Axial Positions Research Articles

Study on the structure of energy‐saving bend pipes in a decanter centrifuge

AbstractDecanter centrifuges are widely used in solid–liquid separation, and saving their energy consumption is very important. In this paper, a bend pipe installed at the end of the decanter centrifuge was designed to save energy, and the effect of different structural parameters of the energy‐saving bend pipes on the outlet velocity and the reaction torque was investigated. The results revealed that the outlet velocity and the reaction torque were reduced with the increase in the number of pipes, outlet area, and pipe length. Increasing the radial position had little effect on the outlet velocity, but increased the reaction torque. Decreasing the outlet area and increasing the radial position both weaken the separation performance of the decanter centrifuge. The best separation performance and reaction torque effect were achieved in a suitable structure. Furthermore, the turbulent intensity was reduced from 143% to 135% in the new machine installed with bend pipes. The energy‐saving efficiency dropped with the increase of the rotational speed and the value was 13.1% under 2500 rpm. The separation performance of the new machine was similar to that of the original machine, and the dewatering speed was increased with the increase of the axial position.

Structural basis for inhibition of a GH116 β-glucosidase and its missense mutants by GBA2 inhibitors: Crystallographic and quantum chemical study

The crystal structure of the Thermoanaerobacterium xylanolyticum in glycoside hydrolase family 116 (TxGH116) β-glucosidase provides a structural model for human GBA2 glucosylceramidase, an enzyme defective in hereditary spastic paraplegia and a potential therapeutic target for treating Gaucher disease. To assess the therapeutic potential of known inhibitors, the X-ray structure of TxGH116 in complex with isofagomine (IFG) was determined at 2.0 Å resolution and showed the IFG bound in a relaxed chair conformation. The binding of IFG and 7 other iminosugar inhibitors to wild-type and mutant enzymes (Asp508His and Arg786His) mimicking GBA2 pathogenic variants was then evaluated computationally by two-layered ONIOM calculations (at the B3LYP:PM7 level). Calculations showed that six charged residues, Glu441, Asp452, His507, Asp593, Glu777, and Arg786 influence inhibitor binding most. His507, Glu777 and Arg786, form strong hydrogen bonds with the inhibitors (∼1.4−1.6 Å). Thus, the missense mutation of one of these residues in Arg786His has a greater effect on the interaction energies for all inhibitors compared to Asp508His. In line with the experimental data for the inhibitors that have been tested, the favorable interaction energy between the inhibitors and the TxGH116 protein followed the trend: isofagomine > 1-deoxynojirimycin > glucoimidazole > N-butyl-deoxynojirimycin ≈ N-nonyl-deoxynojirimycin > conduritol B epoxide ≈ azepane 1 > azepane 2. The obtained structural and energetic properties and comparison to the GBA2 model can lead to understanding of structural requirement for inhibitor binding in GH116 to aid the design of high potency GBA2 inhibitors.

Effect of NMR solvent on 1,4-dinitrocyclohexane-2,3,5,6-tetranitrate structure

It is very difficult to characterize cyclohexane structures due to the presence of chair and boat conformers. These conformers are continuously converting into each other, and an intermediate form of them is observed. In this research, 1,4-dinitrocyclohexane-2,3,5,6-tetranitrate was synthesized and investigated for structural studies by 1H NMR in chloroform and dimethyl sulfoxide solvents. The very special structure of 1,4-dinitrocyclohexane-2,3,5,6-tetranitrate in the chair conformer was well observed in the chloroform solvent, and in this solvent, the chair conformer was observed without converting the two conformers. While in dimethyl sulfoxide solvent, no such special conformer was observed. This research showed that the choice of NMR solvent could affect the spatial structure of 1,4-dinitrocyclohexane-2,3,5,6-tetranitrate, and to observe the unique conformer of the chair, chloroform solvent is a suitable solvent.

Investigation of Two Zr-p-NO2Bn-DOTA Isomers via NMR and Quantum Chemical Studies.

A combination of NMR studies and quantum chemical calculations were employed to investigate the structure and energetics of Zr4+ chelates of pNO2Bn-DOTA. We have demonstrated that two discrete regioisomeric chelates are generated during the complex formation. The nitrobenzyl substituent can adopt either an equatorial corner or side position on the macrocyclic ring. These regioisomers are incapable of interconversion and were isolated by HPLC. The corner isomer is more stable than the side, and the SAP conformer of both regioisomers is energetically more favorable than the corresponding TSAP conformer.

