Miracle-dz/UniFAR-FTUs huggingface dataset:
para-Bisvinylhexaisobutyl-substituted T8 caged monomer: synthesis and hydrosilylation polymerization

The selective introduction of functional groups at the para-position in mono-functionalized T8-caged silsesquioxanes would enable us to design new organic inorganic hybrid polymers. Here, a para-substituted bisvinylhexaisobutyl-T8 caged monomer was successfully synthesized via a selective corner-opening reaction of the vinylheptaisobutyl-T8 cage followed by a subsequent corner-capping reaction.
Structural Selectivity of CO Oxidation on Fe/N/C Catalysts

Fe/N/C electrocatalysts are attractive for electrocatalytical applications in fuel cells due to their low cost and high electrocatalytic activity. Because of its complex nature, the mechanism of CO oxidation on Fe/N/C electrocatalysts remains largely unknown. Aiming to provide insight into the mechanism of CO oxidation, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Fe/N/C active sites, including Fe-N4 and Fe-N3 porphyrin-like carbon nanotube (T-FeN4 and T-FeN3), Fe-N4 porphyrin-like graphene (G-FeN4), and Fe-N2 nanoribbon (R-FeN2). It is found that CO adsorption and oxidation are very sensitive to the active site structures. CO adsorption is energetically more favorable than O2, and CO oxidation to CO2 hardly occurs on T-FeN4 and G-FeN4. In comparison, O2 prefers to adsorb and CO can easily be oxidized on T-FeN3 and R-FeN2, suggesting the CO tolerant property of T-FeN3 and R-FeN2.
Synthetic Approach to Ruthenium Vinylidene Complexes and Their Applications in Metathesis Catalysis

Convenient routes for synthesis of ruthenium vinylidene complexes have been described, the majority of which use alkynes along with a ruthenium source as the main starting materials. Their successful application as efficient precatalysts in synthesis of heterocyclic and carbocyclic compounds by ring-closing metathesis of alpha,omega-dienes and in the synthesis of polymers by ring-opening metathesis polymerization of cyclooctene, norbornene, 5-substituted norbornene and dicyclopentadiene are fully illustrated. Relevant aspects concerning the activity and stereoselectivity in metathesis reactions of this type of Ru complexes are highlighted
Cardanol-based oligomers with “hard core, flexible shell” structures: from synthesis to UV curing applications

Two hyperbranched oligomers with renewable cardanol side groups and multiple photopolymerizable acrylates were designed and synthesized. The structures of the hyperbranched oligomers were characterized by 1H NMR and FTIR spectroscopy. The synthesized oligomers contain rigid carbon rings as “hard cores” and long reactive fatty chains as “flexible shells”. The photopolymerization kinetics, thermodynamic properties and mechanical properties of the UV cured films were studied and compared with a petrochemical based hyperbranched acrylate CN2302. The cardanol-based polymers with “hard core, flexible shell” structures have higher double bond conversion and higher Tg but lower thermal stability. Much improved surface mechanical properties such as nanoindentation hardness, reduced modulus, surface storage modulus and storage stiffness can be obtained for the plant oil-based polymers. These biorenewable, UV curable cardanol-based oligomers show promise in “green + green” materials technologies.
Alignment of energy levels at the ZnS/Cu(In,Ga)Se2 interface

