Consecutive Reductions Research Articles

Development of a semi-empirical bond strength model for multi-pass hot roll bonding based on the characterizations using the truncated-cone experiment

With special reference to the modelling of hot roll bonding, new experimental procedures to measure the resulting bond strength for a combination of AA6016 and AA8079 aluminum alloys at elevated temperatures and various strain rates using laboratory tests are proposed. The data acquired by this procedure is used to developed and calibrate a semi-empirical model, which accurately predicts the resulting bond strength within an error of 2 MPa on average. It is shown that the bond strength generally follows the flow stress regarding the dependency on temperature and strain. Additionally, inter-pass times can increase the bond strength, provided that both a suitable temperature and timespan are realized. Contrary, multiple consecutive height reductions were found to reduce the bond strength.

Introducing Novel Redox-Active Bis(phenolate) N-Heterocyclic Carbene Proligands: Investigation of Their Coordination to Fe(II)/Fe(III) and Their Catalytic Activity in Transfer Hydrogenation of Carbonyl Compounds.

A simple and efficient procedure for synthesizing novel pincer-type tridentate N-heterocyclic carbene bisphenolate ligands is reported. The synthesis of pincer proligands with N,N'-disubstituted imidazoline core, 5 and 6, was carried out via triethylorthoformate-promoted cyclization of either N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)cyclohexanediamine, 3, or N,N'-bis(2-hydroxyphenyl)cyclohexanediamine, 4, in the presence of concentrated hydrochloric acid. Cyclic voltammograms of the ligands revealed ligand-centered redox activity, indicating the noninnocent nature of the ligands. The voltammograms of the ligands exhibit two successive one-electron oxidations and two consecutive one-electron reductions. In contrast to previous reports, the redox-active ligands in this study exhibit one-electron oxidation and reduction processes. All products were thoroughly characterized by using 1H and 13C NMR spectroscopy. The base-promoted deprotonation of the proligands and subsequent reaction with iron(II) and iron(III) chlorides yielded compounds 7 and 8. These compounds are binuclear and tetranuclear iron(III) complexes that do not contain carbene functional groups. Complexes 7 and 8 were characterized by using elemental analysis and single-crystal X-ray crystallography. At low catalyst loadings, both 7 and 8 exhibited high catalytic activity in the transfer hydrogenation of selected aldehydes and ketones.

Numerical Investigation of Some Reductions for the Gatenby–Gawlinski Model

Two (consecutive) reductions of the complete Gatenby–Gawlinski model for cancer invasion are proposed in order to investigate the mathematical framework, mainly from a computational perspective. After a brief overview of the full model, we proceed by examining the case of a two-equations-based and one-equation-based reduction, both obtained by means of a quasi-steady-state assumption. We focus on invasion fronts, exploiting a numerical strategy based on a finite volume approximation, and perform corresponding computational simulations to study the sharpness/smoothness of the traveling waves. Then, we employ a space-averaged wave speed estimate—referred to as the LeVeque–Yee formula—to quantitatively approach the propagation phenomenon. Concerning the one-equation-based model, we propose a scalar degenerate reaction-diffusion equation, which proves to be effective in order to qualitatively recover the typical trends arising from the Gatenby–Gawlinski model. Finally, we carry out some numerical tests in a specific case where the analytical solution is available.

Electrocatalytic Reduction of CO2 to CO by Molecular Cobalt-Polypyridine Diamine Complexes.

Cobalt complexes have previously been reported to exhibit high faradaic efficiency in reducing CO2 to CO. Herein, we synthesized capsule-like cobalt-polypyridine diamine complexes [Co(L1)](BF4)2 (1) and [Co(L2) (CH3CN)](BF4)2 (2) as catalysts for the electrocatalytic reduction of CO2. Under catalytic conditions, complexes 1 and 2 demonstrated the electrocatalytic reduction of CO2 to CO in the presence or absence of CH3OH as a proton source. Experimental and computational studies revealed that complexes 1 and 2 undergo two consecutive reversible one-electron reductions on the cobalt core, followed by the addition of CO2 to form a metallocarboxylate intermediate [CoII(L)-CO22-]0. This crucial reaction intermediate, which governs the catalytic cycle, was successfully detected using high resolution mass spectrometry (HRMS). In situ Fourier-transform infrared spectrometer (FTIR) analysis showed that methanol can enhance the rate of carbon-oxygen bond cleavage of the metallocarboxylate intermediate. DFT studies on [CoII(L)-CO22-]0 have suggested that the doubly reduced species attacks CO2 on the C atom through the dz2 orbital, while the interaction with CO2 is further stabilized by the π interaction between the metal dxz or dxz orbital with p orbitals on the O atoms. Further reductions generate a metal carbonyl intermediate [CoI(L)-CO]+, which ultimately releases CO.

