Composition of the Defensive Secretion in Three Species of European Millipedes

Three European julid species, Cylindroiulus boleti, Leptoiulus trilineatus, and Megaphyllum bosniense, secrete mixtures of up to 12 different quinones. The major components in these species are 2-methoxy-3-methyl-1,4-benzoquinone and 2-methyl-1,4-benzoquinone. 2-Methoxy-5-methylhydroquinone is detected for the first time in the Class Diplopoda. 2-Hydroxy-3-methyl-1,4-benzoquinone, 2,3-dimethoxyhydroquinone, 2-methyl-3,4-methylendioxyphenol, and 2,3-dimethoxy-5-methylhydroquinone are registered for the first time in representatives of the family Julidae. The similar chemical composition of defense secretions in all analyzed European julids and Pacific spirobolids supports the idea of the chemical consistency of defensive compounds in juliform millipedes.     

CO2 laser-assisted preparation of transparent Eu2Ti2O7 thin films

We present a laser-assisted preparation of transparent europium-titanate Eu₂Ti₂O₇ thin films with tailored structural and optical properties. We have evaluated the effects of the irradiation time on the structural and the optical properties of the films. This approach allows the preparation of nanocrystalline crack-free films and micro patterns. The amorphous thin films were prepared by a sol-gel method. The films were annealed by a CO₂ laser beam for various time intervals. The laser irradiation induced a crystallization process that resulted in the formation of Eu₂Ti₂O₇ nanocrystals. The nanocrystals regularly grew with increasing irradiation time reaching the size from 25?nm to 45?nm. A film of a thickness 480?nm exhibited an optical transmission of 91.9% that is close to the maximal theoretical limit. The film's refractive index at 632?nm was 2.26. A micrometric pattern was prepared by a direct laser writing followed by a wet chemical etching. Feasibility of the demonstrated approach, together with the high film's quality, and europium-titanate chemical resistivity open up many opportunities for advanced applications. The approach can be used for a preparation of protective coatings and integrated photonic devices such as planar optical waveguides and couplers.     

COSMO‐based computer‐aided molecular/mixture design: A focus on reaction solvents

In this article, we investigate reaction solvent design using COSMO‐RS thermodynamics in conjunction with computer‐aided molecular design (CAMD) techniques. CAMD using COSMO‐RS has the distinct advantage of being a method based in quantum chemistry, which allows for the incorporation of quantum‐level information about transition states, reactive intermediates, and other important species directly into CAMD problems. This work encompasses three main additions to our previous framework for solvent design (Austin et al., Chem Eng Sci. 2017;159:93–105): (1) altering the group contribution method to estimate hydrogen‐bonding and non‐hydrogen‐bonding σ‐profiles; (2) ab initio modeling of strong solute/solvent interactions such as H‐bonding or coordinate bonding; and (3) solving mixture design problems limited to common laboratory and industrial solvents. We apply this methodology to three diverse case studies: accelerating the reaction rate of a Menschutkin reaction, controlling the chemoselectivity of a lithiation reaction, and controlling the chemoselectivity of a nucleophilic aromatic substitution reaction. We report improved solvents/mixtures in all cases. © 2017 American Institute of Chemical Engineers AIChE J, 63: 104–122, 2018     

Cyp1 Inhibition Prevents Doxorubicin-Induced Cardiomyopathy in a Zebrafish Heart-Failure Model