Further understanding of the electronic structure at the ZnS/Cu(In,Ga)Se2 interface is necessary to enhance the electron injection across the interface in Cu(In,Ga)Se2 solar cells. The valence band structure and shallow core levels were investigated by ultraviolet photoelectron spectroscopy depth profile analysis with He II line excitation. ZnS film was grown by a chemical bath deposition on a Cu(In,Ga)Se2 absorber deposited by the co-evaporation of Cu, In, Ga, and Se elemental sources. The discontinuity of 2.0 eV in the valence band edge at the ZnS/Cu(In0.7Ga0.3)Se2 interface was directly determined. This type of valence band offset yields a spike conduction band alignment of 0.25 eV. The positions of the VBM and the Zn 3d core-level emission of the buffer underwent the substantial shifts of 0.36 eV and 0.64 eV to a lower binding energy levels during the etching process. The shifts are ascribed to the contribution of the band bending in the ZnS buffer layer and its graded chemical composition. This study is the first to determine the small conduction band offset at the interface formed by the chemical bath deposited ZnS layer and the Cu(In0.7Ga0.3)Se2 absorber. Our results also provide information toward the design optimization of the optoelectronic properties of the ZnS/Cu(In0.7Ga0.3)Se2 interface. To enhance the electron injection from Cu(In0.7Ga0.3)Se2 absorber to ZnS layer further lowering of the energy barrier is required. For this purpose, the bandgap of ZnS should be reduced by controlling the crystal structure and composition or its Fermi level should be upward shifted by appropriate doping.
The theory of magnetic resonance experiments on salts of the rare earths

A general account is given of the theory of paramagnetic resonance in rare-earth crystals, assuming that the crystalline electric field splitting is less than the spin-orbit splitting. The treatment is related, as far as possible, to numerical parameters, which are sufficiently comprehensive for it to be a straightforward process to pass from a given crystalline field to the spin-Hamiltonian.
Elimination of leukemic cells from human transplants by laser nano-thermolysis

We describe novel ex vivo method for elimination of tumor cells from bone marrow and blood, Laser Activated Nano-Thermolysis for Cell Elimination Technology (LANTCET) and propose this method for purging of transplants during treatment of leukemia. Human leukemic cells derived from real patients with different diagnoses (acute lymphoblastic leukemias) were selectively damaged by LANTCET in the experiments by laser-induced micro-bubbles that emerge inside individual specifically-targeted cells around the clusters of light-absorbing gold nanoparticles. Pretreatment of the transplants with diagnosis-specific primary monoclonal antibodies and gold nano-particles allowed the formation of nanoparticle clusters inside leukemic cells only. Electron microscopy found the nanoparticulate clusters inside the cells. Total (99.9%) elimination of leukemic cells targeted with specific antibodies and nanoparticles was achieved with single 10-ns laser pulses with optical fluence of 0.2 - 1.0 J/cm2 at the wavelength of 532 nm without significant damage to normal bone marrow cells in the same transplant. All cells were studied for the damage/viability with several control methods after their irradiation by laser pulses. Presented results have proved potential applicability of developed LANTCET technology for efficient and safe purging (cleaning of residual tumor cells) of human bone marrow and blood transplants. Design of extra-corporeal system was proposed that can process the transplant for one patient for less than an hour with parallel detection and counting residual leukemic cells.
Synthesis of liquid crystalline poly(1‐pentyne)s and fabrication of polyacetylene–perovskite hybrids

Poly(1-pentyne)s containing biphenyl and phthalimido pendant groups with different spacer lengths {P1(m); -[HC=C(CH 2 ) 3 O-Biph-OCO(CH 2 ) m N(CO) 2 C 6 H 4 ] n -, Biph=4,4'-biphenylyl; m = 7, 10) are synthesized in satisfactory yields by WCl 6 -Ph 4 Sn catalyst in toluene at elevated temperatures. The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, and XRD analyses. Both of the polymers are thermally stable (T d ≥ 300 C) and exhibit nematicity at high temperatures. Their phthalimido groups are converted into amino groups by hydrolysis, which can, after acidification, complex with lead(II) bromide to furnish polyacetylene-perovskite hybrids in high yields. The organic components contribute good solubility to the hybrids, while the perovskite framework induces the polyacetylene chains to align within the inorganic sheets. The hybrids emit a strong UV light of 374 nm upon photoexcitation, whose quantum yield increases with an increase in the spacer length.
Adsorption of cationic flocculants to paper slurries