Trochanteric Claw Plate Fixation for Greater Trochanteric Fracture or Osteotomy in Total Hip Arthroplasty.

This study retrospectively evaluated 41 consecutive open reductions and internal fixations following primary or revision total hip arthroplasty, which required trochanteric claw plate fixation for greater trochanteric fracture or osteotomy between January 2008 and December 2020. The mean duration of clinical follow-up was 4.2 years (range, 1-13 years). The patients included 13 men and 28 women, with a mean age of 68 years (range, 32-87 years). The indications for intervention included trochanteric osteotomy, intraoperative fracture, and non-union including postoperative fracture in 6, 9, and 26 cases, respectively. The mean Merle d'Aubigné Clinical Score improved from 9.4 points (range, 5-15 points) pre-operatively, to 14.3 points (range, 9-18 points) at the last follow-up. Bone union occurred in 35 cases (85%), while implant breakage occurred in four cases. At the last follow-up, the mean Merle d'Aubigné Clinical Scores of bone union and non-union were 15.3 and 14.1, respectively (p=0.48). The Kaplan-Meier survival rate, with the endpoint being revision surgery for pain, non-union, dislocation, or implant breakage, at 10 years was 80.0% (95% confidence interval: 62.6-97.4%). Greater trochanteric fixation using a trochanteric claw plate yielded successful results.

Viability of AMURA biomarkers from single-shell diffusion MRI in clinical studies.

Diffusion Tensor Imaging (DTI) is the most employed method to assess white matter properties using quantitative parameters derived from diffusion MRI, but it presents known limitations that restrict the evaluation of complex structures. The objective of this study was to validate the reliability and robustness of complementary diffusion measures extracted with a novel approach, Apparent Measures Using Reduced Acquisitions (AMURA), with a typical diffusion MRI acquisition from a clinical context in comparison with DTI with application to clinical studies. Fifty healthy controls, 51 episodic migraine and 56 chronic migraine patients underwent single-shell diffusion MRI. Four DTI-based and eight AMURA-based parameters were compared between groups with tract-based spatial statistics to establish reference results. On the other hand, following a region-based analysis, the measures were assessed for multiple subsamples with diverse reduced sample sizes and their stability was evaluated with the coefficient of quartile variation. To assess the discrimination power of the diffusion measures, we repeated the statistical comparisons with a region-based analysis employing reduced sample sizes with diverse subsets, decreasing 10 subjects per group for consecutive reductions, and using 5,001 different random subsamples. For each sample size, the stability of the diffusion descriptors was evaluated with the coefficient of quartile variation. AMURA measures showed a greater number of statistically significant differences in the reference comparisons between episodic migraine patients and controls compared to DTI. In contrast, a higher number of differences was found with DTI parameters compared to AMURA in the comparisons between both migraine groups. Regarding the assessments reducing the sample size, the AMURA parameters showed a more stable behavior than DTI, showing a lower decrease for each reduced sample size or a higher number of regions with significant differences. However, most AMURA parameters showed lower stability in relation to higher coefficient of quartile variation values than the DTI descriptors, although two AMURA measures showed similar values to DTI. For the synthetic signals, there were AMURA measures with similar quantification to DTI, while other showed similar behavior. These findings suggest that AMURA presents favorable characteristics to identify differences of specific microstructural properties between clinical groups in regions with complex fiber architecture and lower dependency on the sample size or assessing technique than DTI.

HBpin/MoO2Cl2(H2O)2 as an efficient catalytic system for the reduction of esters, lactones and polyester plastic waste

In this work we report a very efficient protocol for the reduction of esters and lactones and for the reductive depolymerization of various polyester plastic waste with the catalytic system HBpin/MoO2Cl2(H2O)2 under mild reaction conditions with excellent yields. This method has the advantage of using the inexpensive and environmentally friendly MoO2Cl2(H2O)2 catalyst capable of catalyzing at least 8 consecutive PCL reductions with good yields.

Phenalenyl Radical: Smallest Polycyclic Odd Alternant Hydrocarbon Present in the Graphene Sheet.

