A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality.

Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)3/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg gCr-1 h-1) and C8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C6 + 1-C8) selectivities, exceeding 90 wt%, as a result of high 1-C6 purity (>90 wt%) in the C6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C6 cyclics controlled highly α-selective ethylene oligomerization.

Does the asymmetry and extension function of the preoperative cervical paraspinal extensor predict postoperative cervical sagittal deformity in patients who undergo modified laminoplasty?

BACKGROUND CONTEXT: A previous study found that the cross-sectional area (CSA) of the preoperative cervical paraspinal extensors (CPEs) was associated with loss of cervical lordosis after laminoplasty, while a recent study found that CPE asymmetry was associated with symptoms of degenerative cervical myelopathy. Whether preoperative CPE asymmetry can predict cervical sagittal deformity (CSD) after laminoplasty is unknown. PURPOSE: To assess whether asymmetry, degree of degeneration, and extension function of the CPE can be used as predictors of postoperative CSD in patients who undergo laminoplasty. STUDY DESIGN: A retrospective study. PATIENT SAMPLE: From January 2017 to December 2019, 55 patients with multilevel cord compression and myelopathic symptoms were enrolled. OUTCOME MEASURES: The visual analog scale (VAS), neck disability index (NDI), and modified Japanese Orthopedic Association (mJOA) were used to assess cervical spinal function and quality of life. METHODS: From January 2017 to December 2019, 55 patients undergoing modified laminoplasty were included. The following parameters were measured preoperatively and 24 months postoperatively on X-ray: (1) C0-C2 Cobb angle; (2) C2-C7 Cobb angle (CL); (3) T1 slope (T1S); (5) C2-C7 sagittal vertical axis (SVA); (6) T1S minus CL; (7) Preoperative extension function: Extension CL minus Neutral CL (EF). Preoperative global alignment parameters: (8) spino cranial angle, (9) C7-S1 sagittal vertical axis (C7 SVA), (10) pelvic incidence, (11) lumbar lordosis, (12) thoracic kyphosis. (13) Preoperative CPE parameters: Summation of bilateral total cross-sectional area (STCSA), summation of bilateral total cross-sectional area ratio (STCSAR), total cross-sectional area asymmetry, summation of bilateral functional cross-sectional area of muscle (SFCSA), summation of bilateral functional cross-sectional area of muscle ratio (FCSAR), and functional cross-sectional area of muscle asymmetry (FCSAA). The VAS, mJOA, and NDI were used to evaluate cervical spine function and quality of life. Patients were divided into the CSD group and the non-deformed group (N-CSD) group postoperatively, and the parameters between the two groups were compared. The Pearson correlation coefficient was used to evaluate the relationship between the parameters, and multiple regression analysis and ROC curve analysis were used to determine the predictors and key values. RESULTS: Compared with functional scores, mJOA in the CSD group was significantly lower than that in the N-CSD group, while NDI and VAS were significantly higher. Postoperative CL was significantly correlated with EF, SFCSA/STCSA (C3-C6), SFCSAR (C4 and C6), STCSAR (C6), and FSCAA (C6). T1S minus CL was significantly correlated with EF, SFCSA/STCSA (C3-4 and C6), SFCSAR (C4 and C6), STCSAR (C6) and FSCAA (C6). C2-7 SVA was significantly correlated with EF, SFCSAR (C4 and C6), STCSAR (C6), and FSCAA (C6). Multiple regression analysis showed that FCSAA (C6), SFCSAR (C6), SFCSAR (C4), and EF were significant predictors of postoperative CSD. ROC curve analysis showed that the optimal cutoff points were 18.405, 2.95, 4.47, and 11.96. CONCLUSIONS: The present study found that preoperative extension dysfunction of CPEs, asymmetry at the C6 level cervical extensors, and cervical extensor CSAs without fatty infiltration at the C4 and C6 levels were associated with cervical sagittal imbalance after modified laminoplasty. These factors can be considered when future spine surgeons formulate surgical plans.

