Asymmetric Phase-Transfer Catalysis

Both in the laboratory and industrially , phase-transfer catalysis offers the potential to induce asymmetry into reactions with anionic intermediates. Equation (a) provides an example (conditions: a) 10 mol % phase-transfer catalyst, BnBr, CsOH⋅H₂O, PhMe, 15–24 h, −78°C).     

A Convergent Strategy for the Asymmetric Synthesis of Enantiomerically Pure Bicyclic Compounds by Using a Silicon-Directed Cycloaddition Reaction: The Synthesis of Enantiomerically Pure Bicyclo[3.2.0]hept-2-en-6-one

An asymmetric allylmetalation followed by a silicon-stereodirected cycloaddition gives enantiomerically pure bicyclic compounds. The synthesis of enantiopure 1 (see scheme) in a yield of 65–74 %, 93 % ee, and >98 % de provides an illustration of the efficacy of the method. The preferential formation of 1 rather than its diastereoisomer (32:1), during the cycloaddition step, matches the result predicted by RHF and density functional theory studies.     

Human Group IIA Phospholipase A2—Three Decades on from Its Discovery

Phospholipase A₂ (PLA₂) enzymes were first recognized as an enzyme activity class in 1961. The secreted (sPLA₂) enzymes were the first of the five major classes of human PLA₂s to be identified and now number nine catalytically-active structurally homologous proteins. The best-studied of these, group IIA sPLA₂, has a clear role in the physiological response to infection and minor injury and acts as an amplifier of pathological inflammation. The enzyme has been a target for anti-inflammatory drug development in multiple disorders where chronic inflammation is a driver of pathology since its cloning in 1989. Despite intensive effort, no clinically approved medicines targeting the enzyme activity have yet been developed. This review catalogues the major discoveries in the human group IIA sPLA₂ field, focusing on features of enzyme function that may explain this lack of success and discusses future research that may assist in realizing the potential benefit of targeting this enzyme. Functionally-selective inhibitors together with isoform-selective inhibitors are necessary to limit the apparent toxicity of previous drugs. There is also a need to define the relevance of the catalytic function of hGIIA to human inflammatory pathology relative to its recently-discovered catalysis-independent function.     

Light scattering and dielectric relaxation studies of glass forming liquids

Extended Abstract: Glass forming organic liquids and polymers exhibit long range density fluctuations with correlation length ξ in the range of 10–300 nm at temperatures above T_g (1 - 6). This follows from dynamic and static light scattering experiments revealing some unexpected features, which cannot be explained on the basis of conventional liquid state theories: (i) In static light scattering the intensity I(q → 0) is no longer proportional to the isothermal compressibility, (ii) This excess scattering I_exc shows a strong q-dependence (q = (4π/Λ.)sin(θ/2)) corresponding to a correlation length ξ in the above mentioned range, (iii) The Landau-Placzek ratio I_Rayleigh/2I_Brillouin is much too high compared with the results of light scattering theories, (iv) In photon correlation spectroscopy a new ultraslow hydrodynamic mode (Γ ˜ q²) is detected with relaxation rates Γ about 10⁻⁶ to 10⁻⁹ lower than those of the α-process at a given temperature. In order to explain these observations, a two-state fluid model is proposed, which starts from the coexistence of “liquid-like” and “aperiodic solid-like” regions within the liquids. Such ideas have been discussed many times before, so for example A.R. Ubbelohde (7) speculates about “anticrystalline” clusters in liquids. Molecular dynamics simulations of atomic liquids showed that long range orientational fluctuations appear upon supercooling (8). A preferred icosahedral ordering is observed (9) and the number of icosahedral clusters increases with decreasing temperature (10). In connection with the interpretation of the dynamics of supercooled liquids different “two-state” models have been proposed (11 - 15). For the explanation of the light scattering results we propose that the molecules in the different dynamic states (“liquid” or “solid”) aggregate during annealing of the liquid at temperatures above T_g. Experiments showed that the equilibration times can be rather long (3 - 5), but nevertheless the liquids exhibiting long range density fluctuations are in the state of lowest free energy. We claim that our observations are the first experimental proof of the existence of such different dynamic states, which have been discussed many times before. The extended secondary clusters can also be detected by ultra small angle X-ray scattering.     

