Continuous Flow Research Articles

Scalable approach for growing hexagonal boron nitride on silicon and its role in III-nitride van der Waals epitaxy

Hexagonal boron nitride (h-BN) stands out among 2D materials for its insulating properties, making it promising for the integration of 2D and 3D materials. However, achieving wafer-scale growth on silicon substrates remains a significant challenge. In this study, growth strategies for depositing h-BN on Si substrates are explored utilizing the wafer scalable metalorganic chemical vapor deposition. Our investigations reveal that employing a pulsed flow mode scheme is preferable over the conventional continuous flow mode scheme in growing h-BN thin films on 150 mm Si substrates. The as-grown h-BN film on Si exhibits uniform coverage with h-BN[0001]//Si[111]. With the successful wafer-scale growth of h-BN on Si, its role in aiding the van der Waals epitaxy of III-nitrides on Si substrates and subsequent epitaxial lift-off (ELO) of III-nitrides is further exemplified. An optimized h-BN thickness for the ELO process is also determined.

Genomic Architecture Underlying the Striking Colour Variation in the Presence of Gene Flow for the Guinan Toad-Headed Lizard.

How divergence occurs between closely related organisms in the absence of geographic barriers to gene flow stands as one of the long-standing questions in evolutionary biology. Previous studies suggested that the interplay between selection, gene flow and recombination strongly affected the process of divergence with gene flow. However, the extent to which these forces interact to drive divergence remains largely ambiguous. Guinan toad-headed lizards (Phrynocephalus guinanensis) in the Mugetan Desert exhibit striking colour differences from lizards outside the desert and provide an excellent model to address this question. Through extensive sampling and whole genome sequencing, we obtained genotypes for 191 samples from 14 populations inside and outside the desert. Despite the colour differences, continuous and asymmetric gene flow was detected across the desert border. More importantly, 273 highly diverged regions (HDRs) were identified between them, accounting only for 0.47% of the genome but widely distributed across 20 (out of the total 24) chromosomes. Strong signatures of selection were identified in HDRs, and local recombination rates were repressed. Furthermore, five HDRs exhibited significantly higher divergence, which contained key genes associated with crucial functions in animal coloration, including pteridine and melanocyte pigmentation. Genes related to retinal cells and steroid hormones were identified in other HDRs, which might have also contributed to the formation of colour variation in the presence of gene flow. This study provided novel insights into the understanding of the evolutionary mechanisms of genetic divergence in the presence of gene flow.

Aeration‐Free Photo‐Fenton‐Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants

The regulation of peroxymonosulfate (PMS) activation by photo‐assisted heterogeneous catalysis is under in‐depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well‐coupled dual‐defect VO‐M‐Co3O4@CNx S‐scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo‐thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO‐M‐Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min‐1 g‐2) than in aerobic conditions (1.67 min‐1 g‐2). Experimental evidence reveals that VO‐M‐Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect‐induced electron, revealing the competitive effect between O2 and PMS over VO‐M‐Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO‐M‐Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Aeration-Free Photo-Fenton-Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants.

The regulation of peroxymonosulfate (PMS) activation by photo-assisted heterogeneous catalysis is under in-depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well-coupled dual-defect VO-M-Co3O4@CNx S-scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo-thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO-M-Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min-1 g-2) than in aerobic conditions (1.67 min-1 g-2). Experimental evidence reveals that VO-M-Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect-induced electron, revealing the competitive effect between O2 and PMS over VO-M-Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO-M-Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Visible Light Excitation of Poly‐(para‐Phenylene Ethynylene) Enables Heterogeneous Photocatalytic Oxidations of Amines in Flow

AbstractHeterogeneous visible light photocatalysis is a compelling approach to address sustainability in synthetic photochemistry. However, the use of solid‐state photocatalysts remains very unpopular in organic synthesis because of their limited accessibility and the black‐box effect associated to the lack of rational between their molecular structure and their photochemical properties. Herein, we disclose the synthesis, characterization, photocatalytic properties and synthetic applications of a simple and readily available solid‐state conjugated organic polymer, poly‐(para‐phenylene ethynylene) 1, which exhibits a strong oxidative power upon irradiation with visible light (E(1*/1⋅−)=+1.67 V vs SCE). Comparisons with structural analogues highlighted the superior photocatalytic activity of this linear semiconductor, on account of its fully conjugated architecture. The associated excited‐state reactivity enabled the transformation of various amines into imines in batch and continuous flow reactors together with straightforward photocatalyst recycling. Mechanistic investigations revealed concomitant photoredox and energy transfer pathways, that led to the formation of the desired products. Ultimately, the inline generation of imines was exploited in telescoped three‐component Ugi reactions (3CR) in batch and flow toward biologically relevant α‐acylaminoamides.