Computer-assisted catalyst development via automated modelling of conformationally complex molecules: application to diphosphinoamine ligands.

Simulation of conformationally complicated molecules requires multiple levels of theory to obtain accurate thermodynamics, requiring significant researcher time to implement. We automate this workflow using all open-source code (XTBDFT) and apply it toward a practical challenge: diphosphinoamine (PNP) ligands used for ethylene tetramerization catalysis may isomerize (with deleterious effects) to iminobisphosphines (PPNs), and a computational method to evaluate PNP ligand candidates would save significant experimental effort. We use XTBDFT to calculate the thermodynamic stability of a wide range of conformationally complex PNP ligands against isomeriation to PPN (ΔGPPN), and establish a strong correlation between ΔGPPN and catalyst performance. Finally, we apply our method to screen novel PNP candidates, saving significant time by ruling out candidates with non-trivial synthetic routes and poor expected catalytic performance.

Functional Single-Walled Carbon Nanotubes for Anion Sensing.

We report an anion-sensing platform wherein conductance changes are triggered by chemical interactions between selectors and anions. The selector design incorporates both a cationic moiety (i.e., pyridinium) and a thiourea-based dual-hydrogen-bond donor. Anion binding by a model selector (2) was studied using 1H NMR and UV-vis titrations, which reveal a binding strength toward acetate ions (AcO-) followed by Cl- > Br- > NO3-. These studies reveal that selector 2 is deprotonated upon addition of AcO-, whereas it undergoes hydrogen bonding associated with Cl-, Br-, and NO3-. The cationic pyridinium moiety improves anion binding affinity by lowering the pKa value of selector 2 and enhancing the hydrogen-bond donor capability as confirmed by spectroscopic titrations and DFT calculations. The selector is covalently attached to poly(4-vinylpyridine) (P4VP), which wraps single-walled carbon nanotubes (SWCNTs) (i.e., P4VP-2-SWCNT) to transduce an electrical signal. As a result, continuous anion sensing was achieved with high sensitivity represented by a normalized resistance change of 101.9 ± 10.3% toward 16.7 mM AcO-, whereas negligible sensitivity was observed toward Cl-, Br-, and NO3-. The sensitivity transition was attributed to the internal charge transfer of 2 by deprotonation of the thiourea proton upon addition of AcO-.

Thiophene-fused polyaromatics: synthesis, columnar liquid crystal, fluorescence and electrochemical properties.

Efficient syntheses that incorporate thiophene units into different extended conjugation systems are of interest as a result of the prevalence of sulfur-rich aromatics in organic electronics. Self-organization by using liquid crystal properties is also desirable for optimal processing of organic electronics and optical devices. In this article, we describe a two-step process to access extended regioisomers of polyaromatics with different shapes. This method involves an efficient single or double benzannulation from an alkyne precursor followed by Scholl cyclization. In spite of their unconventional nondiscoid shape, these materials display stable columnar liquid crystal phases. We examine the photophysical and electrochemical properties and find that structurally very similar thiophene-fused polyaromatics display significant differences in their properties.

Exo-selective, Reductive Heck Derived Polynorbornenes with Enhanced Molecular Weights, Yields, and Hydrocarbon Gas Transport Properties.

Next-generation membranes use highly engineered polymeric structures with enhanced chain rigidity, yet difficulties in polymerization often limit molecular weights required for film formation. Addition-type polynorbornenes are promising materials for industrial gas separations, but suffer from these limitations owing to endo-exo monomeric mixtures that restrict polymerization sites. In this work, a synthetic approach employing the reductive Mizoroki-Heck reaction resulted in exo-selective products that polymerized up to >99% yields for ROMP and addition-type polymers, achieving molecular weights an order of magnitude higher than addition-type polymers from endo-exo mixtures and impressive side group stereoregularity. Due to this increased macromolecular control, these polynorbornenes demonstrate unique solubility-selective permeation with mixed gas selectivities that exceed commercially used PDMS. In addition to thermal and structural characterization, XRD and computational studies confirmed the results of pure and mixed-gas transport testing, which show highly rigid membranes with favorably disrupted chain packing.

