Er<Superscript>3+</Superscript> as glass structure modifier of Ga–Ge–S chalcogenide system

Er³⁺ clustering phenomenon in Ga–Ge–S chalcogenide system is studied using Raman spectroscopy. The Raman spectra from 10 to 500 cm⁻¹ for glasses (100−y)[15Ga₂S₃–85GeS₂]–yEr₂S₃ (y=0.08−5.00 mol. %) have been analyzed. To reveal the influence of the chemical composition on the glass structure the intensity of the peak corresponding to Ge–Ge (Ga–Ga) homopolar bonds has been examined. The peak intensity increase with Er₂S₃ concentration change in the region 0<C(Er₂S₃)<2 mol. % has been interpreted in terms of the sulphur deficiency in the glass resulting in the formation of S₃Ge–GeS₃ (S₃Ga-GaS₃) structural units. The further increase in concentration beyond 2 mol. % reduces the sulphur deficiency, which can be attributed to the formation of the ternary compound Er₃GaS₆. The structural units Er₃GaS₆ contain a large mol. fraction of Er³⁺ or, in other words, Er³⁺ clusters. The data obtained from the low-frequency Raman spectra (boson band) indicate strong variations of the medium-range order (MRO) in the glasses induced by Er³⁺. The observed behavior of the MRO size (the correlation length) with increasing of Er₂S₃ concentration provides for additional evidence of the Er³⁺ clustering.     

Anomalous Odd–Even Effects in Columnar and Smectic Phases of Discotic Tetraphenylenes

Rather uncommon but pronounced odd–even effects in the clearing temperatures of liquid crystals are found for three new homologous series of discotic tetraphenylenes (see figure). Detailed similarities to the well‐known odd‐even effects in calmitic mesogens point towards a more general understanding of odd‐even effects in liquid crystals.

     

Fracture Analysis for a Frictional Fastener Hole with Edge Cracks in an Anisotropic Plate∗

Abstract

Stress intensity factors are evaluated for a singly or doubly cracked fastener hole with frictional traction in an anisotropic plate, using a special kernel boundary integral equation (BIE) approach. The integration kernel (Green's function) used in this BIE approach has already taken the presence of the crack (or cracks) into account, thus.avoiding the need for element discretization to model the stress singularity at the crack tip. The Green's function employed is that of an infinite anisotropic plate containing an elliptical hole or crack, and subjected to an arbitrarily positioned point force. Several types of normal and shear traction conditions at the pinhole interface are considered. Numerical results are obtained for various geometrical and loading conditions and are compared with known solutions, where available, for their isotropic counterparts.     

Electroless silver plating on tetraethoxy silane-bridged fiber glass

Tetraethoxy silane was used to functionalize the surface of fiber glass (FG) for adsorption with the electroless plated silver shell. The performance of electroless silver plated FG with tetraethoxy silane modification was compared to that of unmodified FG in terms of mechanical and electrical properties. The silane bridge provided more stability for binding with different concentrations of electroless plating silver ions. The characterization was investigated by using field emission scanning electron microscope (FESEM), X-ray diffraction patterns (XRD), energy-dispersion X-ray (EDX), metal microscope (MM) and electric resistance. The Ag coating on TEOS modified FG was more durable than that of unmodified FG in the ball milling test, as confirmed by the data of electric resistance and residue weight. The optimized conditions for producing the Ag coating FG were also investigated. The Ag-Si-FG-3-c product in this study has the lowest electrical resistance of 1.56 × 10³ Ω/cm² and good mechanical stability as exhibited in ball milling tests.     

Cytotoxic phenylpropanoids and a new triterpene, turformosinic acid, from Turpinia formosana Nakai

One new phenylpropanoid, turformosin A (1), and one new triterpene, turformosinic acid (2), together with 16 known compounds, were isolated from the stems of Turpinia formosana Nakai. All structures were elucidated on the basis of spectroscopic analysis, including 1D- and 2D-NMR techniques and MS analysis. Selected isolated compounds were evaluated for in vitro cytotoxicity against four human cancer cell lines and antioxidant scavenging effects on DPPH. (-)-(7'S,8'S)-threo-carolignan X (3) exhibited cytotoxicity against Hep2, WiDr, Daoy, and MCF-7 cell lines with ED(50) values of 3.60, 4.45, 6.07, and 13.7 μg/mL, respectively. Turformosin A (1), (-)-(7'S,8'S)- threo-carolignan X (3), methoxyhydroquinone-4-β-D-glucopyranoside (5), and methoxy-hydroquinone-1-β-D-glucopyranoside (6), exhibited similar anti-oxidative activity. Hep2 cells treated with 10 μg/mL of 3 showed elevation of sub-G1 population (from 20% at 8 h to 60% at 48 h), and activation of caspase-9/caspase-3/PARP cascade. Compound 3 induced intrinsic apoptotic pathway in Hep2 cells with dose and time dependence (10 μg/mL for 8 h).     