Quantitative comparison of selectivities in the polymerization of cyclic esters

Chain transfer processes (k_tr) taking place in the polymerization (anionic and pseudoanionic) of cyclic esters (lactones) are reviewed. These reactions are mostly responsible for the departure of these systems from the fully controlled (living) polymerizations. The ratios of k_p/k_tr have been determined for a number of initiating systems and the structures of the growing species are related to their selectivity, expressed by k_p/k_tr. It has been shown that the less reactive and more sterically crowded active species polymerize more selectively.     

Scale-up and Sustainability Evaluation of Biopolymer Production from Citrus Waste Offering Carbon Capture and Utilisation Pathway

Poly(limonene carbonate) (PLC) has been highlighted as an attractive substitute to petroleum derived plastics, due to its utilisation of CO₂ and bio-based limonene as feedstocks, offering an effective carbon capture and utilisation pathway. Our study investigates the techno-economic viability and environmental sustainability of a novel process to produce PLC from citrus waste derived limonene, coupled with an anaerobic digestion process to enable energy cogeneration and waste recovery maximisation. Computational process design was integrated with a life cycle assessment to identify the sustainability improvement opportunities. PLC production was found to be economically viable, assuming sufficient citrus waste is supplied to the process, and environmentally preferable to polystyrene (PS) in various impact categories including climate change. However, it exhibited greater environmental burdens than PS across other impact categories, although the environmental performance could be improved with a waste recovery system, at the cost of a process design shift towards energy generation. Finally, our study quantified the potential contribution of PLC to mitigating the escape of atmospheric CO₂ concentration from the planetary boundary. We emphasise the importance of a holistic approach to process design and highlight the potential impacts of biopolymers, which is instrumental in solving environmental problems facing the plastic industry and building a sustainable circular economy.     

Manufacturing of Volumetric Glass–Based Composites with Single‐ and Double‐QD Doping

Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels.     

Enhanced Ar-K X-ray emission observed in EBIT at electron energies around 6,500 eV

Recently (2015) at the Institute of Physics of the Jagiellonian University, a commercial electron beam ion source (Dresden EBIT, DREEBIT Co.) was installed for teaching and scientific purposes. The first experiments were focused on observation of radiative recombination and dielectronic recombination (DR). A good resolution of the X-ray spectra for DR in argon encouraged a more detailed search. An investigation of higher order resonances, namely, trielectronic recombination (TR: KK-LLL, KK-LLM,…) in argon ions, was initiated. The present experiment was conducted while scanning the electron beam energy of the EBIT over the region 5,700–7200 eV. This electron energy region was expected to manifest an enhancement of the Ar-K X-ray emission due to TR processes mentioned above. Indeed, a maximum-like behavior of the radiation intensity was observed.     

A computational investigation of the finite-time blow-up of the 3D incompressible Euler equations based on the Voigt regularization

We report the results of a computational investigation of two blow-up criteria for the 3D incompressible Euler equations. One criterion was proven in a previous work, and a related criterion is proved here. These criteria are based on an inviscid regularization of the Euler equations known as the 3D Euler–Voigt equations, which are known to be globally well-posed. Moreover, simulations of the 3D Euler–Voigt equations also require less resolution than simulations of the 3D Euler equations for fixed values of the regularization parameter \(\alpha >0\). Therefore, the new blow-up criteria allow one to gain information about possible singularity formation in the 3D Euler equations indirectly, namely by simulating the better-behaved 3D Euler–Voigt equations. The new criteria are only known to be sufficient criterion for blow-up. Therefore, to test the robustness of the inviscid-regularization approach, we also investigate analogous criteria for blow-up of the 1D Burgers equation, where blow-up is well known to occur.     

Nonnegative Discrete Symbols and Their Probabilistic Interpretation

We review the quantizer–dequantizer formalism of constructing symbols of the density operators and quantum observables, such as Wigner functions and tomographic-probability distributions. We present a tutorial consideration of the technique of obtaining minimal sets of dequantizers (quorum) related to the observable eigenvalues for one-qubit states. We discuss a generalization of the quantizer–dequantizer scheme on the example of spin-1/2 states. We consider the possibilities of extending the results to two-qubit systems using spin tomograms of the state density matrix.