Novel insight on aromaticity enhancement of pyridone heterocycles using the anomeric effect-Schleyer hyperconjugation aromaticity: A DFT and NBO study

Considering the value of 2-pyridone and 4-pyridone heterocyclic groups in organic chemistry, in this study, the anomeric effect and Schleyer hyperconjugation aromaticity for the first time have been used to increase the aromaticity of these heterocycles. The anomeric effect in tetrahydropyrans containing 2-pyridone or 4-pyridone ring on the anomeric carbon in axial and equatorial conformers has been investigated using the DFT-B3LYP/6–311++G(d,p) calculation method. On the other hand, the aromaticity of 2-pyridone and 4-pyridone in the considered conformers was investigated by nucleus-independent chemical shift indices (NICS) and the harmonic oscillator model of electron delocalization index (HOMED). The results illustrate that placing 2-pyridone and 4-pyridone in the axial position increases their aromaticity through the anomeric effect. Furthermore, connecting the ring from the carbon atom to the anomeric position is better than the nitrogen atom for aromaticity increment. Aromaticity indices show that the anomeric effect-Schleyer hyperconjugation interaction is more robust in the presence of nitrogen atoms than oxygen or sulfur atom.

Electrowetting liquid lens integrating adaptive liquid iris

Multifunctional integration is the development direction of electrowetting liquid lenses. We propose an electrowetting liquid lens integrating adaptive liquid iris (ELL-LI) with adjustable radial aperture and axial position. The liquid iris and the liquid lens are both driven by electrowetting on dielectric and integrated in the same chamber together, and share the same conductive liquid part. The liquid iris does not need the flat support of a traditional liquid iris. The aperture can change from 1.16 to 5.11 mm. The iris can move up and down in the axial direction, according to different working electrodes on the side wall. Experiments show that our proposed ELL-LI has the functions of depth of field expansion and field adjustment, which has a great application prospect in imaging systems, such as camera imaging systems, etc.

Prediction of IOL decentration, tilt and axial position using anterior segment OCT data

BackgroundIntraocular lenses (IOLs) require proper positioning in the eye to provide good imaging performance. This is especially important for premium IOLs. The purpose of this study was to develop prediction models for estimating IOL decentration, tilt and the axial IOL equator position (IOLEQ) based on preoperative biometric and tomographic measures.MethodsBased on a dataset (N = 250) containing preoperative IOLMaster 700 and pre-/postoperative Casia2 measurements from a cataractous population, we implemented shallow feedforward neural networks and multilinear regression models to predict the IOL decentration, tilt and IOLEQ from the preoperative biometric and tomography measures. After identifying the relevant predictors using a stepwise linear regression approach and training of the models (150 training and 50 validation data points), the performance was evaluated using an N = 50 subset of test data.ResultsIn general, all models performed well. Prediction of IOL decentration shows the lowest performance, whereas prediction of IOL tilt and especially IOLEQ showed superior performance. According to the 95% confidence intervals, decentration/tilt/IOLEQ could be predicted within 0.3 mm/1.5°/0.3 mm. The neural network performed slightly better compared to the regression, but without significance for decentration and tilt.ConclusionNeural network or linear regression-based prediction models for IOL decentration, tilt and axial lens position could be used for modern IOL power calculation schemes dealing with ‘real’ IOL positions and for indications for premium lenses, for which misplacement is known to induce photic effects and image distortion.

The reactive Graetz problem for a first order homogeneous decomposition reaction, and the limit of moderately large reaction constants