Abstract Polymers of varying molecular weights and charges are extensively used for diverse papermaking operations such as retention, drainage, and waste treatment/recovery. Owing to the heterogeneous nature of both the polymer and the paper slurry and to the high shear environment in which paper is made, it is a challenging task to study polymer adsorption in this system and, more importantly, to be able to correlate the results with paper machine performance. In this study, the technique of fluorescence microscopy was adapted to determine the adsorption characteristics of a fluorescent cationic flocculant on three different papermaking slurries. In the absence of fillers and dissolved and colloidal substances (DCS), polymer is shown to adsorb on high surface area regions of the fiber resulting from mechanical fiber processing operations. However, in a composite alkaline furnish containing CaCO3 filler and under conditions and time scales prevalent on a papermachine, the polymer preferentially adsorbs to the filler. The filler flocs in turn are adsorbed to the fibrils. In a mechanical furnish with DCS, polymer–DCS complexes are formed that alter the adsorption characteristics of the polymer. Results are discussed in terms of kinetics of adsorption, shear-induced collisions, and interactions with solution species. Furthermore, the utility of the fluorescence microscopy technique to study adsorption in complex industrial matrices is demonstrated.
Ab initio molecular orbital calculations of the protonation reaction of propylene and isobutene by acidic OH groups of isomorphously substituted zeolites

Ab initio molecular-orbital calculations using the 3-21G basis set are performed to study the protonation reaction of propylene and isobutene by zeolite bridged hydroxyls ZOH, which are simulated by a cluster model which consists of two Si tetrahedra and one Al tetrahedron. We have extended this study to include clusters with different compositions by introducing B and Ga in T III positions. The calculations show that in all reactions the adsorption of the olefin molecule on the acidic OH group takes place, leading to a stable π-complex with a structure similar to those of the isolated olefin and clusters constituents. The π-complex is transformed into a zeolite-alkoxide of covalent characteristics
Exploring photochemistry of 2-(phenylazo)pyridine dye by using TDDFT/DFT methods†

The non-emissive behaviour of 2-(phenylazo)pyridine, azpy, observed in the fluorescence experiment was explained by investigating its photoisomerisation mechanism. By using the Density Functional Theory and Time-dependent Density Functional Theory (DFT/TDDFT) methods, the two-dimensional potential energy surfaces in the ground state, and the first and second excited states which are relevant to the trans-to-cis isomerisation were constructed. The pathways related to the inversion, rotation and their concerted motion of the phenyl and pyridyl groups around NN bond were considered. The energy profiles depend not only on the type of pathways but also on the moving group. The concerted-inversion pathways show the possibility of S1/S2 and S0/S1 conical intersections. The relaxation through such intersections should increase the non-radiative transition rate to the extent that the compound does not emit fluorescence. © 2011 Canadian Society for Chemical Engineering
Formation of W/O Microemulsions in the Extraction System Rh(III)-HCl-Kelex 100 and Its Impact on Rh(III) Distribution

Abstract The extraction behavior of chloro complexes of rhodium (III) into an organic phase of Kelex 100 extractant has been investigated from the standpoint of aquation and microemulsion formation. The aquation of Rh-chloro complexes has been confirmed experimentally to be the main factor which suppresses the liquid-liquid extraction of rhodium. In addition, the formation of Kelex 100-acid-water aggregates in the organic phase has been unequivocally demonstrated by performing various measurements such as water uptake, viscosity, interfacial tension, and light scattering. Due to aquation which is promoted by the formation of microemulsions, very limited overall rhodium extraction can be effected by direct liquid-liquid extraction.
Effect of voltage waveform on dielectric barrier discharge ozone production efficiency