Evaluation of an ionization chamber characteristics for 222Rn calibration.

The National Metrology Institute of Japan plan to use an inner-through-type ionization chamber (IC) as a working standard to calibrate radon monitors. Novel methods to calibrate the IC were described, and the calibration factor, CF [Bqm -3 A-1], of the IC with its expanded uncertainty (k=2) was evaluated to be (2.0±0.2)×1016Bqm-3 A-1 in the order of 10-13 A in the IC output current. In this study, the CFs, evaluated under sampling conditions between continuous gas flowing and stationary gas filled inside the IC, were in agreement within the uncertainty.

Rapid parameter estimation for merging massive black hole binaries using continuous normalizing flows

Abstract Detecting the coalescences of massive black hole binaries (MBHBs) is one of the primary targets for space-based gravitational wave observatories such as laser interferometer space antenna, Taiji, and Tianqin. The fast and accurate parameter estimation of merging MBHBs is of great significance for the global fitting of all resolvable sources, as well as the astrophysical interpretation of gravitational wave signals. However, such analyses usually entail significant computational costs. To address these challenges, inspired by the latest progress in generative models, we explore the application of continuous normalizing flows (CNFs) on the parameter estimation of MBHBs. Specifically, we employ linear interpolation and trig interpolation methods to construct transport paths for training CNFs. Additionally, we creatively introduce a parameter transformation method based on the symmetry in the detector’s response function. This transformation is integrated within CNFs, allowing us to train the model using a simplified dataset, and then perform parameter estimation on more general data, hence also acting as a crucial factor in improving the training speed. In conclusion, for the first time, within a comprehensive and reasonable parameter range, we have achieved a complete and unbiased 11-dimensional rapid inference for MBHBs in the presence of astrophysical confusion noise using CNFs. In the experiments based on simulated data, our model produces posterior distributions comparable to those obtained by nested sampling.

Advanced sensing and analytical techniques for quality control of tobacco flavoring

Abstract Assuring stability and uniformity in tobacco cut filler flavoring is crucial for cigarette product quality. This review focuses on advanced sensing and analytical techniques like gas chromatography-mass spectrometry and electronic nose technology. These methods analyze the chemical composition of flavoring liquids and detect volatile components in tobacco cut filler samples, thereby evaluating flavoring stability and uniformity. The review also acknowledges additional technologies like near-infrared spectroscopy and continuous flow analysis. Strengths and weaknesses of these detection techniques are discussed, providing insights into quality control of tobacco cut filler flavoring.

An Improved Transformer Model for Sap Flow Prediction that Efficiently Utilizes Environmental Information

AbstractAs an important reference for assessing plant water consumption and estimating plant transpiration, it is of great significance to achieve accurate prediction of plant sap flow. A number of deep learning models were established and compared using approximately 3 years of continuous eucalyptus flow time series data collected from the SAPFLUXNET open dataset and 6 environmental factors, including shortwave solar incident radiation, air temperature, air relative humidity, net radiation, vapor pressure deficit, and photosynthetic photon flux density. The experimental results show that the improved Transformer model, with the introduction of a two-step self-attention mechanism and simplified design, maintains significant predictive performance advantages compared to the original Transformer model, long short-term memory, gated recurrent unit, and temporal convolutional neural network models. In the shorter 1-h forecast, the mean squared error and coefficient of determination (R2) of the improved Transformer model are 0.0191 and 0.965, respectively. Compared to the suboptimal typical Transformer model, the MSE is reduced by 22.9%, and R2 is increased by 1.0%. Additionally, the improved model maintains stable predictive performance advantages in long-term plant flow prediction. In the longest 8-h advance prediction, the MSE is reduced by 14.9% compared to the suboptimal Transformer model, and R2 increases by 3.0% compared to the Transformer model. The comprehensive experimental results show that the improved Transformer model makes more effective use of environmental information to achieve more accurate and long-term plant flow prediction. This study emphasizes the basic principle and validity of the two-step self-attention network structure and provides a valuable basis for developing more effective methods for predicting plant sap flow.