Phenalenyl, a zigzag-edged odd alternant hydrocarbon unit can be found in the graphene nanosheet. Hückel molecular orbital calculations indicate the presence of a nonbonding molecular orbital (NBMO), which originates from the linear combination of atomic orbitals (LCAO) arising from 13 carbon atoms of the phenalenyl molecule. Three redox states (cationic, neutral radical, and anionic) of the phenalenyl-based molecules were attributed to the presence of this NBMO. The cationic state can undergo two consecutive reductions to result in neutral radical and anionic states, stepwise, respectively. The phenalenyl-based radicals were found as crucial building blocks and attracted the attention of various research fields such as organic synthesis, material science, computation, and device physics. From 2012 onward, a strategy was devised using the cationic state of phenalenyl-based molecules and in situ generated phenalenyl radicals, which created a new domain of catalysis. The in situ generated phenalenyl radicals were utilized for the single electron transfer (SET) process resulting in redox catalysis. This emerging range of applications rejuvenates the more than six decades-old phenalenyl chemistry. This review captures such developments ranging from fundamental understanding to multidirectional applications of phenalenyl-based radicals.

Imide-Based Multielectron Anolytes as High-Performance Materials in Nonaqueous Redox Flow Batteries

Recent developments toward high-energy-density all-organic redox flow batteries suggest the advantageous use of molecules exhibiting multielectron redox events. Following this approach, organic anolytes are developed that feature multiple consecutive one-electron reductions. These anolytes are based on N-methylphthalimide, which exhibits a single reversible reduction at a low potential with good cycling stability. Derivatives with two or three imide groups were synthesized to enable multielectron reduction events. By incorporating suitably designed side chains, a volumetric capacity of 65 Ah/L is achieved in electrolyte solutions. Bulk-electrolysis experiments and UV–vis–NIR absorption spectroscopy revealed good cycling stability for the first and second reduction of monoamides and diimides, respectively, but a loss of stability for the third reduction of triimides. We identify N-2-pentyl-N′-2-(2-(2-methoxyethoxy)ethoxy)ethylaminepyromellitic diimide as a very promising multielectron anolyte with an excellent volumetric capacity and superior cycling and shelf-life stability compared to monoimides and triimides. The outstanding performance of this anolyte was demonstrated in proof-of-principle redox flow batteries that reach an energy density of 24.1 Wh/L.

Bayesian reconstruction of the inflaton’s speed of sound using CMB data

We update the search for features, due to transient reductions in inflaton's speed of sound, in the Cosmic Microwave Background (CMB) angular power spectrum using Planck 2018 temperature, polarization and lensing data. We develop a new methodology to test more flexible templates to reconstruct the reduction of the speed of sound based on Gaussian Processes. We formally derive a dynamical prior for the shape of the reduction using a \textit{maximum-entropy} approach to ensure the physical conditions of the model are satisfied. The posterior allows for one or more consecutive reductions, fitting apparent features in the CMB power spectra in multipoles from a few tens to $\ell\simeq 2000$. As expected, these fits are not statistically favored with respect to the $\Lambda$CDM model. The methodology derived here allows for the inclusion of additional data sets (in particular, Large Scale Structure data), which in principle will increase the statistical significance of the reconstruction of the inflaton's speed of sound.

Reduction of copper from dilute acid solutions by hydrolysis of wood carbohydrates

ABSTRACT Copper reduction to metallic copper from dilute acid solutions containing Cu+2 was studied by means of sawdust from Radiata Pine as a reducing agent. Influence of the temperature, copper concentration and reaction time on the reduction of copper was investigated using an autoclave reactor. Furthermore, maximum reduction capacity of the sawdust was calculated through consecutive reductions. Results obtained show that diluted acid solutions containing Cu+2 can be effectively reduced to metallic copper by sawdust from Radiata Pine above 120°C. For a 0.5 g L−1 Cu+2 solution at 120°C and in 60 min, close to 90% of the copper can be reduced to metallic copper, which crystalises on the surface of the wood particles. At 120°C and for 90 min reaction time up to 95% of the copper can be reduced, generating an effluent with 0.02 g L−1 of copper. This value is similar to those obtained using activated carbon. Consecutive steps of reductions of the sawdust with fresh solutions with 0.5 g L−1 Cu+2 indicate that for 6 steps, the copper load of the sawdust is about 11.9 kg Cu/ton sawdust (dry basis) while for more concentrated solutions of 16.7 gL−1 Cu+2 the copper load reaches 15.0 kg Cu/ton sawdust. These results indicate that this process could be an alternative to conventional electrowinning.

C-N Bond Formation by Consecutive Continuous-Flow Reductions towards A Medicinally Relevant Piperazine Derivative.