Dielectric barrier discharges (DBDs) are commonly used for gas effluent cleanup and ozone generation. For these applications, the energy efficiency of the discharge is a major concern. This paper reports on investigations carried out on the voltage shape applied to DBD reactor electrodes, aiming to evaluate a possible energy efficiency improvement for ozone production. Two DBD reactor geometries were used: pin-to-pin and cylinder-to-cylinder, both driven either by a bi-directional power supply (voltage rise rate 1 kV/ μ s) or by a pulsed power supply (voltage rise rate 1 kV/ns). Ozone formed in dry air was measured at the reactor outlet. Special attention was paid to discharge input power evaluation using different methods including instantaneous current-voltage product and transferred charge-applied voltage figures. The charge transferred by the discharges was also correlated to the ozone production. It is shown that, in the case of the DBD reactors under investigation, the applied voltage shape has no influence on the ozone production efficiency. For the considered voltage rise rate, the charge deposit on the dielectric inserted inside the discharge gap is the important factor (as opposed to the voltage shape) governing the efficiency of the discharge – it does this by tailoring the duration of the current peak into the tens of nanosecond range.
Multilevel Design of Sandwich Composite Armors for Blast Mitigation using Bayesian Optimization and Non-Uniform Rational B-Splines

I n regions at war, the increasing use of improvised explosive devices (IEDs) is the main threat against military vehicles. Large cabin”s penetrations and high gross accelerations are primary threats against the occupants” survivability. The occupants” survivability under an IED event largely depends on the design of the vehicle armor. Under a blast load, a vehicle armor should maintain its structural integrity while providing low cabin penetrations and low gross accelerations. This investigation employs Bayesian global optimization (BGO) and non-uniform rational B-splines (NURBS) to design sandwich composite armors that simultaneously mitigate the cabin”s penetrations and the reaction force at the armor”s supports. The armors are made of four layers: steel, carbon fiber reinforced polymer (CFRP), aluminum honeycomb, and CFRP. BGO is a methodology to solve optimization problems that require the evaluation of expensive black-box functions such as the finite element (FE) simulations of the vehicle armor under a blast event. BGO has two main components: the surrogate model of the black-box function and the acquisition function that guides the optimization. In this study, the surrogate models are Gaussian processes and the acquisition function is the multi-objective expected improvement function. NURBS generate the armor”s shape. The numerical examples show three alternatives to optimize the armor at two levels: (1) thicknesses of the sandwich”s layers and (2) the armor”s shape. The three design alternatives differ in the number of optimized levels and the optimization approach (sequential or simultaneous). The results show that the simultaneous optimization of the thicknesses of the sandwich”s layers and the armor”s shape is the most effective approach to design vehicle armors for blast mitigation.
10H+‐2,3‐Benzo‐1,4‐dioxa‐7,10,13‐triazacyclopentadec‐2‐ene‐6,14‐dione Picrate Hydrate (1/1/1)

The title compound, C14H20N3O4+ C6H2N3O7−. H2O, contains a 15-membered macrocycle which has two ether O atoms, two pairs of amide N and O atoms, and an amine N atom as potential donor atoms. The macrocycle has undergone protonation at the amine N atom. The picrate ion interacts through its phenolic O atom with the –NH2 group via an N-H⋯O hydrogen bond. The water molecule is linked in an endocyclic manner to the macrocyclic ring through both the amide groups by forming an O⋯H-N hydrogen bond. The ether O atoms do not participate in any hydrogen-bonding interactions. The water molecule is also intermolecularly linked to one symmetry-related nitro group O atom of the picrate and to one amide O atom.
Polymerization of 1,5-dioxepan-2-one. II: Polymerization of 1,5-dioxepan-2-one and its cyclic dimer, including a new procedure for the synthesis of 1,5-dioxepan-2-one

Nouvelle methode de preparation de la dioxepannone par oxydation de Baeyer Villiger de la tetrahydro pyrannone-4 avec un rendemnt de 48%. La polymerisation du monomere et du dimere amorcee par des catalyseurs de transesterification en masse ou un μ-oxo alcoolate bimetallique en solution donne des polymeres amorphes de MW comprise entre 10000 et 50000 et avec une Tg de −39 o C
Retention and Uptake by Plants of Added Selenium in Peat Soils

