Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

NHC-Adducts of Cyclopentadienyl-Substituted Alanes

The mono- and bis-iodo-substituted NHC-stabilized alanes (NHC) ⋅ AlH₂I and (NHC) ⋅ AlHI₂ offer a convenient entry for further substitution reactions at aluminum. Reactions of (NHC) ⋅ AlH₂I 1 – 4 with one equivalent of NaCp afforded the adducts (NHC) ⋅ AlH₂Cp 9 – 12 (NHC=Me₂Im^Me ( 9 ), iPr₂Im^Me ( 10 ), iPr₂Im ( 11 ), Dipp₂Im ( 12 )). Alane adducts with two Cp substituents (NHC) ⋅ AlHCp₂ 13 – 16 (NHC=Me₂Im^Me ( 13 ), iPr₂Im^Me ( 14 ), iPr₂Im ( 15 ), Dipp₂Im ( 16 )) were prepared by the analogous reaction of (NHC) ⋅ AlHI₂ 5 – 8 using two equivalents of NaCp. The unusual dimeric adducts ((NHC) ⋅ AlH₂Cp ⋅ CpMgI)₂ 17 – 19 (NHC=Me₂Im^Me ( 17 ), iPr₂Im^Me ( 18 ), iPr₂Im ( 19 )) were obtained from the reaction of 1 – 3 with MgCp₂.     

Application of the Tris(acetylacetonato)iron(III)/(II) Redox Couple in p‐Type Dye‐Sensitized Solar Cells

An electrolyte based on the tris(acetylacetonato)iron(III)/(II) redox couple ([Fe(acac)₃]^0/1?) was developed for p‐type dye‐sensitized solar cells (DSSCs). Introduction of a NiO blocking layer on the working electrode and the use of chenodeoxycholic acid in the electrolyte enhanced device performance by improving the photocurrent. Devices containing [Fe(acac)₃]^0/1? and a perylene–thiophene–triphenylamine sensitizer (PMI–6T–TPA) have the highest reported short‐circuit current (J_SC=7.65 mA cm^?2), and energy conversion efficiency (2.51 %) for p‐type DSSCs coupled with a fill factor of 0.51 and an open‐circuit voltage V_OC=645 mV. Measurement of the kinetics of dye regeneration by the redox mediator revealed that the process is diffusion limited as the dye‐regeneration rate constant (1.7×10⁸ M ^?1 s^?1) is very close to the maximum theoretical rate constant of 3.3×10⁸ M ^?1 s^?1. Consequently, a very high dye‐regeneration yield (>99 %) could be calculated for these devices.     

Supramolecularly engineered phospholipids constructed by nucleobase molecular recognition: upgraded generation of phospholipids for drug delivery

Despite of great advances of phospholipids and liposomes in clinical therapy, very limited success has been achieved in the preparation of smart phospholipids and controlled-release liposomes for in vivo drug delivery and clinical trials. Here we report a supramolecular approach to synthesize novel supramolecularly engineered phospholipids based on complementary hydrogen bonding of nucleosides, which greatly reduces the need of tedious chemical synthesis, including reducing the strict requirements for multistep chemical reactions, and the purification of the intermediates and the amount of waste generated relative more traditional approaches. These upgraded phospholipids self-assemble into liposome-like bilayer structures in aqueous solution, exhibiting fast stimuli-responsive ability due to the hydrogen bonding connection. In vitro and in vivo evaluations show the resulted supramolecular liposomes from nucleoside phospholipids could effectively transport drug into tumor tissue, rapidly enter tumor cells, and controllably release their payload in response to an intracellular acidic environment, thus resulting in a much higher antitumor activity than conventional liposomes. The present supramolecularly engineered phospholipids represent an important evolution in comparison to conventional covalent-bonded phospholipid systems.     

Band-dominated operators on metric measure spaces

We generalise the notion of band-dominated operators originally introduced for the space ℓ_p(ℤⁿ) to the setup of metric measure spaces and show various algebraic properties of this space of operators. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Selective,Transition Metal-free 1,2-Diboration of Alkyl Halides,Tosylates, and Alcohols

Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program.     

Effects of Periodic Excitation on the Flow Around a D-Shaped Cylinder at Low Reynolds Numbers

The baseline and forced flow around a bluff body with semi-elliptical D-shape was investigated by solving the 2D Navier–Stokes equations at low Reynolds numbers. A D-shape rather than the canonic circular-cylinder was selected due to the fixed separation points in the latter, enabling to study a pure wake rather than boundary-layer control. The correlation between Strouhal and Reynolds numbers, the mean drag, the lift and drag oscillations vs. the Reynolds number and wake structure were investigated and compared to experimental and numerical data. Effects of open-loop forcing, resulting from the influence of zero-mass-flux actuators located at the fixed separation points, were studied at a Reynolds number of 150. Fluidic rather than body motion or volume forcing was selected due to applicability considerations. The motivation for the study was to quantify the changes in the flow field features, as captured by Proper Orthogonal Decomposition (POD) analysis, due to open-loop forcing, inside and outside the “lock-in” regime. This is done in order to evaluate the suitability of low-order-models based on POD modes of this changing flow field, for future feed-back flow control studies. The evolution of the natural and the excited vortices in the Kármán wake were also investigated. The formation and convection regions of the vortex evolution were documented. It was found that the forcing causes an earlier detachment of the vortices from the boundary-layers, but does not affect their circulation or convection speeds. The results of the POD analysis of the near-wake flow show that the influence of the bluff body shape (“D”-shaped versus circular cylinder) on the baseline POD wake modes is small. It was found that the eigenfunctions (mode-shapes) of the POD velocity modes are less sensitive to slot excitation than the vorticity modes. As a result of the open-loop excitation, two types of mode-shape-change were observed: a mode can be exchanged with a lower-energy mode or shifted to a low energy level. In the latter case, the most energetic mode becomes the “actuator” mode. The evolution of one-slot excitation on still fluid (“Synthetic jet”) was studied and compared to published data and to “actuator” modes with external flow present. Based on the current findings, it is hypothesized that the cross-flow velocity POD modes are suitable for feedback control of wake flow using periodic excitation, due to their low sensitivity to the excitation as compared to the streamwise velocity or vorticity modes.     

Optimality of the quantified Ingham–Karamata theorem for operator semigroups with general resolvent growth

We prove that a general version of the quantified Ingham–Karamata theorem for $$C_0$$-semigroups is sharp under mild conditions on the resolvent growth, thus generalising the results contained in a recent paper by the same authors. It follows in particular that the well-known Batty–Duyckaerts theorem is optimal even for bounded $$C_0$$-semigroups whose generator has subpolynomial resolvent growth. Our proof is based on an elegant application of the open mapping theorem, which we complement by a crucial technical lemma allowing us to strengthen our earlier results.