Microstructure evolution of TI-SN-NB alloy prepared by mechanical alloying

In the present study, Ti-16Sn-4Nb alloy was prepared by mechanical alloying (MA). Optical microscopy, scanning electron microscopy combined with energy dispersive X-ray analysis (SEM-EDX), and X-ray diffraction analysis (XRD) were used to characterise the phase transformation and the microstructure evolution. Results indicated that ball milling to 8 h led to the formation of a supersaturated hcp α-Ti and partial amorphous phase due to the solid solution of Sn and Nb into Ti lattice. The microstructure of the bulk sintered Ti-16Sn-4Nb alloy samples made from the powders at shorter ball milling times, i.e. 20 min- 2 h, exhibited a primary α surrounded by a Widmanstätten structure (transformed β); while in the samples made from the powders at longer ball milling times, i.e. 5- 10 h, the alloy evolved to a microstructure with a disordered and fine β phase dispersed homogeneously within the α matrix. These results contribute to the understanding of the microstructure evolution in alloys of this type prepared by powder metallurgy.

Effects of process control agent on the microstructure and mechanical properties of Ti-Sn-Nb alloy prepared by mechanical alloying

In the present study, the influence of process control agent (PCA) on the characteristics of powder and bulk sintered Ti-16Sn-4Nb (wt. %) alloy prepared by mechanical alloying has been investigated. The elemental Ti, Sn and Nb powders were mechanically alloyed in a planetary ball mill for a short period of time using two types of PCA, namely stearic acid (SA) and ethylene bis-stearamide (EBS). The powder morphology, microstructural evolution of the bulk sintered alloy, phase formation and hardness of the alloy have been studied as a function of PCA. Results indicated that the addition of PCA leads to a delay in aIloy formation and introduces contaminations (mainly carbon and oxygen) into the material. The microstructural observation of the bulk alloy revealed a homogeneous distribution of fine Nb-rich colonies (ß-phase) within the a-Ti matrix for small amount of PCA. The hardness values of samples exhibited a significant increase with increasing amount of PCA, reaching a value of ~ 600 BV.

Synthesis of Al-doped Mg2Si1-xSnx compound using magnesium alloy for thermoelectric application

Abstract Mg2Si1-xSnx thermoelectric compounds were synthesized through a solid-state reaction at 700 °C between chips of Mg2Sn-Mg eutectic alloy and silicon fine powders. The Al dopants were introduced by employing AZ31 magnesium alloy that contains aluminum. The as-synthesized Mg2Si1-xSnx powders were consolidated by spark plasma sintering at 650-700 °C. X-ray diffraction and scanning electron microscopy revealed that the Mg2Si1-xSnx bulk materials were comprised of Si-rich and Sn-rich phases. Due to the complex microstructures, the electrical conductivities of Mg2Si1-xSnx are lower than Mg2Si. As a result, the average power factor of Al0.05Mg2Si0.73Sn0.27 is about 1.5 × 10^-3 W/mK² from room temperature to 850 K, being less than 2.5 × 10^-3 W/mK² for Al0.05Mg2Si. However, the thermal conductivity of Mg2Si1-xSnx was reduced significantly as compared to Al0.05Mg2Si, which enabled the ZT of Al0.05Mg2Si0.73Sn0.27 to be superior to Al0.05Mg2Si. Lastly, the electric power generation from one leg of Al0.05Mg2Si and Al0.05Mg2Si0.73Sn0.27 were evaluated on a newly developed instrument, with the peak output power of 15-20 mW at 300 °C hot-side temperature.

Hexameric trimethylsilylmethyloxotin acetate, [(Me3SiCH2)Sn(O)(OAc)]6

The centrosymmetric hexanuclear title compound, hexa-^μ₂-acetato-hexa-^μ₃-oxo-hexakis[(trimethylsilylmethyl)tin], [Sn₆O₆(C₂H₃O₂)₆(C₄H₁₁Si)₆], adopts a 'drum' structure in which two [(Me₃SiCH₂)SnO]₃ caps are linked to each other via six ^μ₃-O atoms and six bidentate bridging acetate groups. A CO₅ donor set defines a distorted octahedral environment for each of the three independent Sn atoms.

