The substituent effect in ethylenes and acetylenes – AIM analysis

The calculations on disubstituted ethylenes YCHCHX with Y = Li, H, F and X = H, F, Li, Na, OH, BeH, NH₂, BH₂, NO₂ were performed at MP2/6-311++G(d,p) level of theory. The analysis of bond lengths and atoms in molecules based theory (AIM) topological parameters such as the characteristics of bond critical points (electron densities and their Laplacians) and atomic radii leads to the conclusion that the AIM parameters are much more sensitive to the action of intramolecular perturbations like substituents than traditional structural parameters such as bond lengths. A comparison of substituted ethylenes with the previously analyzed substituted acetylenes is also given.     

Tandem Stille/Suzuki-Miyaura coupling of a hetero-bis-metalated diene. Rapid, one-pot assembly of polyene systems

[structure: see text]. The synthesis of a hetero-bis-metallo 1,3-butadiene is reported, and its use as an orthogonal Stille and Suzuki-Miyaura coupling partner is detailed. The tin/boron diene participated successfully in a one-pot, sequential Stille and Suzuki-Miyaura coupling protocol, and its utility was demonstrated in the two-step construction of the pentaene side chain of the Fusarium metabolite lucilactaene.     

Titanocene catalyzed 4-exo cyclizations: mechanism, experiment, catalyst design

A method for the preparation of a variety of cyclobutanes via 4-exo cyclization of radicals is presented. Radical generation is carried out by electron transfer from titanocene(III) chlorides to epoxides. The reaction relies on the acceleration of the cyclization through the use of alpha,beta-unsaturated carbonyl compounds as radical traps and the thermodynamic stabilization of the cyclobutylcarbinyl radicals through conjugation. The mechanism of the transformation was investigated by a combined theoretical and experimental study. The computational results provide the crucial energetic and structural features of pertinent intermediates and transition structures. Moreover, the origins of the diastereoselectivity of the 4-exo cyclization are outlined for the first time. Catalysts for those cases where "Cp2TiCl" did not perform in a satisfactory manner have been devised. Through the introduction of tert-butyl or cyclo-hexyl substituted cyclopentadienyl ligands the longevity of the pivotal beta-titanoxy radicals is increased sufficiently enough to enable the slow but often surprisingly diastereoselective formation of the cyclobutylcarbinyl radical. The resulting transformation constitutes the first general approach to cyclobutanes using radical chemistry.     

Classification of data with missing elements and outliers

Missing elements and outliers can often occur in experimental data. The presence of outliers makes the evaluation of any least squares model parameters difficult, while the missing values influence the adequate identification of outliers. Therefore, approaches that can handle incomplete data containing outliers are highly valued. In this paper, we present the expectation-maximization robust soft independent modeling of class analogy approach (EM-S-SIMCA) based on the recently introduced spherical SIMCA method. Several important issues like the possibility of choosing the complexity of the model with the leverage correction procedure, the selection of training and test sets using methods of uniform design for incomplete data and prediction of new samples containing missing elements are discussed. The results of a comparison study showed that EM-S-SIMCA outperforms the classic expectation-maximization SIMCA method. The performance of the method was illustrated on simulated and real data sets and led to satisfactory results.     

Simulation and optimization of 2.6–2.8 μm GaSb-based VCSELs

We present the simulation results of threshold operation of mid-infrared GaSb-based vertical-cavity surface-emitting lasers (VCSELs) obtained with the use of comprehensive fully self-consistent optical-electrical-thermal-recombination numerical model. The results show that by a proper design of VCSEL structure and composition of the active region it is theoretically possible to achieve room-temperature (RT) threshold operation for wavelength of 2.8 μm which is about 0.2 μm longer than those reported so far in the literature for III-V VCSELs with type-I quantum wells. Calculated values of the RT threshold current were equal to 2.5 and 4.0 mA for tunnel-junction diameters of 2 and 4 μm, respectively.     

The Exploration of Chemokines Importance in the Pathogenesis and Development of Endometrial Cancer

Endometrial cancer (EC) is one of the most frequent female malignancies. Because of a characteristic symptom, vaginal bleeding, EC is often diagnosed in an early stage. Despite that, some EC cases present an atypical course with rapid progression and poor prognosis. There have been multiple studies conducted on molecular profiling of EC in order to improve diagnostics and introduce personalized treatment. Chemokines—a protein family that contributes to inflammatory processes that may promote carcinogenesis—constitute an area of interest. Some chemokines and their receptors present alterations in expression in tumor microenvironment. CXCL12, which binds the receptors CXCR4 and CXCR7, is known for its impact on neoplastic cell proliferation, neovascularization and promotion of epidermal–mesenchymal transition. The CCL2–CCR2 axis additionally plays a pivotal role in EC with mutations in the LKB1 gene and activates tumor-associated macrophages. CCL20 and CCR6 are influenced by the RANK/RANKL pathway and alter the function of lymphocytes and dendritic cells. Another axis, CXCL10–CXCR3, affects the function of NK-cells and, interestingly, presents different roles in various types of tumors. This review article consists of analysis of studies that included the roles of the aforementioned chemokines in EC pathogenesis. Alterations in chemokine expression are described, and possible applications of drugs targeting chemokines are reviewed.     