In soil, adsorption of selenium (Se) onto mineral surfaces is accompanied by poorly known retention via organic matter. The effects of these components on the availability of Se were examined in two pot experiments. Spring wheat was grown with increasing amounts of selenate (SeO4 2–) in one sand and three peat soils, and ryegrass with selenate and selenite (SeO3 2–) in sphagnum peat manipulated by iron (Fe) hydroxide. Selenate persisted in soluble form, whereas selenite was fixed in the soil. In wheat, 5–50% of the selenate addition was recovered in the plant, the proportion increasing with increasing Se. In ryegrass, 30–40% of the added selenate but less than 2% of the selenite was found within the leaves. The Fe hydroxide enrichment enhanced the selenite uptake. Phosphate buffer desorbed a minor proportion of the added selenite, except in peat amply enriched with Fe hydroxide. The results suggest that the retention mechanism of selenite was changed due to the hydroxide amendment.
Ultrafast dynamics of the 11Bu-state of 1,3-butadiene after excitation at 204 nm

The ultrafast dynamics of the 11Bu state of 1,3-butadiene was investigated in real time in a femtosecond pump–probe experiment utilizing the RE2PI scheme. A lifetime of 35 ± 10 fs was found for the 11Bu state of the jet-cooled molecule.
Blue-Emitting Anthracenes with End-Capping Diarylamines

A new series of 2-tert-butyl-9,10-bis(bromoaryl)anthracenes have been synthesized from 2-tert-butyl-9,10-anthraquinone. Palladium-catalyzed C−N bond formation between these bromo compounds and diarylamines provides stable 2-tert-butyl-9,10-diarylanthracenes containing two peripheral diarylamines (anth). They possess high thermal decomposition temperature (Td > 450 °C) and form a stable glass (Tg > 130 °C). Furthermore, they are fluorescent in the blue region with moderate to good quantum efficiencies. Two types of light-emitting diodes (LED) were constructed from anth, (I) ITO/anth/TPBI/Mg:Ag and (II) ITO/anth/Alq3/Mg:Ag, where TPBI and Alq3 are 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene and tris(8-hydroxyquinolinato)aluminum, respectively. In type I devices, the anth function as the hole-transporting and emitting material. In type II devices, emission from Alq3 is observed. Several blue-light-emitting type I devices exhibit good maximum brightness and physical performance. The relation between the ener.
Removal of Nitrogen Oxides in Diesel Engine Exhaust by Plasma Assisted Molecular Sieves

This paper reports the studies conducted on removal of oxides of nitrogen (NOx) from diesel engine exhaust using electrical discharge plasma combined with adsorbing materials such as molecular sieves. This study is being reported for the first time. The exhaust is taken from a diesel engine of 6 kW under no load conditions. The characteristic behavior of a pulse energized dielectric barrier discharge reactor in the diesel exhaust treatment is reported. The NOx removal was not significant (36%) when the reactor without any packing was used. However, when the reactor was packed with molecular sieves (MS -3A, -4A & -13X), the NOx removal efficiency was increased to 78% particularly at a temperature of 200 °C. The studies were conducted at different temperatures and the results were discussed.
The adsorption of water in finite carbon pores

Grand canonical Monte Carlo simulations were applied to the adsorption of SPCE model water in finite graphitic pores with different configurations of carbonyl functional groups on only one surface and several pore sizes. It was found that almost all finite pores studied exhibit capillary condensation behaviour preceded by adsorption around the functional groups. Desorption showed the reverse transitions from a filled to a near empty pore resulting in a clear hysteresis loop in all pores except for some of the configurations of the 1.0 nm pore. Carbonyl configurations had a strong effect on the filling pressure of all pores except, in some cases, in 1.0 nm pores. A decrease in carbonyl neighbour density would result in a higher filling pressure. The emptying pressure was negligibly affected by the configuration of functional groups. Both the filling and emptying pressures increased with increasing pore size but the effect on the emptying pressure was much less. At pressures lower than the pore filling pressure, the adsorption of water was shown to have an extremely strong dependence on the neighbour density with adsorption changing from Type IV to Type III to linear as the neighbour density decreased. The isosteric heat was also calculated for these configurations to reveal its strong dependence on the neighbour density. These results were compared with literature experimental results for water and carbon black and found to qualitatively agree.