Solvolysis of 1,1-dimethyl-4-alkenyl chlorides: evidence for pi-participation

Tertiary 1,1-dimethyl-4-alkenyl chloride (1) solvolyzes with significantly reduced secondary beta-deuterium kinetic isotope effect (substrate with two trideuteromethyl groups) and has a lower entropy and enthalpy of activation than the referent saturated analogue 4 (k(H)/k(D) = 1.30 +/- 0.03 vs k(H)/k(D) = 1.79 +/- 0.01; Delta Delta H(++) = -9 kJ mol(-1), Delta Delta S(++) = -36 J mol(-1) K(-1), in 80% v/v aqueous ethanol), indicating participation of the double bond in the rate-determining step. Transition structure 1-TS computed at the MP2(fc)/6-31G(d) level of theory revealed that the reaction proceeds through a late transition state with considerably pronounced double bond participation and a substantially cleaved C-Cl bond. The doubly unsaturated compound 3 (1,1-dimethyl-4,8-alkadienyl chloride) solvolyzes with further reduction of the isotope effect, and a drastically lower entropy of activation (k(H)/k(D) = 1.14 +/- 0.01; DeltaS(++) = -152 +/- 12 J mol(-1) K(-1), in 80% v/v aqueous ethanol), suggesting that the solvolysis of 3 proceeds by way of extended pi-participation, i.e., the assistance of both double bonds in the rate-determining step.     

Experimental and modeling study of charge carriers release from traps by interaction with molecular vibrations in silicon organic polymers

Abstract

The dependence of the charge carrier’s release from traps on the polymer ordering and the widths of the vibration bands are investigated in five silicon organic polymers using thermoluminescence in the 5–200?K temperature range and the Raman spectra. The influence of the vibrations on the thermoluminescence is caused by the processes of the charge carriers’ release from traps via the absorption of vibration quanta. The effect manifests itself in both the appearance of discrete levels of the carriers’ activation energy which coincides with the energy of the vibration quanta and the formation of a structure on the thermoluminescence curve. It is shown, that the magnitude of effects depends on the widths of optical vibration bands and the ordering of the polymers. The mechanisms of interactions of trapped charges with molecular vibrations are analyzed and the values of microscopical parameters of such interactions are determined. It is shown that the contribution of molecular vibrations in the charge release from the trap is great.     

Influence of additives and post-synthesis treatment on the structural properties of sol-gel prepared alumina-doped zirconia studied by EXAFS-spectroscopy and X-ray diffraction

Alumina- (5 and 10 wt%) doped zirconia samples were prepared by sol-gel processing of aluminum sec-butoxide and zirconium butoxide in the presence of acids (acetic, sulfuric or nitric acid) or organic additives (Pluronic P123). X-ray absorption spectroscopy, X-ray diffraction and nitrogen adsorption experiments showed that the structure of the synthesized mixed oxides is strongly influenced by the chemical synthesis parameters.     

A Biomorphic Model of Cortical Column for Content—Based Image Retrieval

How do living systems process information? The search for an answer to this question is ongoing. We have developed an intelligent video analytics system. The process of the formation of detectors for content-based image retrieval aimed at detecting objects of various types simulates the operation of the structural and functional modules for image processing in living systems. The process of detector construction is, in fact, a model of the formation (or activation) of connections in the cortical column (structural and functional unit of information processing in the human and animal brain). The process of content-based image retrieval, that is, the detection of various types of images in the developed system, reproduces the process of “triggering” a model biomorphic column, i.e., a detector in which connections are formed during the learning process. The recognition process is a reaction of the receptive field of the column to the activation by a given signal. Since the learning process of the detector can be visualized, it is possible to see how a column (a detector of specific stimuli) is formed: a face, a digit, a number, etc. The created artificial cognitive system is a biomorphic model of the recognition column of living systems.     

Columnar Aggregates of Azobenzene Stars: Exploring Intermolecular Interactions,Structure, and Stability in Atomistic Simulations

