Heterotermetallic indium lithium halostannates: low-temperature single-source precursors for tin-rich indium tin oxides and their application for thin-film transistors

The syntheses and structural elucidation of dimeric [Sn(OCyHex)(2)] (1), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)(3)Sn}(2)] (M = Li (2), Na (3), K (4)), and of the first heteroleptic heterotermetallic Li/In/Sn-haloalkoxide clusters [X(2)In{LiSn(2)(OCyHex)(6)}] (X = Br (5), Cl (6)) with a double seco-norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin-rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy-dispersive X-ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin-containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2θ values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In(2)O(3) lattice and partially occupied In(3+) sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin-film field-effect transistors (FETs) were fabricated by spin-coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25-700?°C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge-carrier mobility of 6.36×10(-1) cm(2) V(-1) s (calcination at 250?°C) and an on/off current ratio of 10(6).     

Heterotermetallic Indium Lithium Halostannates: Low‐Temperature Single‐Source Precursors for Tin‐Rich Indium Tin Oxides and Their Application for Thin‐Film Transistors

The syntheses and structural elucidation of dimeric [Sn(OCyHex)₂] ( 1 ), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)₃Sn}₂] (M=Li ( 2 ), Na ( 3 ), K ( 4 )), and of the first heteroleptic heterotermetallic Li/In/Sn–haloalkoxide clusters [X₂In{LiSn₂(OCyHex)₆}] (X=Br ( 5 ), Cl ( 6 )) with a double seco‐norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin‐rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy‐dispersive X‐ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin‐containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2θ values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In₂O₃ lattice and partially occupied In³⁺ sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin‐film field‐effect transistors (FETs) were fabricated by spin‐coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25–700 °C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge‐carrier mobility of 6.36×10^?1 cm² V^?1 s (calcination at 250 °C) and an on/off current ratio of 10⁶.     

Synthesis of new water-soluble phosphonate calixazacrowns and their use as drug solubilizing agents

This study presents the selective chloromethylation of calix[4](aza)crown ethers 2a–c, using chloromethyl n-octyl ether and SnCl₄ in chloroform at room temperature in good yield for the first time. Chloromethylated products 2a–c are used as key intermediates to synthesize new water-soluble p-phosphonato calix[4](aza)crown ethers 5a–c. Liquid–liquid phase extraction and phase solubility studies with poor water soluble drug molecules such as nifedipine, niclosamide and furosemide are performed to evaluate their binding properties. Among the studied drugs, furosemide was the most effectively dissolved drug by p-phosphonato calix[4](aza)crown ethers 5a–c in water.     

Three-dimensional flow structure on a maneuvering wing

Unsteady plunging (heaving) of a wing in the form of a flat plate can give rise to pronounced axial flow in the small-scale leading-edge vortex, during its initial stage of formation. Opposing axial flows along the vortex interact at the plane of symmetry giving rise to large-scale patterns of streamwise-oriented vorticity, which can dominate the tip vortices over part of the oscillation cycle.     

WADM and radiation MHD simulations of compact multi-planar and cylindrical wire arrays at 1 MA currents

The radiative performance of Z-pinches created by the imploding wire array loads is defined by the ablation and implosion dynamics of these loads. Both these processes can be effectively modeled by the Wire Ablation Dynamics Model (WADM), which extends the formalism exploited earlier for the cylindrical wire arrays to the loads of arbitrary geometries. The WADM calculates the ablation rates for each array wire and provides the important dynamic parameters, such as the specific mass and velocity of the imploding plasma, which can be used to estimate the shapes of the x-ray pre-pulse and, partially, the main x-ray burst. The applications of the WADM also extend to combined material wire array loads. The ablation and implosion dynamics of novel Prism Planar Wire Array (PPWA) and combined material (Mo/Al/Mo) Triple Planar Wire Array (TPWA) loads are discussed in detail. The combined WADM and radiation MHD simulation is applied to model the radiative performance of the precursor plasma column, created by the imploding stainless steel compact cylindrical wire array. As the radiation effects intensify with the mass accumulation at the array center, the simulation reveals the transformation of quasi-uniform precursor column into a heterogeneous plasma structure with strong density and temperature gradients. We find that radiative performance of the precursor plasma is greatly affected by the load geometry as well as by the wire material.     