Abstract 4113336: Characteristics and Outcomes of Ventricular Tachycardia Ablation in Patients with the HeartMate 3 Left Ventricular Assist Devices: Results From a Large Single-Center Registry

HeartMate 3 (HM3) is a fully magnetically levitated continuous flow left ventricular assist device (LVAD). In patients with HM3 and recurrent ventricular tachycardia (VT), data on the outcomes of catheter ablation (CA) are insufficient. We report our institutional experience with CA of VT in patients with the HM3.Consecutive patients with HM3 and recurrent drug-refractory VT undergoing CA were included. Ablation sites were identified using activation/entrainment mapping (stable VTs) and/or late/fractionated potential ablation and pace-mapping (unstable VTs). Between 2016-2023 a total of 431 patients (age 58±13, INTERMACS 3±0.98, 44% ischemic cardiomyopathy) received an HM3 LVAD at our institution. Of these, 15 (3.4%) underwent CA for recurrent VT despite therapy with 1.3±0.8 antiarrhythmic drugs a median of 700 days from the LVAD surgery (2 patients <1 month from the surgery). The LV access was transseptal in 12 (80%) cases, retrograde aortic in 2 (13%) and both in 1 (7%). A total of 23 distinct VTs were targeted. Of these, 21 (91%) were mapped with activation/entrainment mapping, always utilizing an intracardiac RV reference due to excessive surface ECG noise, and 2 (9%) were hemodynamically unstable with reduced LVAD flows and targeted with substrate-based ablation. A total of 3 (13%) VTs were targeted adjacent to the HM3 inflow cannula, and 20 (87%) from substrate remote from the HM3 cannula. At post-procedural programmed ventricular stimulation, non-inducibility of all targeted VTs was achieved in 13 (87%) patients, 1 patient had residual inducible clinical VT, and in 1 patient no post-procedural programmed stimulation was performed. Periprocedural complications occurred in 1 (7%) case (small pericardial effusion not requiring intervention). At 12 months follow-up following the index procedure, no death occurred and one patient received heart transplantation. Of the remaining 14 patients, 6 (42%) remained free from VT (2 with VT ablation <1 month post-LVAD and 12 with VT ablation >=1 month post-LVAD). In this large single-center HM3 registry, a minority of patients underwent CA for recurrent drug-refractory VT (3.4% over a 7-year period). CA of VT in HM3 recipients is feasible and appears safe also when performed soon after LVAD surgery. Myocardial scar from the underlying cardiomyopathic process rather than the apical cannula is the dominant substrate responsible for VT in these patients.

Oxoammonium-Catalyzed Oxidation of N-Substituted Amines.

We report the development of oxoammonium-catalyzed oxidation of N-substituted amines via a hydride transfer mechanism. Steric and electronic tuning of catalyst led to complementary sets of conditions that can oxidize a broad scope of carbamates, sulfonamides, ureas, and amides into the corresponding imides. The reaction was further demonstrated on a 100-g scale using a continuous flow setup.

Batch to Continuous Flow Visible‐Light Photooxidations Using Alumina Supported Hydroxyanthraquinones

AbstractThe discovery of new environmentally friendly recyclable photosensitizers is key to develop future applications in photooxidation chemistry. We report here the evaluation of a set of differently substituted biobased hydroxyanthraquinones in the context of visible light mediated singlet oxygen (1O2) photochemistry. This class of compounds is efficiently immobilized on alumina supports, which offers a simple way of removing them from the reaction mixture downstream. An integrated process using a flow reactor with a fixed catalytic bed is also evaluated and its performance is compared with homogeneous conditions.

Electrooxidative C(sp3)-H Cyanation of Sparteine and Lupanine in Undivided Batch and Continuous-Flow Cells.