We present a simulation study of supramolecular aggregates formed by three-arm azobenzene (Azo) stars with a benzene-1,3,5-tricarboxamide (BTA) core in water. Previous experimental works by other research groups demonstrate that such Azo stars assemble into needle-like structures with light-responsive properties. Disregarding the response to light, we intend to characterize the equilibrium state of this system on the molecular scale. In particular, we aim to develop a thorough understanding of the binding mechanism between the molecules and analyze the structural properties of columnar stacks of Azo stars. Our study employs fully atomistic molecular dynamics (MD) simulations to model pre-assembled aggregates with various sizes and arrangements in water. In our detailed approach, we decompose the binding energies of the aggregates into the contributions due to the different types of non-covalent interactions and the contributions of the functional groups in the Azo stars. Initially, we investigate the origin and strength of the non-covalent interactions within a stacked dimer. Based on these findings, three arrangements of longer columnar stacks are prepared and equilibrated. We confirm that the binding energies of the stacks are mainly composed of π–π interactions between the conjugated parts of the molecules and hydrogen bonds formed between the stacked BTA cores. Our study quantifies the strength of these interactions and shows that the π–π interactions, especially between the Azo moieties, dominate the binding energies. We clarify that hydrogen bonds, which are predominant in BTA stacks, have only secondary energetic contributions in stacks of Azo stars but remain necessary stabilizers. Both types of interactions, π–π stacking and H-bonds, are required to maintain the columnar arrangement of the aggregates.     

On Laplace and Stokes potentials

Integral equations associated with the basic boundary value problems for the Laplace and Stokes equations are considered. The integral operators for these integral equations are interpreted as the pseudodifferential operators, and their principal symbols are calculated. The symbols are obtained in terms of the principal curvatures and the coefficients of the first quadratic form of the boundary. As a consequence, the initial approximation is suggested for the iterative methods solving the integral equations. © 1998 by B. G. Teubner Stuttgart–John Wiley & Sons Ltd.     

Dye-sensitized solar cells based on Fe N-heterocyclic carbene photosensitizers with improved rod-like push-pull functionality

A new generation of octahedral iron(ii)–N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push–pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push–pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I⁻/I₃⁻ redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO₂. Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO₂. However, an ultrafast recombination process results in undesirable fast charge recombination from TiO₂ back to the oxidized dye, leaving only 5–10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6–8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work.

Iron-based photosensitizers for dye-sensitized solar cells with a rod-like push–pull design. Solar cell performance was limited by ultrafast (sub-ps) recombination, but yielded better performance than the homoleptic parent photosensitizer.     

Low-Temperature Sputtered Ultralow-Loss Silicon Nitride for Hybrid Photonic Integration

Silicon-nitride-on-insulator (Si₃N₄) photonic circuits have seen tremendous advances in many applications, such as on-chip frequency combs, Lidar, telecommunications, and spectroscopy. So far, the best film quality has been achieved with low pressure chemical vapor deposition (LPCVD) and high-temperature annealing (1200°C). However, high processing temperatures pose challenges to the cointegration of Si₃N₄ with pre-processed silicon electronic and photonic devices, lithium niobate on insulator (LNOI), and Ge-on-Si photodiodes. This limits LPCVD as a front-end-of-line process. Here, ultralow-loss Si₃N₄ photonics based on room-temperature reactive sputtering is demonstrated. Propagation losses as low as 5.4 dB m⁻¹ after 400°C annealing and 3.5 dB m⁻¹ after 800°C annealing are achieved, enabling ring resonators with highest optical quality factors of > 10 million and an average quality factor of 7.5 million. To the best of the knowledge, these are the lowest propagation losses achieved with low temperature Si₃N₄. This ultralow loss enables the generation of microresonator soliton frequency combs with threshold powers of 1.1 mW. The introduced sputtering process offers full complementary metal oxide semiconductor (CMOS) compatibility with front-end silicon electronics and photonics. This could enable hybrid 3D integration of low loss waveguides with integrated lasers and lithium niobate on insulator.     

Solid phase extraction of halogenated pesticides from ground and surface waters and their determination by capillary gas chromatography

A critical study of a solid phase extraction method using C₁₈ SPE columns for the determination of 23 halogenated pesticides is presented. Type of sorbent, sorbent mass, flow rate in the extraction process, sample concentration of the different compounds, sample volume, pH, ionic strength and type of water were evaluated. Recoveries of pesticides under study yield a linear relationship, except for conazole fungicides and captan. Losses can be expected for heptachlor, aldrin, and captan. Sample volume and flow rate of extraction affect recoveries. Matrix effects from surface and groundwaters were observed. Recoveries for vinelozolin and dieldrin from groundwater were lower than those obtained from nanopure water. In river water losses of these compounds are higher. Captan and penconazole were not present and high losses were obtained for trifluralin, α-BHC, γ-BHC, tri-allate and chlorpyriphos. Impurities arising from the sorbent materials of cartridges have been detected.     

Uncertainty Propagation for Compositional Flow Using a Probability Distribution Method

Transport in Porous Media - The paper presents a novel approach for uncertainty propagation in multicomponent two-phase displacements. This approach originates from and extends the frozen...