Ionic Highways from Covalent Assembly in Highly Conducting and Stable Anion Exchange Membrane Fuel Cells.

A major challenge in the development of anion exchange membranes for fuel cells is the design and synthesis of highly stable (chemically and mechanically) conducting membranes. Membranes that can endure highly alkaline environments while rapidly transporting hydroxides are desired. Herein, we present a design using cross-linked polymer membranes containing ionic highways along charge-delocalized pyrazolium cations and homoconjugated triptycenes. These ionic highway membranes show improved performance. Specifically, a conductivity of 111.6 mS cm-1 at 80 °C was obtained with a low 7.9% water uptake and 0.91 mmol g-1 ion exchange capacity. In contrast to existing materials, ionic highways produce higher conductivities at reduced hydration and ionic exchange capacities. The membranes retain more than 75% of their initial conductivity after 30 days of an alkaline stability test. The formation of ionic highways for ion transport is confirmed by density functional theory and Monte Carlo studies. A single cell with platinum metal catalysts at 80 °C showed a high peak density of 0.73 W cm-2 (0.45 W cm-2 from a silver-based cathode) and stable performance throughout 400 h tests.

Carbon Nanotube Chemical Sensors.

Carbon nanotubes (CNTs) promise to advance a number of real-world technologies. Of these applications, they are particularly attractive for uses in chemical sensors for environmental and health monitoring. However, chemical sensors based on CNTs are often lacking in selectivity, and the elucidation of their sensing mechanisms remains challenging. This review is a comprehensive description of the parameters that give rise to the sensing capabilities of CNT-based sensors and the application of CNT-based devices in chemical sensing. This review begins with the discussion of the sensing mechanisms in CNT-based devices, the chemical methods of CNT functionalization, architectures of sensors, performance parameters, and theoretical models used to describe CNT sensors. It then discusses the expansive applications of CNT-based sensors to multiple areas including environmental monitoring, food and agriculture applications, biological sensors, and national security. The discussion of each analyte focuses on the strategies used to impart selectivity and the molecular interactions between the selector and the analyte. Finally, the review concludes with a brief outlook over future developments in the field of chemical sensors and their prospects for commercialization.

A Semiconducting Conjugated Radical Polymer: Ambipolar Redox Activity and Faraday Effect.

Investigations of magnetism in electronically coupled polyradicals have largely focused on applications in photonic and magnetic devices, wherein radical polymers were found to possess molecularly tunable and cooperative magnetic properties. Radical polymers with nonconjugated insulating backbones have been intensively investigated previously; however the integration of radical species into conducting polymer backbones is at an early stage. We report herein 1,3-bisdiphenylene-2-phenylallyl (BDPA)-based conjugated radical polymers that display ambipolar redox activities and conductivities. Moreover, these radical polymers were demonstrated to be promising magneto-optic (MO) materials with Faraday rotations wherein the sign is modulated by the radical character and display absolute Verdet constants up to (2.80 ± 0.84) × 104 deg T-1 m-1 at 532 nm. These values rival the performance of the present-day commercial inorganic MO materials (e.g., terbium gallium garnet, V = -1.0 × 104 deg T-1 m-1 at 532 nm). The structure property studies detailed herein reveal the promise of multifunctional conjugated radical polymers as responsive MO materials.

Carbon Nanotube Formic Acid Sensors Using a Nickel Bis( ortho-diiminosemiquinonate) Selector.

Formic acid is corrosive, and a sensitive and selective sensor could be useful in industrial, medical, and environmental settings. We present a chemiresistor for detection of formic acid composed of single-walled carbon nanotubes (CNTs) and nickel bis( ortho-diiminosemiquinonate) (1), a planar metal complex that can act as a ditopic hydrogen-bonding selector. Formic acid is detected in concentrations as low as 83 ppb. The resistance of the material decreases on exposure to formic acid, but slightly increases on exposure to acetic acid. We propose that 1 assists in partial protonation of the CNT by formic acid, but the response toward acetic acid is dominated by inter-CNT swelling. This technology establishes CNT-based chemiresistive discrimination between formic and acetic acid vapors.