The long term goal of the present study is to facilitate the inversion of experimental data on cluster evaporation in laminar flow inside tubes. This requires the determination of reactant and product fluxes as functions of three dimensionless governing parameters: the axial position x along the tube, the reaction rate coefficient K, and the ratio γ of product and reactant diffusivities. The reactant flux is first calculated by separation of variables, including the accurate determination of the first 35 eigenvalues for 13 discrete values of K in the range 0<K<500. This approach is far less efficient for the product flux because the eigenfunctions are not standard functions. A numerical solution is also implemented for the reactant and its product, though it can hardly cover the full range of the three relevant parameters. The most common experimental situation involves relatively large values of K, for which a three term asymptotic solution is developed in negative powers of K1/2, with errors of order K−2. These approximate results represent well the numerically calculated reactant fluxes for K > 10 in terms of two functions, H0(s) and H1(s), reported in tables. The product fluxes require two functions, I0(s,γ), I1(s,γ). These we compute for six values of γ, and report as simple analytical fits covering continuously the full physically relevant range 1<γ<1.5. The desired ability to analyze experimental data to yield kinetic information is therefore achieved without the need for additional numerical solutions to partial differential equations.

Soluble Ruthenium Phthalocyanines as Semiconductors for Organic Thin‐Film Transistors

AbstractRuthenium phthalocyanine (RuPcs) are multipurpose compounds characterized by their remarkable reactivity and photoelectronic properties, which yield a broad synthetic scope and easy derivatization at the axial position. However, RuPcs have been underexplored for use in organic thin‐film transistors (OTFTs), and therefore new studies are necessary to provide basic insight and a first approach in this new application. Herein, two novel RuPc derivatives, containing axial pyridine substituents with aliphatic chains (RuPc(CO)(PyrSiC6) (1) and RuPc(PyrSiC6)2 (2), were synthesized, characterized, and tested as the organic semiconductor in OTFTs. RuPc thin‐films were characterized by X‐ray diffraction (XRD), and atomic force microscopy (AFM) to assess film morphology and microstructure. 1 displayed comparable p‐type device performance to other phthalocyanine‐based OTFTs of similar design, with an average field effect mobility of 2.08×10−3 cm2 V−1 s−1 in air and 1.36×10−3 cm2 V−1 s−1 in nitrogen, and threshold voltages from −11 V to −20 V. 2 was found to be non‐functional as the semiconductor in the device architecture used, likely as a result of significant differences in thin‐film formation. The results of this work illustrate a promising starting point for future development of RuPc electronic devices, particularly in this new family of OTFTs.

Design and Experimental Analysis of an Optical Fiber Coupling System for a Ground-based Telescope with Adaptive Optics

Astronomy photonics has opened up a new era for the application of astronomical optical instruments. The fiber coupling system serves as the crucial link between the telescope and photonic devices. This paper explores a beam shaping method that utilizes a coupled lens to enhance the efficiency of coupling light into an optical single mode fiber. Compared to directly coupling the telescope beam into the fiber, this approach offers improved coupling efficiency and greater adjustment tolerance. The laboratory-based optical fiber coupling system described in this study comprises an imaging component with an F/50 ratio and a fiber coupling component. Theoretical analysis indicates that optimal coupling efficiency is achieved when the diameter of the focusing spot, limited by diffraction, matches the fiber core size. Any axial error, position error, or tip-tilt error between the lens and the fiber will reduce the coupling efficiency. Experimental results confirm that the coupling system achieves an efficiency of approximately 70%, which is close to the theoretical limit of 78%. These findings underscore the effectiveness of the fiber coupling method.

Effectiveness of vertical error budget model for portable multi-beam echo-sounder in shallow water bathymetric survey

With the increasing availability of portable survey equipment and platforms, hydrographic data acquisition now offers a diverse range of device options and installation methods. Tailoring the mounting and installation of hydrographic survey devices to fit the boat or platform dimensions has become common practice. The use of portable equipment is essential, given the wide selection of combined options available in the market. Consequently, sensor offsets and device performance differ for each survey conducted, necessitating the constant verification of accuracy performance.This paper examines the capabilities of portable multibeam echosounder (MBES) deployments on various types of survey boats. The investigation focuses on error budget modeling and field tests. A model is developed to estimate the propagated uncertainty resulting from different sources of measurement uncertainties. The model primarily considers vertical sources of error in MBES surveys, as they have the most significant impact on hydrographic data quality. To validate the model, field tests are conducted at two different locations using different boat and device configurations. The results demonstrate that the modeled uncertainties align with the measured standard deviations, particularly in the Pramuka area, where the standard deviation of data acquired at the widest beam angle of ±60° is 0.25m, close to the predicted value of 0.28m. However, in the Patimban area, the model overestimates the uncertainty, predicting 0.27m compared to the measured standard deviation of 0.17m.