Incorporation of group 14 elements into siloxane-bridged paracyclophanes cyclo-[p,p´-Me2SiC6H4EMe2C6H4SiMe2O]2 (E = C, Si, Ge, Sn)§

The bis(arylene silanes) p,p'-HMe₂SiC₆H₄EMe₂C₆H₄SiMe₂H (E = C (10), Si (11), Ge (12), Sn(13)) were prepared by the in situ Grignard reaction of p,p'-BrC₆H₄CMe₂C₆H₄Br, Mg turnings, and HSiMe₂Cl (for 10) and the Grignard reaction using p-HMe₂SiC₆H₄Br, Mg turnings, and Me₂ECl₂ (E = Si for 11, Ge for 12, Sn for 13). The oxidation of 10-13 using Pearlman's catalyst, Pd(OH)₂/C, in aqueous THF provided the bis(arylene silanols) p,p'-HOMe₂SiC₆H₄EMe₂C₆H₄SiMe₂OH (E = C (14), Si (15), Ge (16), Sn(17)). The HCl-catalyzed condensation of 14-17 in highly diluted solutions of acetone/water afforded the siloxane-bridged paracyclophanes cyclo-[p,p'-Me₂SiC₆H₄EMe₂C₆H₄SiMe₂O]₂ (6-9) that incorporate the group 14 elements E = C, Si, Ge, and Sn. Compounds 6-17 were investigated by multinuclear solution and solid-state NMR spectroscopy and 6 and 9 also by X-ray crystallography.

Copper-transporting P-Type ATPase, ATP7A, confers multidrug resistance and its expression is related to resistance to SN-38 in clinical colon cancer

We and others have shown that the copper transporters ATP7A and ATP7B play a role in cellular resistance to cisdiaminedichloroplatinum (II) (CDDP).  In this study, we found that ATP7A transfection of Chinese hamster ovary  cells (CHOK1) and fibroblasts isolated from Menkes disease patients  enhanced resistance not only to CDDP but also to various anticancer drugs, such as vincristine, paclitaxel, 7-ethyl-10- hydroxy-camptothecin (SN-38),  etoposide, doxorubicin, mitoxantron, and 7-ethyl-10-[4-(1-piperidino)-1-piperidino] carbonyloxycamptothecin (CPT-11). ATP7A preferentially localized
doxorubicin fluorescence to the Golgi apparatus in contrast to the more intense nuclear staining of doxorubicin in the parental cells. Brefeldin A   partially and monensin completely altered the distribution of doxorubicin to the nuclei in the ATP7A-expressing cells. ATP7A expression also enhanced the efflux rates of doxorubicin and SN-38 from cells and increased the uptake of SN-38 in membrane vesicles. These findings strongly suggested that   ATP7A confers multidrug resistance to the cells by compartmentalizing drugs in the Golgi apparatus and by enhancing efflux of these drugs, and the trans-Golgi network has an important role of ATP7A-related drug resistance. ATP7A was expressed in 8 of 34 (23.5%) clinical colon cancer specimens but not in the adjacent normal epithelium. Using the histoculture drug response assay that is useful for the prediction of drug sensitivity of clinical cancers, ATP7A-expressing colon cancer cells were significantly more  resistant to SN-38 than ATP7Anegative cells. Thus, ATP7A confers  resistance to various anticancer agents on cancer cells and might be a good index of drug resistance in clinical colon cancers.

Preparation and characterisation of new titanium based alloys for orthopaedic and dental applications

Various types of titanium alloys with high strength and low elastic modulus and, at the same time, vanadium and aluminium free have been developed as surgical biomaterials in recent years. Moreover, porous metals are promising hard tissue implants in orthopaedic and dentistry, where they mimic the porous structure and the low elastic modulus of natural bone. In the present study, new biocompatible Ti-based alloy foams with approximate relative densities of 0.4, in which Sn and Nb were added as alloying metals, were synthesised through powder metallurgy method.
The new alloys were prepared by mechanical alloying and subsequently sintered at high temperature using a vacuum furnace. The characteristics and the processability of the ball milled powders and the new porous titanium-based alloys were characterised by X-ray diffraction, optical
microscopy and scanning electron microscopy .The mechanical properties of the new titanium alloys were examined by Vickers microhardness measurements and compression testing.

Simultaneous determination of irinotecan (CPT-11) and SN-38 in tissue culture media and cancer cells by high performance liquid chromatography: Application to cellular metabolism and accumulation studies

A simple and sensitive HPLC method was developed to simultaneously determine CPT-11 and its major metabolite SN-38 in culture media and cell lysates. Camptothecin (CPT) was used as internal standard (I.S.). Compounds were eluted with acetonitrile–50 mM disodium hydrogen phosphate buffer containing 10 mM sodium 1-heptane-sulfonate, with the pH adjusted to 3.0 using 85% (w/v) orthophosphoric acid (27/73, v/v) by a Hyperclon ODS (C18) column (200 mm × 4.6 mm i.d.), with detection at excitation and emission wavelengths of 380 and 540 nm, respectively. The average extraction efficiencies were 96.9–108.3% for CPT-11 in culture media and 94.3–107.2% for CPT-11 in cell lysates; and 87.7–106.8% for SN-38 in culture media and 90.1–105.6% for SN-38 in cell lysates. Within- and between-day precision and accuracy varied from 0.1 to 10.3%. The limit of quantitation (precision and accuracy <20%) was 5.0 and 2.0 ng/ml for CPT-11 and 1.0 and 0.5 ng/ml for SN-38 in culture media and cell lysates, respectively. This method was successfully applied to quantitate the cellular accumulation and metabolism of CPT-11 and SN-38 in H4-II-E, a rat hepatoma cell line.