Bioactive pregnane-type steroids from the soft coral Scleronephthya gracillimum

Nine new steroids, sclerosteroids A-I (1, 5, 6, 8-13), along with 18 known metabolites (2-4, 7, 14-27), were isolated from the soft coral Scleronephthya gracillimum. These structures were elucidated on the basis of detailed spectroscopic analysis. The absolute configurations of sugar moieties in steroidal glycosides 10-13 were determined by HPLC analysis of the o-tolylthiocarbamate derivatives of the liberated sugars from hydrolysis of these steroidal giycosides. Cytotoxic and anti-inflammatory activities of these compounds were measured in vitro.     

peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetate esters: a model for mandelate racemase

The rate constants for exchange of hydrogen for deuterium at the α-CH(2) positions of 8-(N,N-dimethylaminonaphthalen-1-yl)acetic acid tert-butyl ester 1 and naphthalen-1-ylacetic acid tert-butyl ester 2 have been determined in potassium deuteroxide solutions in 1 : 1 D(2)O : CD(3)CN, in order to quantify the effect of the neighbouring peri-dimethylamino substituent on α-deprotonation. Intramolecular general base catalysis by the (weakly basic) neighbouring group was not detected. Second-order rate constants, k(DO), for the deuterium exchange reactions of esters 1 and 2 have been determined as 1.35 × 10(-4) M(-1) s(-1) and 3.95 × 10(-3) M(-1) s(-1), respectively. The unexpected 29-fold decrease in the k(DO) value upon the introduction of a peri-dimethylamino group is attributed to an unfavourable steric and/or electronic substituent effect on intermolecular deprotonation by deuteroxide ion. From the experimental k(DO) values, carbon acid pK(a) values of 26.8 and 23.1 have been calculated for esters 1 and 2.     

Theoretical investigation of plasmonic enhancement of silica-coated gold nanorod on molecular fluorescence

The plasmonic enhancement or quenching effects of a silica-coated gold nanorod (GNR@SiO₂) on the fluorescence of a molecule doped in the silica layer are studied using the multiple multipole method. The enhancement factors (EF) of a GNR with a typical aspect ratio of 3 coated by a 13 nm silica layer upon the fluorescence of a molecule embedded at different locations with various orientations irradiated by a plane wave are analyzed, particularly at the longitudinal surface plasmon resonance (SPR) of GNR. The numerical results show that the EF of a GNR@SiO₂ on the fluorescence is sensitive to the molecular location and orientation. Furthermore, an effective EF (EEF), which is an average of EF over all possible orientations at a specific location, is calculated. According to EEF, the proximities of the end-caps of a GNR are strong enhancing zones. In contrast, the waist area is the weak zone. Moreover, a bigger GNR (a=10 nm) possesses a higher EEF than a smaller one (a=7 nm) for the same aspect ratio and the molecular relative location. Hence, a strong enhancement on the fluorescence is obtained using bigger GNR, if the molecule is near the end-cup and the dipole orientation is along the long axis. On the contrary, the consequence could be quenching, if the molecule is near the waist of a small GNR. The Stokes shift of fluorescence can also affect the EF, except the excitation wavelength.     

Nitric oxide turn-on fluorescent probe based on deamination of aromatic primary monoamines

The stable, water-soluble, and nonfluorescent FA-OMe can sense nitric oxide (NO) and form the intensely fluorescent product dA-FA-OMe via reductive deamination of the aromatic primary amine. The reaction is accompanied by a notable increase of the fluorescent quantum yield from 1.5 to 88.8%. The deamination mechanism of FA-OMe with NO was proposed in this study. The turn-on fluorescence signals were performed by suppression of photoinduced electron transfer (PeT), which was demonstrated by density functional theory (DFT) calculations of the components forming FA-OMe and dA-FA-OMe. Furthermore, FA-OMe showed water solubility and good stability at physiological pHs. Moreover, the selectivity study indicated that FA-OMe had high specificity for NO over other reactive oxygen/nitrogen species. In an endogenously generated NO detection study, increasing the incubation time of FA-OMe with lipopolysaccharide (LPS) pretreated Raw 264.7 murine macrophages could cause an enhanced fluorescence intensity image. In addition, a diffusion/localization cell imaging study showed that FA-OMe could be trapped in Raw 264.7 cells. These cell imaging results demonstrated that FA-OMe could be used as a turn-on fluorescent sensor for the detection of endogenously generated NO.