Analysis of the flow phenomenon of fluid undergoing a sudden contraction to an annular gap

The paper presents the visualization results of the sudden contraction flow field with an annular gap downstream of the contraction cross section. The contraction ratio directly influences the flow phenomena. No stationary vortices were observed upstream of the contraction cross section, and flow separation divided the flow field within the annular gap into a recirculation zone, a shear layer, and a mainstream zone. Vena-contracta point and reattachment point occurred within the flow field of the annular gap. The production of Reynolds stress varied with the contraction ratio, and the momentum exchange mainly occurred in the recirculation zone and the shear layer, while the flow state in the mainstream zone tended to become isotropic. Rapid changes in turbulent kinetic energy primarily occurred in the shear layer, and the production term of turbulent kinetic energy contributed the most. Applying computational fluid dynamics and experimental results, this study has formulated an expression for the contraction coefficient of the proposed model. The axial positions of the vena-contracta point and reattachment point have a strong correlation with the contraction ratio, which can be represented by an exponential function.

Speed and Axial Position Control for a Linear-Rotary Switched Reluctance Motor With Two Radial Windings

For 6/4 Linear-Rotary Switched Reluctance Motors (LRSRMs), the magnetic-flux paths of the two windings are coupled in the radial direction, thus it is difficult to design the two-winding current algorithm for the linear and rotary control simultaneously. To solve this problem and achieve linear motion and rotation at the same time, speed and axial position control method is proposed through employing the equal magnetomotive force of two windings to calculate the given currents. This control method has advantages of simple principle, easy implementation and can realize the coordinated control of rotation and linear motion. In addition, the mathematical model of LRSRM is established to facilitate the design of current algorithm. Simulation and various experiments are completed to verify the demonstrated performance of the proposed control method.

Experimental study on radial diffusion characteristics of diesel–pentanol spray

It is always a hot topic to find alternative fuel for diesel. Pentanol is a potential alternative fuel for diesel. In this study, different volume ratios of fuel were obtained by adding pentanol to diesel. On the high-pressure common rail experimental platform, the spray processes of pure diesel and diesel–pentanol blends were observed and analyzed, and the differences of radial diffusion capability between different experimental fuel sprays were evaluated. The maximum radial diffusibility was analyzed through the maximum width and the maximum width corresponding to the axial position. The radial diffusion capacity of the whole was analyzed by means of the average width and spray cone angle, and the area of the gas entrainment area was analyzed. The results showed that the addition of pentanol enhanced the radial diffusion ability and gas entrainment ability of diesel sprays.

Experimental analysis of temperature and vapor core pressure for an annular heat pipe

The main contribution of this study is the effects of the operating conditions on the internal vapor pressure and temperature in an annular screen wick heat pipe, using distilled water as the working fluid. High-resolution pressure transducers, optical fiber distributed temperature sensors, and K-type thermocouples were employed to measure the internal and external temperatures as well as the local static pressures at different axial positions of the heat pipe. Temporal and frequency analysis using a one-dimensional continuous wavelet transform was performed on the differential pressure data to characterize flow behavior and infer the flow regime occurring within the heat pipe. The heat pipe was tested in multiple orientations with respect to the horizon (θ=0°, 45°, and 90°), heat loads (25, 50, and 75 W), and condenser coolant temperatures (Tw,in= 10 °C, 20 °C, and 30 °C). To estimate the vapor-phase flow friction factor for multiple Reynolds numbers, the Lockhart–Martinelli correlation was employed. This study provides critical experimental data and analyses for complex two-phase flow behavior in an annular wick heat pipe geometry. The thermal resistance and effective thermal conductivity were estimated as a function of the heat pipe orientation and power input. The experimental investigation revealed that power input and orientation influence both the internal vapor core and external surface temperatures, as well as the local pressure response. The outcomes from this study provide a valuable database that supports the advancement of heat pipe design, modeling, and validation.