Enhanced Electrocatalytic N2 Reduction via Partial Anion Substitution in Titanium Oxide–Carbon Composites

The electrochemical conversion of N₂ at ambient conditions using renewably generated electricity is an attractive approach for sustainable ammonia (NH₃) production. Considering the chemical inertness of N₂, rational design of efficient and stable catalysts is required. Therefore, in this work, it is demonstrated that a C‐doped TiO₂/C (C‐Ti_xO_y/C) material derived from the metal–organic framework (MOF) MIL‐125(Ti) can achieve a high Faradaic efficiency (FE) of 17.8 %, which even surpasses most of the established noble metal‐based catalysts. On the basis of the experimental results and theoretical calculations, the remarkable properties of the catalysts can be attributed to the doping of carbon atoms into oxygen vacancies (OVs) and the formation of Ti?C bonds in C‐Ti_xO_y. This binding motive is found to be energetically more favorable for N₂ activation compared to the non‐substituted OVs in TiO₂. This work elucidates that electrochemical N₂ reduction reaction (NRR) performance can be largely improved by creating catalytically active centers through rational substitution of anions into metal oxides.     

The Assessment of Meloxicam Phototoxicity in Human Normal Skin Cells: In Vitro Studies on Dermal Fibroblasts and Epidermal Melanocytes

Meloxicam (MLX), which belongs to the oxicam nonsteroidal anti-inflammatory drug derivatives, is an inhibitor of the cyclooxygenase-2 (COX-2) enzyme. Cutaneous adverse effects caused by interaction between UVA radiation and exogenous factors can manifest as phototoxic reactions. Phototoxicity may be a reason for the accumulation of genetic and molecular changes in long-lived cells with low proliferation potential, leading to tumor development. There are several potentially phototoxic drugs, the active component of which is meloxicam. The research aimed to evaluate the influence of MLX and UVAR on skin cells—fibroblasts and melanocytes homeostasis. The obtained results indicated that co-treatment with MLX and UVAR inhibited skin cell proliferation, proportionally to the drug concentration. The observation was confirmed by cytometric analysis of the cell number and viability. The phototoxic effect of MLX was revealed in morphological changes. It was stated that MLX with UVAR lowered the mitochondrial transmembrane potential and changed the cell cycle profile. Additionally, MLX and UVAR caused the disruption of redox homeostasis by lowering the intracellular level of reduced thiols. The presented study revealed that the phototoxic activity of MLX is associated with oxidative stress induction and disruptions in cell homeostasis. The differences in the phototoxic effects of MLX at the cellular level may be related to the different content of melanin pigments.     

Oligoether-strapped meso-pyrimidinylporphyrins

Bis(oligoether-strapped) zinc(II)-meso-pyrimidinylporphyrins were readily synthesized via nucleophilic aromatic substitution reactions of biscathechol-substituted tri- or tetraethylene glycol straps on the upper and lower faces of a Zn(II)-A₂B₂-meso-dichloropyrimidinylporphyrin precursor. The crown ether-like bridges surrounding the porphyrin core create peculiar cavities above and below the macrocyclic plane with appealing features for supramolecular host–guest chemistry.     

Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps

Porphyrin molecules offer immense potential as the light harvesting component of dye-sensitised nanocrystalline TiO(2) solar cells. Synthetic porphyrin dyes were amongst the first dyes trialled for sensitisation of inorganic semiconducting oxides. Today, they exhibit the best performance reported for dye-sensitised solar cells. Accompanying the significant performance improvement over the last two decades is a much improved understanding of efficiency-determining fundamental electron transfer steps, from charge photogeneration to recombination. In this feature article we highlight our recent discoveries of the influence of porphyrin molecule structure on efficiency determining electron transfer kinetics and device performance by systematically changing the molecular structure and observing electron injection and recombination kinetics using time-resolved optical and electrical probes. Despite our observation of ultrafast charge injection for all porphyrin dyes studied by transient absorption spectroscopy, the injection yield estimated using an internal standard remains below 100% and depends strongly on the molecular structure. The observed discrepancy between kinetic competition and the injection yield is attributed to non-injecting dyes, probably arising due to inhomogeneity. A very interesting sub-ns (0.5 ns to 100 ns) charge recombination channel between photo-injected electrons and porphyrin cations is observed, which is found to be more prominent in free-base porphyrin dyes with a conjugated linker. Charge recombination between the acceptor species in the redox containing electrolyte and injected electrons is shown to be an important limitation of most porphyrin-sensitised solar cells, accelerated by the presence of porphyrin molecules at the TiO(2)-electrolyte interface. This recombination reaction is strongly dependent on the porphyrin molecular structure. Bulky substituents, using a porphyrin dimer instead of a porphyrin monomer, a light soaking treatment of freshly prepared films and co-sensitization of TiO(2) with multiple dyes are shown to be successful strategies to improve electron lifetime. Finally, new developments unique to porphyrin dye-sensitised solar cells, including performance enhancements from a light exposure treatment of a zinc porphyrin dye, a significant performance improvement observed after co-sensitisation of TiO(2) with free-base and zinc porphyrin dyes and the use of porphyrin dimers with increased light harvesting in thin-film TiO(2) solar cells are described.