Trimethylene-bridged tetraorganodistannoxanes{[Me3SiCH2(RCOO)Sn(CH2)3Sn(OOCR)CH2SiMe3]O}n(R=Ph,2,4-Me2C6H3): control of structure by variation of R*

The synthesis of trimethylene-bridged carboxylate-substituted tetraorganodistannoxanes {[Me_3SiCH_2(RCOO)Sn(CH_2)_3Sn(OOCR)CH_2SiMe_3]O}_n (1, R = Ph; 2, R = 2,4-Me_2C_6H_3) is reported. Depending on the structure of R, in the solid state these compounds are either dimers (1, n = 2, cis-isomer) with a ladder-type structure or tetramers (2, n = 4) with a double ladder-type structure.

Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. synthesis, characterization and XRPD structures of [Sn(pcp)] and [Cu(pcp)]

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp = CH₂(PhPO₂)₂^2-, have been synthesized and structurally chracterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H₂pcp) in water with SnCl₂·2H₂O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H₂pcp acid and Cu(O₂CMe)₂·H₂O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2₁Ic, a = 11.2851(1), b = 15.4495(6), c = 8.6830(1) Å, ^β= 107.546(1)°, V = 1443.44(9) Å, Z = 4. Crystal data for [Cu(pcp)]: triclinic, space group P, a = 10.7126(4), b = 13.0719(4), c = 4.9272(3) Å, α= 92.067(5), β= 95.902(7), γ= 87.847(4)°, V = 685.47(7), Z = 2. The tin compound has been characterized by ¹¹⁹Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

Preparation of Mg55Ni35Si10 amorphous powders by mechanical alloying and consolidation by vacuum hot pressing

Amorphous 55Mg35NilOSi alloy powder has been synthesized by mechanical alloying technique using pure Mg, Ni and Si elemental powders. The transformation of the crystalline powders into an amorphous one has been investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and differential scanning calorimetry. The new material produced has a higher thermal stability than reported results, which is beneficial to the fabrication of Mg-Ni-Si bulk amorphous components through powder metallurgy.

Simultaneous determination of the lactone and carboxylate forms of irintecan (CPT-11) and its actie metabolite SN-38 by high-performance liquid chromatography: Application to plasma pharmacokinetic studies in the rat.

Irinotecan (CPT-11) and its main metabolite SN-38 are potent anticancer derivatives of camptothecin (CPT), with active lactone and inactive carboxylate forms coexisting. A simple and sensitive HPLC method using the ion-pairing reagent tetrabutylammonium hydrogen sulfate (TBAHS) was developed to simultaneously determine all four analytes in rat plasma samples. Camptothecin (CPT) was used as internal standard. The mobile phase was 0.1 M potassium dihydrogen phosphate containing 0.01 M TBAHS (pH 6.4)–acetonitrile (75:25, v/v). Separation of the compounds was carried out on a Hypersil C18 column, monitored at 540 nm (excitation wavelength at 380 nm). All four compounds gave linear response as a function of concentration over 0.01–10 μM. The limit of quantitation in rat plasma was 0.01, 0.008, 0.005 and 0.005 μM for CPT-11 lactone, CPT-11 carboxylate, SN-38 lactone and SN-38 carboxylate, respectively. The method was successfully used in the study on the effect of coadministered thalidomide on the plasma pharmacokinetics of CPT-11 and SN-38 in rats. Coadministered thalidomide (100 mg/kg body weight by intraperitoneal injection) significantly increased the AUC_0–10h values of CPT-11 lactone and CPT-11 carboxylate by 32.6% and 30.3 %, respectively, (P < 0.01), but decreased the values by 19.2% and 32.4% for SN-38 lactone and carboxylate, respectively, (P < 0.05). Accordingly, the value of total body clearance (CL) of CPT-11 lactone was significantly lower in combination group compared to the control (1.329 versus 1.837 L/h/kg, P = 0.0002). Plasma t_1/2β values for SN-38 lactone and carboxylate were significantly (P < 0.01) smaller in rats with coadministered thalidomide, as compared to rats receiving CPT-11 alone. Further studies are needed to explore the underlying mechanisms for the observed kinetic interaction between CPT-11 and thalidomide.