A new, continuous-flow consecutive reduction method was developed for the C-N bond formation in the synthesis of the key intermediate of the antipsychotic drug cariprazine. The two-step procedure consists of a DIBAL-H mediated selective ester reduction conducted in a novel, miniature alternating diameter reactor, followed by reductive amination using catalytic hydrogenation on 5% Pt/C. The connection of the optimized modules was accomplished using an at-line extraction to prevent precipitation of the aluminum salt byproducts.

Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications

Non-aqueous redox flow batteries (RFBs) have been gaining increased attention in the energy storage arena. Some of their attractive features include the promise for high energy densities, wider voltage windows compared to aqueous systems, as well as wider operating temperature ranges. One of the major challenges in the development of these systems is the lack of electroactive materials that can undergo reversible redox events within the larger potential window of organic solvents. Herein, we present the design, synthesis, and measurement of electrochemical properties of some iron-based imine- and iminopyridine complexes as promising candidates for RFB applications. Synthesized complexes afforded three reversible redox couples over a ~3 V range. The redox events were also computationally explored and are in good agreement with experimental data. Theoretical calculations show that the redox event at the positive potential can be characterized as metal-centered event corresponding to Fe3+→ Fe2+ reduction, while the two redox events at negative potentials are associated with the consecutive reductions of iminopyridine or diimine moieties. This work has led to the identification of a promising anolyte material, [tris(imino)pyridine)Fe][OTf]2 (1), which is soluble in acetonitrile and is synthesized in two simple steps. This species shows outstanding performance when cycled between 1.0 V and 2.35 V, with 93% coulombic efficiency, 84% energy efficiency, and a capacity decay rate of 0.61% per cycle at 5 mA cm−2. Further modifications to this kind of charge carrier may lead to the development of high energy density materials for grid scale energy storage applications.

Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives: Synthesis, Spectroscopy, Structure, and Electrochemistry

As an extension of our continuing work in metallocenium chemistry, we report here on new functionalized rhodocenium salts. In contrast to isoelectronic cobaltocenium compounds, rhodium as a 4d metal allows synthetic routes via prefunctionalized cyclopentadienyl half‐sandwich precursors, thereby facilitating access to monofunctionalized rhodocenium salts containing substituents comprising methyl, trimethylsilyl, carboxylate and carboxylate ester as well as amide derivatives. Synthetic aspects, scope and limitations, as well as spectroscopic (1H/13C‐NMR, IR, HR‐MS), and structural (XRD) properties are reported. Like the parent rhodocenium ion, all new derivatives undergo two chemically consecutive reductions at potentials that depend on the respective ring substituent. The second reduction competes with a rapid reaction of the corresponding rhodocenes to their 18 VE dimers. Rate constants for this process range from 2 × 103 s–1 to 2.5 × 105 s–1 as estimated from digital simulations of experimental voltammograms. Rhodocenium carboxylic acid (8) constitutes a special case in that proton instead of metal reduction is observed at Pt or Au electrodes.

TetrazineBox: A Structurally Transformative Toolbox.

Synthetic macrocycles capable of undergoing allosteric regulation by responding to versatile external stimuli are the subject of increasing attention in supramolecular science. Herein, we report a structurally transformative tetracationic cyclophane containing two 3,6-bis(4-pyridyl)-l,2,4,5-tetrazine (4-bptz) units, which are linked together by two p-xylylene bridges. The cyclophane, which possesses modular redox states and structural post-modifications, can undergo two reversibly consecutive two-electron reductions, affording first its bisradical dicationic counterpart, and then subsequently the fully reduced species. Furthermore, one single-parent cyclophane can afford effectively three other new analogs through box-to-box cascade transformations, taking advantage of either reductions or an inverse electron-demand Diels-Alder (IEDDA) reaction. While all four new tetracationic cyclophanes adopt rigid and symmetric box-like conformations, their geometries in relation to size, shape, electronic properties, and binding affinities toward polycyclic aromatic hydrocarbons can be readily regulated. This structurally transformative tetracationic cyclophane performs a variety of new tasks as a result of structural post-modifications, thus serving as a toolbox for probing the radical properties and generating rapidly a range of structurally diverse cyclophanes by efficient divergent syntheses. This research lays a solid foundation for the introduction of the structurally transformative tetracationic cyclophane into the realm of mechanically interlocked molecules and will provide a toolbox to construct and operate intelligent molecular machines.

Viologen/Bromide Dual-Redox Electrochemical Capacitor with Two-Electron Reduction of Viologen.