Bio-Inspired Carbon Monoxide Sensors with Voltage-Activated Sensitivity.

Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the strong specific interaction between CO and the iron porphyrin provides a highly selective and customizable sensor. We report the development of chemiresistive sensors with voltage-activated sensitivity for the detection of CO comprising iron porphyrin and functionalized single-walled carbon nanotubes (F-SWCNTs). Modulation of the gate voltage offers a predicted extra dimension for sensing. Specifically, the sensors show a significant increase in sensitivity toward CO when negative gate voltage is applied. The dosimetric sensors are selective to ppm levels of CO and functional in air. UV/Vis spectroscopy, differential pulse voltammetry, and density functional theory reveal that the in situ reduction of FeIII to FeII enhances the interaction between the F-SWCNTs and CO. Our results illustrate a new mode of sensors wherein redox active recognition units are voltage-activated to give enhanced and highly specific responses.

Lewis Acid Accelerated Aryl Ether Bond Cleavage with Nickel: Orders of Magnitude Rate Enhancement Using AlMe3.

Study of the kinetics of intramolecular aryl ether C-O bond cleavage by Ni was facilitated by access to a family of metal complexes supported by diphosphines with pendant aryl-methyl ethers. The nature of the aryl substituents was found to have little effect on the rate of cleavage. In contrast, soluble Lewis acidic additives accelerate the aryl ether cleavage dramatically. The effect of AlMe3 was studied in detail, and showed an increase in rate by several orders of magnitude. Low temperature NMR spectroscopy studies demonstrate quantitative coordination of ether to Al. From the Lewis acid-bound precursor, the activation parameters for ether cleavage are significantly lower. These findings provide a mechanistic basis for milder catalyst design for the activation of strong bonds.

An Organocobalt-Carbon Nanotube Chemiresistive Carbon Monoxide Detector.

A chemiresistive detector for carbon monoxide was created from single-walled carbon nanotubes (SWCNTs) by noncovalent modification with diiodo(η5: η1-1-[2-(N,N-dimethylamino)ethyl]-2,3,4,5-tetramethylcyclopentadienyl)-cobalt(III) ([Cp^CoI2]), an organocobalt complex with an intramolecular amino ligand coordinated to the metal center that is displaced upon CO binding. The unbound amino group can subsequently be transduced chemiresistively by the SWCNT network. The resulting device was shown to have a ppm-level limit of detection and unprecedented selectivity for CO gas among CNT-based chemiresistors. This work, the first molecular-level mechanistic elucidation for a CNT-based chemiresistive detector for CO, demonstrates the efficacy of using an analyte's reactivity to produce another chemical moiety that is readily transduced as a strategy for the rational design of chemiresistive CNT-based detectors.

Combination of redox-active ligand and lewis acid for dioxygen reduction with π-bound molybdenum-quinonoid complexes.

A series of π-bound Mo-quinonoid complexes supported by pendant phosphines have been synthesized. Structural characterization revealed strong metal-arene interactions between Mo and the π system of the quinonoid fragment. The Mo-catechol complex (2a) was found to react within minutes with 0.5 equiv of O(2) to yield a Mo-quinone complex (3), H(2)O, and CO. Si- and B-protected Mo-catecholate complexes also react with O(2) to yield 3 along with (R(2)SiO)n and (ArBO)(3) byproducts, respectively. Formally, the Mo-catecholate fragment provides two electrons, while the elements bound to the catecholate moiety act as acceptors for the O(2) oxygens. Unreactive by itself, the Mo-dimethyl catecholate analogue reduces O(2) in the presence of added Lewis acid, B(C(6)F(5))(3), to generate a Mo(I) species and a bis(borane)-supported peroxide dianion, [[(F(5)C(6))(3)B](2)O(2)(2-)], demonstrating single-electron-transfer chemistry from Mo to the O(2) moiety. The intramolecular combination of a molybdenum center, redox-active ligand, and Lewis acid reduces O(2) with pendant acids weaker than B(C(6)F(5))(3). Overall, the π-bound catecholate moiety acts as a two-electron donor. A mechanism is proposed in which O(2) is reduced through an initial one-electron transfer, coupled with transfer of the Lewis acidic moiety bound to the quinonoid oxygen atoms to the reduced O(2) species.