Effect of operating parameters on selective separation of heavy metals from binary mixtures via polymer enhanced ultrafiltration

Performance of continuous polymer enhanced ultrafiltration (PEUF) method was investigated for removal of mercury and cadmium from binary mixtures. This method includes the addition of polyethyleneimine (PEI) as a water soluble polymer to bind the metals, which was followed by ultrafiltration operation performed on both laboratory and pilot scale systems. The influence of various operating parameters such as temperature, metal/polymer ratio, presence of calcium ions and pH on retention of metals and permeate flux was investigated. To investigate the possibility of selective separation of mercury and cadmium, experiments were conducted for binary solutions at different pH and loading ratios. It was seen that the retention of mercury decreased and permeate flux increased when the temperature increased. The increased pH and decreased metal/polymer ratio, loading (L), resulted in higher retention of both metals. Shapes of retention vs. pH or L curves were very similar for both metals. Retentions stay almost constant at a value very close to unity until a critical L or pH value was reached, then, R decreases almost linearly with L or pH. However, retention of cadmium was affected more than that of mercury as the pH decreased and L increased. This leads to the selective separation of mercury and cadmium. At low pH values (about 5) and at high L values (about 0.3), mercury was removed by ultrafiltration operation while almost all cadmium passed through the membrane. At pH 5.5 and cadmium/polymer ratio about 0.35 and mercury/polymer ratio about 0.39, the highest separation factor was obtained as 49.     

Chiral recognition and separation of beta2-amino acids using non-covalently molecularly imprinted polymers

Non-covalently molecularly imprinted polymers (MIPs) for beta2-amino acids were prepared for the first time. N-(2-chlorobenzyloxycarbonyl)-(R)-beta2-homophenylalanine (N-2-ClZ-(R)-beta2-HPhe) was imprinted with methacrylic acid (MAA) and/or 4-vinylpyridine (4-VPy) as the functional monomers, with ethylene glycol dimethacrylate (EDMA) as the cross-linker. The MIPs made with different ratios of MAA:4-VPy were studied in HPLC mode. The results show that MIPs made with 4-VPy yielded the best chiral separation factor (alpha= 1.86) for the template molecule. The importance for an efficient separation of pi-stacking interactions between the MIPs and the template molecule is demonstrated. Racemates of Z-alpha-amino acids and beta-amino acid analogues of the template were either not or poorly resolved by the MIPs, thus demonstrating the close three-dimensional complementarity of the MIPs' recognition sites with the template.     

Light harvesting and efficient energy transfer in a boron-dipyrrin (BODIPY) functionalized perylenediimide derivative

[reaction: see text] Click chemistry has been successfully applied in the synthesis of a bay region tetraboron-dipyrrin (BODIPY) appended perylenediimide (PDI). This light-harvesting molecule presents a large cross section for the absorption of light in the visible region. Excitation energy is efficiently channeled to the perylenediimide core. This novel antenna system is the first demonstration of the efficiency of energy transfer in a BODIPY-PDI bichromophoric system and appears to be highly promising for the design and synthesis of similar dendritic structures.     

Natural radioactivity in soil samples of Kocaeli basin, Turkey

The city of Kocaeli is in the western part of Anatolia in Turkey and has a population of approximately 1.000.000. There is no information about radioactivity in the Kocaeli soils samples so far. For this reason, the concentrations of the natural radionuclides in soil samples from 27 different sampling stations in Kocaeli Basin and its surroundings have been determined. The results have been compared with other radioactivity measurements in different country"s soils. The typical concentrations of ¹³⁷Cs, ²³⁸U, ⁴⁰K, ²²⁶Ra, ²³²Th found in surface soil samples ranged from 2±0.6 to 25±6 Bq/kg, from 11±4 to 49±10 Bq/kg, from 161±30 to 964±127 Bq/kg, from 10±4 to 58±11 Bq/kg, and from 11±3 to 65±13 Bq/kg, respectively.     

Surface growth mechanisms and structural faulting in the growth of large single and spherulitic titanosilicate ETS-4 crystals

Morphological, surface and crystallographic analyses of titanosilicate ETS-4 products, with diverse habits ranging from spherulitic particles composed of submicron crystallites to large single crystals, are presented. Pole figures revealed that crystal surfaces with a-, b- and c- axes corresponded to 110, 010 and 001 directions, respectively. Thus, technologically important 8-membered ring pores and titania chains in ETS-4 run along the b-axis of single crystals and terminate at the smallest crystal face. Height of the spiral growth steps observed on 1 0 0 and 0 0 1 surfaces corresponded to the interplanar spacings associated with their crystallographic orientation, and is equivalent to the thickness of building units that form the ETS-4 framework. Data suggest that the more viscous synthesis mixtures, with a large driving force for growth, increased the two- and three-dimensional nucleation, while limiting the transport of nutrients to the growth surface. These conditions increase the tendency for stacking fault formation on 1 0 0 surfaces and small angle branching, which eventually results in spherulitic growth. The growth of high quality ETS-4 single crystals (from less viscous synthesis mixtures) occurred at lower surface nucleation rates. Data suggest that these high quality, large crystals grew due to one-dimensional nucleation at spiral hillocks, and indicate that under these conditions un-faulted growth is preferred.