA, and H-FeF-BEA compared to framework Al systems (Fe(III)-AlF-BEA). We explore the reduction potential of the framework Fe3+/Fe2+ in BEA zeolite and establish its feasibility in the presence of a Brønsted acid site. Our calculations clearly predict the bimetallic Cu-FeF system to be the best catalyst which supports a recent experimental report by Yue et al. (Chem. Eng. J. 2020, 398, 125515) for a related FeCu-SSZ-13 (CHA) zeolite. We provide a new understanding of the reactivity of Fe-BEA zeolites, suggesting the advantages of framework Fe over Al sites in NH3-SCR reactions, and establishing a foundation for interpretation of the rôle of framework cations in metal-exchanged zeolites.

(Invited) Tunable Infrared Optoelectronics Achieved by the Reversible Intercalation of Ionic Liquid Anions in Multilayer Graphene in the Mid-Infrared Wavelength Range

We report the use of multilayer graphene (MLG) grown by chemical vapor deposition (CVD) approximately 75 layers (26 nm) thick configured in a simple electrochemical device. Applying a voltage of 3–4 V drives the intercalation of anion [TFSI-] (ion liquid diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide [DEME][TFSI]]) resulting in the reversible modulation of the properties of this optically dense material. Upon intercalation, we observe an abrupt shift of 35 cm−1 in the G band Raman mode, an abrupt increase in FTIR reflectance over the wavelength range from 1.67 to 5 μm (2000–6000 cm−1 ), and an abrupt increase in luminescent background observed in the Raman spectra of graphene. All of these abrupt changes in the optical properties of this material arise from the intercalation of the TFSI− ion and the associated change in the free carrier density (Δn = 1021 cm−3). Suppression of the 2D band Raman mode observed around 3 V corresponds to Pauli blocking of the double resonance Raman process and indicates a modulation of the Fermi energy of ΔEF= 1.1 eV. The thermal emissivity of the MLG device is also substantially modulated over the range from 7 – 14 µm. Using this device, have demonstrated free-space optical communication that utilizes ambient Planck radiation from a warm body and modulates the emitted intensity. We present an experimental demonstration achieving error-free communications at 100 bits per second over laboratory scales. We have also developed an AC Raman technique for measuring the Raman spectra during the intercalation−deintercalation half cycles in a multilayer graphene (MLG) device operating at 0.2−10 Hz. Raman spectra taken just 200 ms apart show the emergence and disappearance of the intercalated G band mode at around 1610 cm−1 . By integration of over hundreds of cycles, a significant Raman signal can be obtained. The intercalation/ deintercalation is also monitored with thermal imaging via voltage-induced changes in the carrier density, complex dielectric function ε(ω), and thermal emissivity of the device. “Dynamic Study of Intercalation/Deintercalation of Ionic Liquids in Multilayer Graphene Using an Alternating Current Raman Spectroscopy Technique” Zhi Cai, Haley Weinstein, Indu Aravind, Ruoxi Li, Sizhe Weng, Boxin Zhang, Jonathan L. Habif, and Stephen B. Cronin. Journal of Physical Chemistry Letters, 14, 7223 (2023).“Gate-tunable modulation of the optical properties of multilayer graphene by the reversible intercalation of ionic liquid anions” Zhi Cai, Indu Aravind, Haley Weinstein, Ruoxi Li, Jiangbin Wu, Han Wang, Jonathan Habif, and Stephen Cronin. Journal of Applied Physics. 132, 095102 (2022).“Harvesting Planck radiation for free-space optical communications in the long-wave infrared band“ Haley A. Weinstein, Zhi Cai, Stephen B. Cronin, and Jonathan L. Habif, Optics Letters. 47, 6225-6228 (2022). Figure 1

Elucidation of discharge mechanisms in He- and Ar-flexible μ-tube plasmas by temporally and spatially resolved plasma optical emission phoresis spectroscopy

A Helium- and Argon-flexible μ-tube plasma (FμTP) driven by a square wave high voltage were investigated by means of temporally and spatially resolved spectroscopy to characterize the discharge mechanisms. These two discharge gases show different discharge behavior in the same FμTP-configuration. The mixtures of different concentration of propane in Ar were used as discharge gases to confirm the role of Ar+ in an Ar-FμTP by tuning the discharge behavior. It was demonstrated that, N2+ are mainly responsible for the excitation and ionization and only small amount of He+ are produced in a He-FμTP, whereas Ar-FμTP lives from Ar+. These ions as well as excited species do not propagate beyond the capillary during the negative half cycle, resulting in a negligible contribution for protonation in this half cycle. The present study proposes a new method to data analysis, Plasma Optical Emission Phoresis Spectroscopy, which allows to distinguish noble gas ions from excited noble gas species.

Quantitative Kinetic Insights from Operando-UV/Vis Spectroscopy: An Application to NH3-SCR of NOx on Cu-CHA Catalysts.

We employ UV/Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show-case the CuII/CuI redox dynamics during the reduction half cycle of the NH3-Selective Catalytic Reduction (SCR) on Cu-CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas-phase evolution during the reaction. These data both on the dynamics of the gas-phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas-phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Quantitative Kinetic Insights from Operando‐UV/Vis Spectroscopy: An Application to NH3−SCR of NOx on Cu‐CHA Catalysts

AbstractWe employ UV/Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show‐case the CuII/CuI redox dynamics during the reduction half cycle of the NH3‐Selective Catalytic Reduction (SCR) on Cu‐CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas‐phase evolution during the reaction. These data both on the dynamics of the gas‐phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas‐phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Preoperative Chemotherapy plus Immune Checkpoint Inhibitors as Conversion Therapy in Pancreatic Cancer Patients with Initially Unresectable Liver-limited Metastases: A Case Report

Pancreatic cancer (PC) is a lethal tumor, and overall survival (OS) is poor, especially for patients with liver metastases. Herein, we report a 55-year-old female who presented with right upper quadrant pain. Computed tomography (CT) of the upper abdomen revealed a large space-occupying lesion (5.5×5.2 cm) in the pancreatic neck with multiple liver metastases. After biopsy confirmation, the patient underwent conversion therapy consisting of doublet chemotherapy (gemcitabine 1,000 mg/m2 and nab-paclitaxel 125 mg/m2) and toripalimab (a novel PD-1 inhibitor, 240 mg). After six and a half cycles, radical pancreaticoduodenectomy combined with resection of liver metastases and portal vein replacement were performed successfully. The patient died from hemorrhage of the pancreaticojejunostomy anastomotic stoma four months after surgery. No recurrence or metastases were detected by CT until the patient died. This is the first study to report the results of conversion surgery in patients with metastatic PC limited to the liver after preoperative chemotherapy plus a PD-1 inhibitor. Stage IV PC should not be considered a general contraindication for surgical resection in well-selected patients. A multicenter randomized controlled study should be performed to investigate the efficacy and safety of this controversial treatment strategy.