Dipalladium(I) terphenyl diphosphine complexes as models for two-site adsorption and activation of organic molecules.

A para-terphenyl diphosphine was employed to support a dipalladium(I) moiety. Unlike previously reported dipalladium(I) species, the present system provides a single molecular hemisphere for binding of ligands across two metal centers, enabling the characterization and comparison of the binding of a wide variety of saturated and unsaturated organic molecules. The dipalladium(I) terphenyl diphosphine toluene-capped complex was synthesized from a dipalladium(I) hexaacetonitrile precursor in the presence of toluene. The palladium centers display interactions with the π-systems of the central ring of the terphenyl unit and that of the toluene. Exchange of toluene for anisole, 1,3-butadiene, 1,3-cyclohexadiene, thiophenes, pyrroles, or furans resulted in well-defined π-bound complexes which were studied by crystallography, nuclear magnetic resonance (NMR) spectroscopy, and density functional theory. Structural characterization shows that the interactions of the dipalladium unit with the central arene of the diphosphine does not vary significantly in this series allowing for a systematic comparison of the binding of the incoming ligands to the dipalladium moiety. Several of the complexes exhibit rare µ-η(2):η(2) or µ-η(2):η(1)(O or S) bridging motifs. Hydrogenation of the thiophene and benzothiophene adducts was demonstrated to proceed at room temperature. The relative binding strength of the neutral ligands was determined by competition experiments monitored by NMR spectroscopy. The relative equilibrium constants for ligand substitution span over 13 orders of magnitude. This represents the most comprehensive analysis to date of the relative binding of heterocycles and unsaturated ligands to bimetallic sites. Binding interactions were computationally studied with electrostatic potentials and molecular orbital analysis. Anionic ligands were also demonstrated to form π-bound complexes.

Nickel-mediated hydrogenolysis of C-O bonds of aryl ethers: what is the source of the hydrogen?

Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel aryl methoxide complex. Formal ß-H elimination from this species produced a nickel aryl hydride which can undergo reductive elimination in the presence of formaldehyde to generate a carbon monoxide adduct of Ni(0). The reported complexes map out a plausible mechanism of aryl ether hydrogenolysis catalyzed by nickel. Investigations of a previously reported catalytic system using isotopically labeled substrates are consistent with the mechanism proposed in the stoichiometric system, involving ß-H elimination from a nickel alkoxide rather than cleavage of the Ni-O bond by H(2).

Nickel hydrides supported by a non-innocent diphosphine arene pincer: mechanistic studies of nickel-arene H-migration and partial arene hydrogenation.

Nickel hydrides supported by a terphenyl diphosphine were synthesized and found to undergo nickel-to-arene H-transfers. Some of the resulting complexes also undergo the reverse (C-to-Ni) H-migration, indicating the potential for storing H-equivalents in this type of pincer ligand. NMR spectroscopy, single crystal X-ray diffraction, and isotopic labeling studies investigating the mechanism of these processes are discussed.

Synthesis and C-C coupling reactivity of a dinuclear Ni(i)-Ni(i) complex supported by a terphenyl diphosphine.

Mono- and bimetallic complexes of nickel supported by a terphenyl diphosphine have been synthesized. The reported complexes show diverse metal-arene interactions in the solid state. Reactions of an o,o'-biphenyldiyl dinickel complex with CO and dichloroalkanes lead to fluorene derivatives, indicating the formation of carbon-carbon bonds at a bimetallic moiety.