Density functional theory studies on IR spectra of the triphenylene derivatives : a scaled quantum mechanical force field approach

Density functional theory, B3-LYP with the 6-31G* basis set was applied to study the structures and vibrational infrared spectra of triphenylene and the hexasubstituted triphenylene derivatives. The calculated force fields were scaled using the scaled quantum mechanical force field method. The predicted vibrational frequencies were compared with the experimental IR spectra (500-4000 cm -1 ). The spectra were interpreted and vibrational assignments were reported. This study shows that the scaled density functional force field approach enables, through the transferability of scale factors, good interpretation of vibrational spectra of large molecules

Experimental and theoretical spectroscopic studies on selected igepals

Several nonionic igepals characterized by the formula (CmH2m+1 )-C6H4-(OCH2CH2 ) n OH were investigated by high resolution NMR and IR spectroscopy. Gauge invariant atomic orbital density functional theory NMR calculations on model molecules in the gas phase additionally supported the assignment of experimental carbon signals. Different orientations of individual sub-units of an aliphatic chain relative to external magnetic field and trans-gαuche transitions were assumed to explain complex patterns of carbon spectra in the aliphatic region of igepals with linear alkyl chain

Quantum effects in electrical conductivity and photoconductivity of single SbSI nanowire

For the first time current quantization is reported for antimony sulfoiodide (SbSI) nanowires. It has been registered in current responses on electric eld switching as well as on illumination on and o . Current steps determined in all experiments have been equal to each other within the experimental error. It has been explained by the quantized change of free carrier concentration in nanowire. Lateral dimensions of SbSI nanowires estimated from quantum steps are comparable with geometrical data reported for the same technology of material preparation

Physicochemical analysis of sediments formed on the surface of hydrophilic intraocular lens after Descemet’s stripping endothelial keratoplasty

An intraocular lens (IOL) is a synthetic, artificial lens placed inside the eye that replaces a natural lens that is surgically removed, usually as part of cataract surgery. The opacification of the artificial lens can be related to the formation of the sediments on its surface and could seriously impair vision. The physicochemical analysis was performed on an explanted hydrophilic IOL and compared to the unused one, considered as a reference IOL. The studies were carried out using surface sensitive techniques, which can contribute to a better understanding of the sedimentation process on hydrophilic IOLs’ surfaces. The microscopic studies allowed us to determine the morphology of sediments observed on explanted IOL. The photoelectron spectroscopy measurements revealed the presence of organic and inorganic compounds at the lens surface. Mass spectroscopy measurements confirmed the chemical composition of deposits and allowed for chemical imaging of the IOL surface. Applied techniques allowed to obtain a new set of information approximating the origin of the sediments’ formation on the surface of the hydrophilic IOLs after Descemet’s stripping endothelial keratoplasty

Evolution of glassy carbon under heat treatment : correlation structure-mechanical properties

In order to accommodate an increasing demand for glassy carbon products with tailored characteristics, one has to understand the origin of their structure-related properties. In this work, through the use of high-resolution transmission electron microscopy, Raman spectroscopy, and electron energy loss spectroscopy it has been demonstrated that the structure of glassy carbon at different stages of the carbonization process resembles the curvature observed in fragments of nanotubes, fullerenes, or nanoonions. The measured nanoindentation hardness and reduced Young’s modulus change as a function of the pyrolysis temperature from the range of 600–2500 °C and reach maximum values for carbon pyrolyzed at around 1000 °C. Essentially, the highest values of the mechanical parameters for glassy carbon manufactured at that temperature can be related to the greatest amount of non-planar sp2-hybridized carbon atoms involved in the formation of curved graphene-like layers. Such complex labyrinth- like structure with sp2-type bonding would be rigid and hard to break that explains the glassy carbon high strength and hardness

The use of ZrO2 waste for the electrolytic production of composite Ni- P-ZrO2 powder

Ni–P–ZrO2 composite powder was obtained from a galvanic nickel bath with ZrO2 powder. Production was conducted under galvanostatic conditions. The Ni–P–ZrO2 composite powder was characterized by the presence of ZrO2 particles covered with electrolytical nanocrystalline Ni–P coating. The chemical composition (XRF method), phase structure (XRD method) and morphology (SEM) of Ni–P–ZrO2 and the distribution of elements in the powder were all investigated. Based on the analyses, it was found that the obtained powder contained about 50 weight % Zr and 40 weight % Ni. Phase structure analysis showed that the basic crystalline component of the tested powder is a mixed oxide of zirconium and yttrium Zr0.92Y0.08O1.96. In addition, the sample contains very large amounts of amorphous compounds (Ni–P). The mechanism to produce the composite powder particles is explained on the basis of Ni2+ ions adsorption process on the metal oxide particles. Current flow through the cell forces the movement of particles in the bath. Oxide grains with adsorbed nickel ions were transported to the cathode surface. Ni2+ ions were discharged. The oxide particles were covered with a Ni–P layer and the heavy composite grains of Ni–P–ZrO2 flowed down to the bottom of the cell