Flame Surface Density and Artificially Thickened Flame Combustion Models Applied to a Turbulent Partially-Premixed Flame

The Sydney Flame provides an excellent framework for systematic analysis of premixed, partially premixed and non-premixed methane/air combustion. It represents (depending on the axial position from the fuel inlet) non-premixed, partially premixed and fully premixed combustion. We simulate the test case FJ200-5GP-Lr75-57, which represents the partially premixed mode. Large-eddy simulations (LES) are conducted using a flame surface density combustion model (FSD) using one-step chemistry and an artificially thickened flame model (ATF) with a global two-step and an analytically reduced multi-step chemistry reaction mechanism. Unity Lewis numbers are assumed (Le=1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$Le=1$$\\end{document}) at first. The FSD and ATF models are compared using the same computational mesh, numerical scheme and boundary conditions. Both models will be analysed regarding their accuracy and computational efficiency in the regime of partially premixed combustion. A comparison of the results points out the strengths and weaknesses of the FSD models. The FSD model with inclusion of flame stretch effects yields good agreement with mean experimental temperature, CO2 and H2O mass fraction distributions in contrast to the ATF model using the global two-step mechanism, which overestimates downstream temperature, CO2 and H2O mass fractions. The FSD model performs well in all regions, which are dominated first by premixed, then partially premixed and finally non-premixed combustion along the flame. The ATF multi-step chemistry shows good results only in the premixed mode region, while mean temperature, CO2 and mass fractions are overestimated in the non-premixed mode regions at higher mixture fraction values. Including differential diffusion into the transport equations improved the ATF model results in comparison with experiments. A mesh study revealed, that the ATF model performs only after mesh refinement. In particular results are improved in the non-premixed combustion region. In contrast, the FSD model is less resolution sensitive and performs very well for both meshes. An evaluation of the Wasserstein metric provides a quantitative assessment of different ATF model setups on simulation accuracy. Finally, computational times for all simulation setups are compared.

Phthalocyanine-Based Organic Thin Film Transistors as a Platform for Cannabinoid Sensors

With a growing international trend of Cannabis legalization, there is a present need for on-the-spot, low cost, and rapid differentiation of cannabinoids. The two primary cannabinoids, Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), obtained from Cannabis, elicit very different pharmacological effects necessitating consumer and industry methods for their detection and rapid speciation. CuPc and F16-CuPc, well characterized p- and n-type semiconductors respectively, are used as the OTFT semiconducting layer in combination with a cannabinoid-sensitive chromophore allowing for the differentiation of THC and CBD. Device analysis of pre- and post-pyrolyzed rapid plant extract samples was able to predict the THC/CBD ratio with HPLC accuracy. Spectroelectrochemistry was used to probe molecular interactions between cannabinoids with and without a cannabinoid sensitive chromophore against a variety of Pcs. Spectroelectrochemical changes to the Q-band region of the Pc spectra in the presence of analytes was related to modified ratios of Pc-Pc orientations in solution, streamlining material selection, reducing manufacturing burden, and expediting sensor development. 2D-NMR was used to further elucidate unique Pc-Pc and Pc-analyte interactions, providing additional insight on atomic level interactions. Through altered Pc-Pc orientations, analytes can induce physical alterations to Pc thin-film morphology and structure, consequently, modifying electrical performance beyond charge trapping effects. Pc peripheral and axial substitutions allow an additional level of Pc tunability and their relationship with analyte interactions, film structure, and OTFT sensing performance was explored.We established relationships between thin-films of phthalocyanines (Pcs) with a variety of central, peripheral, and axial substituents and their response to THC. X-Ray diffraction and UV–vis absorption spectroscopy measurements demonstrate significantly altered film morphologies and the formation of new crystal orientations in response to analytes, which are corroborated by scanning electron microscopy. With exposure to THC, aluminium chloride Pc generates the largest physical film changes as well as the largest changes in OTFT performance. These findings have implications for Pc-based OTFT sensor design, suggesting that the semiconducting Pc thin-film morphologies are not static in the presence of analytes, and that the sensing response is driven both by strong analyte-Pc coordination and bulk film restructuring to accommodate these interactions.References Advanced Functional Materials, 2021, ASAP, doi:10.1002/adfm.202107138ACS Appl. Mater. Interfaces, 2020, 12, 45, 50692–50702ACS Sensors, 2019, 4, 10, 2706-2715. Figure 1