Sparteine is widely used as a chiral ligand in asymmetric synthesis, but methods for providing efficient access to functionalized sparteine derivatives are still limited. Herein, we describe an electrochemical α-cyanation of sparteine-type bis-quinolizidine alkaloids. This method features commercially available setups for batch and single-pass continuous flow conditions, enabling easy gram scale synthesis of valuable racemic and enantiopure products. Moreover, insights into the selectivity of the reaction and overoxidation mechanisms are disclosed. This allows for the development of divergent oxidation pathways depending on the electrolysis conditions.

Isolation of β-O-4-Rich Lignin From Birch in High Yields Enabled by Continuous-Flow Supercritical Water Treatment.

The continuous flow supercritical water (scH2O) treatment of Birch wood (T=372-382 °C; t=0.3-0.7 s; p=260 bar) followed by alkali extraction of lignin allowed for the isolation of lignin and lignin carbohydrate complexes (LCCs) with a high number of β-O-4 moieties in the range 29-57/100 Ar (evaluated by quantitative 13C NMR analysis) in yields ranging between 13-19 wt % with respect to the initial wood. A "lightning rod effect" of carbohydrates has been claimed to explain the low degradation of β-O-4 bonds during the process. The structure of the isolated lignin was thoroughly elucidated via comprehensive NMR studies (HSQC, 13C and 31P). A low degree of condensation (DC)<5 % was found for all the lignin samples, which was only slightly dependent on the reaction severity. The number of aliphatic -OH, phenolic -OH, and -COOH groups was in the range 3.37-5.25, 1.41-2.31 and 0.39-0.73 mmol/g, respectively. The number of -COOH groups increased with increased severity, suggesting that oxidation can occur during the scH2O treatment. Furthermore, by simply varying the reaction severity, it was possible to tune important lignin properties, like the molar mass and the glass transition temperature (Tg).

Roles of Divinylbenzene Co‐Cross‐Linker in a Threefold Cross‐Linked Polystyrene–Phosphine Hybrid Monolith: Impact of Cross‐linking Degree on Catalytic Performance

AbstractContinuous‐flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross‐linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous‐flow reactions via transition‐metal catalysis. Additionally, the cross‐linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material‐based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono‐coordination and effective stabilization of metal complexes. We developed threefold cross‐linked polystyrene‐triphenylphosphine hybrid monoliths with cross‐linking structures adjusted by varying the content of divinylbenzene as co‐cross‐linker. The coordination behaviors and metal‐support interactions of these monoliths were evaluated, highlighting the importance of co‐cross‐linker content in site‐isolating phosphine units and stabilizing metal centers via arene‐metal interactions on the polystyrene network. By optimizing the cross‐linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd‐catalyzed C−Cl transformations, such as Suzuki–Miyaura cross‐couplings and Buchwald‐Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition‐metal catalysis.

High gain Bi-directional KY converter for low power EV applications

In electric vehicles (EVs), the type of electric motor and converter technology have a significant impact on regulating the operational characteristics of the vehicle. Therefore, in this work, the modified bi-directional KY converter (BKYC) is proposed for EV applications. The main contributions of the proposed converter are high step-up/step-down conversion gain, bi-directional power flow, simplified control structure, continuous current, common ground, low volume, and high efficiency. An inductor on either side of the converter ensures continuous current flow and passive components are arranged to operate in series to offer high step-up/step-down conversion. The charging and discharging operations, steady-state analysis, and design process of the proposed converter are discussed in detail and compared with similar bi-directional converter topologies. Further, the efficiency analysis of the proposed converter is presented and found that the efficacy of 95.51 % in charging operation and 96.52 % in discharging operation of operation. The simulations are carried out using MATLAB/Simulink environment. Further, a prototype of a modified bi-directional KY converter is implemented with a TMS320F28335 processor and validated with theoretical and simulation counterparts.