Doxorubicin is a highly effective chemotherapy agent used to treat many common malignancies. However, its use is limited by cardiotoxicity, and cumulative doses exponentially increase the risk of heart failure. To identify novel heart failure treatment targets, a zebrafish model of doxorubicin-induced cardiomyopathy was previously established for small-molecule screening. Using this model, several small molecules that prevent doxorubicin-induced cardiotoxicity both in zebrafish and in mouse models have previously been identified. In this study, exploration of doxorubicin cardiotoxicity is expanded by screening 2271 small molecules from a proprietary, target-annotated tool compound collection. It is found that 120 small molecules can prevent doxorubicin-induced cardiotoxicity, including 7 highly effective compounds. Of these, all seven exhibited inhibitory activity towards cytochrome P450 family 1 (CYP1). These results are consistent with previous findings, in which visnagin, a CYP1 inhibitor, also prevents doxorubicin-induced cardiotoxicity. Importantly, genetic mutation of cyp1a protected zebrafish against doxorubicin-induced cardiotoxicity phenotypes. Together, these results provide strong evidence that CYP1 is an important contributor to doxorubicin-induced cardiotoxicity and highlight the CYP1 pathway as a candidate therapeutic target for clinical cardioprotection.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Engraftment of Prevascularized,Tissue Engineered Constructs in a Novel Rabbit Segmental Bone Defect Model

The gold standard treatment of large segmental bone defects is autologous bone transfer, which suffers from low availability and additional morbidity. Tissue engineered bone able to engraft orthotopically and a suitable animal model for pre-clinical testing are direly needed. This study aimed to evaluate engraftment of tissue-engineered bone with different prevascularization strategies in a novel segmental defect model in the rabbit humerus. Decellularized bone matrix (Tutobone) seeded with bone marrow mesenchymal stromal cells was used directly orthotopically or combined with a vessel and inserted immediately (1-step) or only after six weeks of subcutaneous “incubation” (2-step). After 12 weeks, histological and radiological assessment was performed. Variable callus formation was observed. No bone formation or remodeling of the graft through TRAP positive osteoclasts could be detected. Instead, a variable amount of necrotic tissue formed. Although necrotic area correlated significantly with amount of vessels and the 2-step strategy had significantly more vessels than the 1-step strategy, no significant reduction of necrotic area was found. In conclusion, the animal model developed here represents a highly challenging situation, for which a suitable engineered bone graft with better prevascularization, better resorbability and higher osteogenicity has yet to be developed.     

IR-change and colour changes of long-oil air drying alkyd paints as a result of UV irradiation

In this study the formation of photo-oxidative species was studied by monitoring the changes in the FT-IR spectra and colour changes. To stabilize long-oil air drying alkyd paint, separate and synergistic influence of two stabilizers were used Uvasorb^®S28 as the UV-absorber and Uvasorb^®HA29 as the stabilizer which inhibits the degradation of some groups. In the presence of UV radiation (450 h, λ > 300 nm), the alkyd paint undergoes photodegradation with gradual change of its colour. The photochemical degradation of the alkyd paint is associated with an increase in the hydroxyl content and broadening of the absorption in the carbonyl region. Analysis of the colour changes in alkyd surface during photodegradation was carried out by measuring CIEL*a*b* colour components (L*, a*, b* and ΔE*). Overall, ΔE* colour change correlates well with photodegradation of alkyd paint by relative increase of the concentration of carbonyl and hydroxyl groups determinated by FT-IR measurements.     

Effect of amine-terminated butadiene-acrylonitrile/clay combinations on the structure and properties of epoxy nanocomposites

The effect of the clay content and the method of its combination with amine-terminated butadiene-acrylonitrile (ATBN) on the structure and behavior of epoxy was studied. In the case of the simultaneous addition of both components, the increasing clay content had a very small effect on the size of the reaction-induced phase separation-formed particles at 5% rubber content due to predominant elimination of two major clay effects, i.e., the nucleation due to phase separation and the kinetics. As a result, both the time window between the onset of phase separation and vitrification and the viscosity at the cloud point did not change significantly. The minor change in the particle size/clay content dependences with different curing temperatures indicates that the balance between the two clay effects shifted. The corresponding study of the mechanical behavior indicated that the best balanced mechanical properties were obtained at certain clay/ATBN ratios, and thus, there was synergy between the components. Similar mechanical parameters were obtained for the application of both components in the form of ATBN/montmorillonite intercalate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012