Multi-Redox Systems Based on Boron Subphthalocyanines

Boron subphthalocyanines (SubPcs) are cone-shaped molecules comprised of three isoindole units bridged by aza-linkages and with a central boron atom containing an axial substituent. SubPcs are strong chromophores, but also redox-active molecules undergoing both reversible oxidation and reduction. By linking together SubPc units, multi-redox systems emerge that can take several redox states. Here I will show a variety of such scaffolds where SubPc units are either linked together at axial or peripheral positions by various acetylenic bridges. Bridges include various acyclic oligo(en)ynes and cyclic radiaannulenes containing both endo- and exocyclic carbon-carbon double bonds.1 The length and nature of the bridging unit determines whether the SubPc units are independent redox centers or whether there is communication between the units. Moreover, I will present structures were isoindole units of SubPc are replaced by thienopyrrole units2 as well as structures where the SubPc is linked to another redox-active unit, such as a triangulene.3 Experimentally determined redox potentials were compared to theoretically calculated ones, allowing us to move forward a reliable theoretical method for predicting redox properties. References a) H. Gotfredsen, L. Broløs, T. Holmstrøm, J. Sørensen, A. V. Mu ñ oz, M. D. Kilde, A. B. Skov, M. Santella, O. Hammerich, M. B. Nielsen, Org. Biomol. Chem. 2017, 15, 9809-9823; b) L. Broløs, M. D. Kilde, M. B. Nielsen, Org. Biomol. Chem. 2020, 18, 6077-6085; c) A. U. Petersen, M. G. Rasmussen, M. C. H. Thomsen, A. Ceuninck, M. B. Nielsen, Arkivoc 2020, vii, 145-157; d) H. Lissau, C. L. Andersen, F. E. Storm, M. Santella, O. Hammerich, T. Hansen, K. V. Mikkelsen, M. B. Nielsen, Chem. Commun. 2018, 54, 2763-2766. H. Gotfredsen, F. E. Storm, A. V. Muñoz, M. Santella, A. Kadziola, O. Hammerich, K. V. Mikkelsen, M. B. Nielsen, Chem. Eur. J. 2017, 23, 16194-16198. M. G. Rasmussen, M. F. Jespersen, O. Blacque, K. V. Mikkelsen, M. Juríček, M. B. Nielsen, Energy Sci. Eng. 2022, 10, 1752-1762. Figure 1

Progress on Hybrids and Mixed Alloys of Boron Subphthalocyanines (BsubPc) and Boron Subnaphthalocyanines (BsubNc); Tuning the Electrochemical Properties Towards Organic Electronic Applications