In this work, we report a novel dual-redox electrochemical capacitor (EC) using a modified viologen (V) as anolyte and bromide (Br) as catholyte. In general, modified viologens are dications. When they are used as anolyte in aqueous dual-redox ECs, only one-electron reduction reaction can occur, because most divalent and monovalent viologens are soluble but zerovalent viologens are insoluble. The insoluble and nonconductive zerovalent viologens will block the surface of the activated carbon electrode from subsequent reactions. The energy densities of the dual-redox ECs using viologens are expected to be greatly improved if those viologens can carry out multiple electron reduction reactions. In this work, 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium (NV4+), a tetra-cationic viologen, has been used as anolyte for dual-redox EC. NV2+ produced by two-electron reduction of NV4+ is highly soluble in aqueous solution, so that two consecutive one-electron reductions of viologen can be utilized in dual-redox ECs. To further solve the cross-diffusion issue of the charging products, Br3- and NV cations, of the positive and the negative electrodes, we have used tetrapropyl ammonium cation (TPA+) to complex Br3-, and quaternized styrene ethylene butylene styrene (SEBS-QA) anion exchange membrane (M) to block the cross-diffusion of NV cation. The obtained NV/TPA/Br-M (NV4+/TPA+/Br- electrolyte with SEBS-QA membrane) dual-redox EC exhibits an average Coulombic efficiency over 99%. It also provides a high specific energy of 87 Wh/kgdry at 1 A/gdry and a peak power density of 4.8 kW/kgdry at 5 A/gdry. The functions of TPA+ and SEBS-QA membrane were characterized and are discussed in detail.

Total Syntheses of Herqulines B and C.

An approach for the syntheses of herqulines B and C is reported that takes advantage of an l-tyrosine-derived diketopiperazine, a mycocyclosin analogue, as a synthetic precursor. The strategy relies on a series of consecutive reductions to adjust the mycocyclosin oxidation state to that observed in the herquline class of natural products. The strained and distorted l-tyrosine-based biaryl system characteristic for mycocyclosin is selectively converted to the 1,4-diketone structural motif common to the herqulines via initial hypervalent iodine-mediated dearomatization and a subsequent directed Birch reduction, enabled by an intramolecular H-source. Additionally, the piperazine oxidation state is accessible via an iron-catalyzed reduction of a diketopiperazine intermediate.

Concise Total Synthesis of Herqulines B and C.

A simple total synthesis of herqulines B and C is reported, modeled on the reductive biosynthesis reported previously by other researchers. Commencing from tyrosine, these alkaloids were fashioned through a dimerization, macrocyclization, and four consecutive reductions. Emerging from these studies are strategic insights on the synthesis of these strained alkaloids, as well as mild conditions for the exhaustive reduction of diketopiperizines.

The Critical E4 State of Nitrogenase Catalysis.

The reaction catalyzed by the nitrogenase enzyme involves breaking the stable triple bond of the dinitrogen molecule and is consequently considered among the most challenging reactions in biology. While many aspects regarding its atomic mechanism remain to be elucidated, a kinetic scheme established by David Lowe and Roger Thorneley has remained a gold standard for functional studies of the enzyme for more than 30 years. Recent three-dimensional structures of ligand-bound states of molybdenum- and vanadium-dependent nitrogenases have revealed the actual site of substrate binding on the large active site cofactors of this class of enzymes. The binding mode of an inhibitor and a reaction intermediate further substantiate a hypothesis by Seefeldt, Hoffman, and Dean that the activation of N2 is made possible by a reductive elimination of H2 that leaves the cofactor in a super-reduced state that can bind and reduce the inert N2 molecule. Here we discuss the immediate implications of the structurally observed mode of binding of small molecules to the enzyme with respect to the early stages of the Thorneley-Lowe mechanism of nitrogenase. Four consecutive single-electron reductions give rise to two bridging hydrides at the cluster surface that can recombine to eliminate H2 and enable the reduced cluster to bind its substrate in a bridging mode.

C-Functionalized Cationic Diazaoxatriangulenes: Late-Stage Synthesis and Tuning of Physicochemical Properties.

A series of nine C‐functionalized cationic diazaoxatriangulene (DAOTA) dyes have been successfully synthesized and fully characterized, including X‐ray structural analysis of four derivatives. The introduction of electron‐withdrawing or ‐donating functions enables the tuning of both electro‐ and photochemical properties with, for instance, two consecutive (reversible) reductions or oxidations observed for nitro or amino derivatives, respectively. The substituents also impacted on the optical properties, with absorption maxima varying from λ=528 to 640 nm and fluorescence being shifted from the yellow to the red range, up to λ=656 nm.