Optimizing reverse water gas shift catalysis: Minimizing metal loading and enhancing performance with Pt/ZrO2 catalysts through Rh incorporation

In this study, the optimization of catalysts for the reverse water gas shift reaction by minimizing metal loading and enhancing the performance of supported Pt catalysts through Rh incorporation was done. The catalysts were synthesized by the wet impregnation method, in which the metal noble load in bimetallic samples decreased by approximately one-third compared to the reference platinum catalyst, with varying Rh-Pt ratios. In all materials, m-ZrO2, obtained by the hydrothermal method, was used as support. In the catalytic tests in a continuous packed-bed flow reactor at atmospheric pressure, all samples were active to catalyze CO2 reduction between 200 and 300 °C. Bimetallic samples, particularly those with an Rh-Pt atomic ratio of 20–80, exhibited superior performance in the RWGS reaction despite their lower metal content. Based on the results of H2-TPR, FTIR in situ, and XPS, we propose that the enhanced CO production in bimetallic samples compared to Pt/ZrO2 catalysts can be attributed to Rh increasing the reduction extent of supported Pt. This enhancement facilitates the hydrogenation of bicarbonate species into formate species, which subsequently evolve into Pt0-CO and ultimately into CO. Additionally, Rh incorporation enables an alternative pathway for CO generation, where Pt0-carbonyls, known for their CO-producing capability, are formed via CO2 dissociation on the Pt0 surface. However, higher Rh concentrations favor the CO2 methanation rather than the RWGS reaction.

Forced Vibration Induced by Dynamic Response Under Different Inlet Distortion Intensities

Boundary layer ingestion propulsion systems have attracted much attention due to their significant potential to reduce the fuel consumption of future commercial aircraft. However, the aeroelastic stability of the fan blade is affected by the continuous non-uniform incoming flow induced by the ingestion of the boundary layer. When the fan blades rotate in the junction area between the distorted area and the clean area, blade pressure fluctuations occur. This phenomenon triggers a dynamic response process in the blade. Previous numerical investigations explored the influence of the distorted inflow on the blade vibration amplitude, and found that there are two sources of low-order excitation to the blades: the distorted inflow and the dynamic response of the blade. The results show that the low-order excitation existing in the distorted inflow varies sinusoidally with the distortion extent. However, as a new source of excitation, the key influence mechanism of dynamic response is still unclear. To explore this issue, calculations and analyses were conducted for different distorted inflow intensities. The results show that the blade vibration amplitude increases with the rise in distortion intensity. The total pressure at the leading and trailing edge of the rotor blade was extracted for analysis. It was found that when the blade enters or leaves the distorted area, there is a consistent lag in the change in total pressure at the trailing edge compared to the leading edge. This lag leads to an abrupt variation in the total pressure ratio, which constitutes the dynamic response process of the rotor blade. This periodic change generates a second-order excitation that causes the blade to vibrate.

Multiwalled Carbon Nanotube-Foam Composites for Fixed-Bed Continuous Flow Column Adsorption of Dyes

Multiwalled Carbon Nanotube-Foam Composites for Fixed-Bed Continuous Flow Column Adsorption of Dyes

Hydrodeoxygenation of Isoeugenol-Derived Model Compound over Carbon-Supported Pt and Pt-SnS Catalysts for the Production of Sustainable Jet Fuel.

This study focuses on the sustainable production of bio-jet fuel through the catalytic hydrodeoxygenation (HDO) of isoeugenol (IE). Sucrose-based activated carbon supported bimetallic Platinum-Tin metal sulphides (PtO-SnS/AC) catalyst was prepared for HDO process. Physicochemical properties of catalysts with different spraying synthesis methods (in situ and ex situ metal doping) and Pt loading (0.1-1.0 %) were further investigated. The PtO-SnS/AC catalysts were characterised using various techniques such as X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis (TGA). Both HRTEM and FESEM results show the successful preparation of a spherical nanoparticles doped over activated carbon, and Pt was dispersed on the outer shell of the particles. The catalytic HDO of IE was evaluated in a batch system and showed a high yield and conversion as follows: IE conversion of 100 %, liquid-phase mass balance of 95.92 %, dihydroeugenol (DH) conversion of 99.32 %, propylcyclohexane (PCH) yield of 88.94 % and 2-methoxy-4-propylcyclohexanol (HYD) yield of 76.19 %. Moreover, the PtO-SnS/AC catalyst exhibited high reusability with low metal leaching and high coke resistance for 10 cycles. The catalyst was evaluated in a continuous flow reactor for 100 h at different reaction temperatures, and interestingly, the catalyst showed low deactivation with a high half-time.