Our research and development focus has been on the molecular design, synthetic methodology and in-depth characterization of boron subphthalocyanines (BsubPcs) and subnaphthalocyanines (BsubNcs) to apply them to organic electronic applications. BsubPcs, BsubNcs and their hybrids are macrocycles with a chelated central boron atom via nitrogen bonding, and is a p-conjugated macrocyclic material. Our focal point balances between the basic and applied chemistry, chemical engineering, their in-depth physical properties (electrochemistry included). We also do computational modelling. Once materials are developed, we merge them into organic electronics to function as light emitting, light absorbing and electronic conducting materials within organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs)/organic solar cells (OSCs). The basic electrochemical and photophysical properties, developing and evaluating the properties is critical to move onto such applications.For this presentation, I will focus on our progress on the development of hybrids and mixed alloys of BsubPcs and BsubNcs.Regarding hybrids, they are a mixture of BsubPcs and BsubNcs, and are formed via a reaction of a statistical distribution of phthalonitrile and 2,3-dicyanonaphthalene intermediates on reaction with BCl3; we have named them X-RnBsub(Pcx-Ncy); X the axial substituent, Rn the number of peripheral substitutions, Pcx being the number of 6 p-conjugated bonds, Ncy being the number of 10 p-conjugated bonds (Figure). On first study, we found that X-RnBsub(Pc1-Nc2) have low photostability. Therefore, we moved onto developing a ‘statistical’ synthetic methodology to target highest yields of X-RnBsub(Pc2-Nc1)s, and we did achieve relatively high yields. X-RnBsub(Pc2-Nc1)s therefore could be purified to enable physical characterization. Within a couple past publications, the unique absorption spectra was noted and we have confirmed its uniqueness. The X-RnBsub(Pc2-Nc1)s absorption spectra is as wide as if BsubPc and BsubNc were mixed together. This therefore has good potential to harvest a larger scope of photons from solar or to achieved FRET transfer from a host to emit via an OLED. We then did in-depth first electrochemical characterization, confirmed their electrochemical oxidation and reduction stability and also did in-depth photoluminescence characterization. Therefore, merging X-RnBsub(Pc2-Nc1)s into organic electronic devices as well as other chemistry to synthesis the hybrids is ongoing.Regarding mixed alloys, in the past as we have shown that BsubNcs ended up being a mixed alloyed composition with random bay-position halogenation, that is formed during the reaction of BCl3 with 2,3-dicyanonaphthalene at temperature, which is the process to form the BsubNcs. The random bay-position halogenation has been shown to be impactful in a positive way within OPV devices, negative within OLED devices and also has electrochemical variations and good reversibility. Ongoing, given it is random halogenation, and some of the positive outcomes, this justifies considering additional mixed alloyed compositions.We have also recently shown that mixed alloyed BsubPcs can be formed with three peripheral halogens in the alpha (a) or beta (b) positions, named as Cl-αCl3BsubPc, Cl-βCl3BsubPc, Cl-αF3BsubPc, and Cl-βF3BsubPc. The alloyed mixtures consisted of C1 and C3 isomers of trihalogenated BsubPcs. The physical properties characterization including photophysics, electrochemistry, and thermal characterization, were studied and were also positive and then were engineered into OSCs as electron donors and electrons acceptors to clarify their impact on device performance which had positivity aspects. Therefore, we moved onto developing a set of additional BsubPc mixtures. To be outlined for this presentation, we considered sets of phthalonitrile mixtures to form peripherally halogenated BsubPc mixtures during the formation of BsubPcs from these intermediates. For example, 4,5-dichlorophthalonitrile (Cl2-pn), 4,5-difluorophthalonitrile (F2-pn), tetrachlorophthalonitrile (Cl4-pn), and tetrafluorophthalonitrile (F4-pn) are commercially available compounds that were mixed together and yields a mixture of BsubPc which we named: X-Cl2nF2mBsubPc and X-Cl4nF4mBsubPc (X = Cl or F being a variant, Figure). We then did physical characterization and found positive aspects including electrochemical oxidation and reduction stability. Merging them into organic electronic devices is ongoing and might be present during this presentation time.We did also recently develop additional chemistry methodology to develop additional mixed alloyed BsubPcs. The methodology was to develop phthalonitrile intermediates that have numbers of hydrogen, chlorine and fluorine substitutions and to take them onto the formation of the BsubPc mixed alloys. This is ongoing and may have some aspects to outline during this presentation.We also do computational modelling to look into other relative impacts of the materials being developed, for example the HOMO and LUMO orbital distributions, the local ionization etc. This will also be outlined during this presentation. Figure 1

Highly Efficient One-Pot Synthesis of Hexakis(m-phenyleneimine) Macrocyle Cm6 and the Thermostimulated Self-Healing Property through Dynamic Covalent Chemistry.

Highly efficient one-pot synthesis of hexakis(m-phenyleneimine) macrocycle Cm6 from acetalprotected AB-type monomer, m-aminobenzaldehyde diethylacetal, was successfully achieved based on imine dynamic covalent chemistry and precipitation-driven cyclization. The structure of Cm6 in the solid state was determined using CP/MAS NMR, X-ray single crystallographic analysis, and WAXD. Macrocycle Cm6 is composed of six phenylene and imine bonds facing the same direction, with nitrogen atoms arranged on the outside of the ring, and has a chair conformation, as predicted from DFT calculation. The macrocycle forms π-stacked columnar aggregates and hexagonally closest-packed structure. The cyclization process was investigated using MALDI-TOF MS and NMR. A mechanism of precipitation-driven cyclization based on imine dynamic covalent chemistry and π-stacked columnar aggregation is proposed. Both the nature of imine linkage and the shape anisotropy of the macrocycle played an important role in the single one-pot synthesis. The water-mediated mutual conversion between macrocycle Cm6 and linear oligomers driven by thermal stimulation was analyzed using MALDI-TOF MS and GPC methods. Macrocycle Cm6 with a dynamic covalent imine bond exhibited self-healing properties when stimulated using heat.