Molecular structure, in vitro anticancer study and molecular docking of new phosphate derivatives of betulin

A series of 30-diethylphosphate derivatives of betulin were synthesized and evaluated for their in vitro cytotoxic activity against human cancer cell lines, such as amelanotic melanoma (C-32), glioblastoma (SNB-19), and two lines of breast cancer (T47D, MDA-MB-231). The molecular structure and activities of the new compounds were also compared with their 29-phosphonate analogs. Compounds 7a and 7b showed the highest activity against C-32 and SNB-19 cell lines. The IC50 values for 7a were 2.15 and 0.91 M, and, for 7b, they were 0.76 and 0.8 M for the C-32 and SNB-19 lines, respectively. The most potent compounds, 7a and 7b, were tested for their effects on markers of apoptosis, such as H3, TP53, BAX, and BCL-2. For the whole series of phosphate derivatives, a lipophilicity study was performed, and the ADME parameters were calculated. The most active products were docked to the active site of the EGFR protein. The relative binding affinity of selected phosphate betulin derivatives toward EGFR was compared with standard erlotinib on the basis of ChemScore and KDEEP score. Positively, all derivatives docked inside the cavity and showed significant interactions. Moreover, a molecular dynamics study also reveals that ligands 7a,b form stable complexes and the plateau phase started after 7 ns

Correlation between locally ordered (hydrogen-bonded) nanodomains and puzzling dynamics of polymethysiloxane derivative

We examined the behavior of poly(mercaptopropyl)methylsiloxane (PMMS), characterized by a polymer chain backbone of alternate silicon and oxygen atoms substituted by a polar pendant group able to form hydrogen bonds (−SH moiety), by means of infrared (FTIR) and dielectric (BDS) spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and rheology. We observed that the examined PMMS forms relatively efficient hydrogen bonds leading to the association of chains in the form of ordered lamellar-like hydrogen-bonded nanodomains. Moreover, the recorded mechanical and dielectric spectra revealed the presence of two relaxation processes. A direct comparison of collected data and relaxation times extracted from two experimental techniques, BDS and rheology, indicates that they monitor different types of the mobility of PMMS macromolecules. Our mechanical measurements revealed the presence of Rouse modes connected to the chain dynamics (slow process) and segmental relaxation (a faster process), whereas in the dielectric loss spectra we observed two relaxation processes related most likely to either the association−dissociation phenomenon within lamellar-like self-assemblies or the sub-Rouse mode (α′-slower process) and segmental (α-faster process) dynamics. Data presented herein allow a better understanding of the peculiar dynamical properties of polysiloxanes and associating polymers having strongly polar pendant moieties

Aromaticity Effect on Supramolecular Aggregation. Aromatic vs. Cyclic Monohydroxy Alcohols

In this paper, the steric hindrance effect related to the presence of either an aromatic or cyclic ring on the self-association process in the series of monohydroxy alcohols (MAs), from cyclohexanemethanol to 4-cyclohexyl-1-butanol and from benzyl alcohol to 4-phenyl-1- butanol, was studied using X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FTIR) spectroscopy, Broadband Dielectric Spectroscopy (BDS) and the Pendant Drop (PD) methods. Based on FTIR results, it was shown that phenyl alcohol (PhA) and cyclohexyl alcohol (CA) derivatives reveal substantial differences in the association degree, the activation energy of dissociation, and the homogeneous distribution of supramolecular nanoassociates suggesting that the phenyl ring exerts a stronger steric impact on the self-assembling of molecules than cyclohexyl one. Additionally, XRD data revealed that phenyl moiety introduces more heterogeneity in the organization of molecules compared to the cyclic one. The changes in the self-association process of alcohols were also reflected in differences in the molecular dynamics of the H-bonded aggregates, as well as in the Kirkwood factor, defining the long-range correlation between dipoles, which were slightly higher for CAs with respect to those determined for PhAs. Unexpectedly it was also found that the surface layers of PhAs were more organized than those formed by CAs. Thus, these findings provided insight into the impact of aromaticity on the self–assembly process, Hbonding pattern, supramolecular structure, and intermolecular dynamics of the studied alcohols