In situ surface modification of molybdenum-doped organic-inorganic hybrid TiO2 nanoparticles under hydrothermal conditions and treatment of pharmaceutical effluent

Molybdenum-doped TiO2 organic-inorganic hybrid nanoparticles were synthesized under mild hydrothermal conditions by in situ surface modification using n-butylamine. This was carried out at 150 degrees C at autogeneous pressure over 18 h. n-Butylamine was selected as a surfactant since it produced nanoparticles of the desired size and shape. The products were characterized using powder X-ray diffraction, Fourier transform infrared spectrometry, dynamic light-scattering spectroscopy, UV-Vis spectroscopy and transmission electron microscopy. Chemical oxygen demand was estimated in order to determine the photodegradation efficiency of the molybdenum-doped TiO2 hybrid nanoparticles in the treatment of pharmaceutical effluents. It was found that molybdenum-doped TiO2 hybrid nanoparticles showed higher photocatalytic efficiency than untreated TiO2 nanoparticles.

Interaction of synthetic analogs of distamycin and netropsin with nucleic acids. Does curvature of ligand play a role in distamycin-DNA interactions?

Distamycin and netropsin, a class of minor groove binding nonintercalating agents, are characterized by their B-DNA and A-T basespecific interactions. To understand the CQI I ~OIT~ ~ I ~ ~aOnMd ~c hemical basis of the above specificities, the DNA-binding characteristics of a novel synthetic analogue of distamycin have been studied. The analogue, mPD derivative, has the requisite charged end groups and a number of potential hydrogen-bonding loci equal to those of distamycin. The difference in the backbone curvatures of the ligands, distamycin, the mPD derivative, and NSC 101327 (another structurally analogous compound),is a major difference between these ligands. UV and CD spectrosoopic studies reported here show the following salient features: The mPD derivative recognizes only B-DNA, to which it binds via the minor groove. On the other hand, unlike distamycin, it binds with comparable affinities to A-T and G-C base pairs in a natural DNA. These DNA-binding properties are compared with those reported earlier for distamycin and NSC 101327 [Zimmer, Ch., & Wahnert, U. (1986) Prog. Biophys. Mol. Biol. 47, 31-1121. The backbone structures of these three ligands were compared to show the progressive decrease in curvatures in the order distamycin, mPD derivative, and NSC 101327. The plausible significance of the backbone curvature vis-&vis the characteristic B-DNA and AT-specific binding of distamycin is discussed. To our knowledge, this is the first attempt (with a model synthetic analogue) to probe the possible influence of backbone curvature upon the specificity of interactions of the distamycin class of groove-binding ligands with DNA.

Synthesis and enhanced green photoluminescence emission from BCT ZnS nanocrystals

Body-centered-tetragonal (BCT) ZnS nanocrystals have been synthesized, for the first time to the best of our knowledge, by using the chemical coprecipitation method at higher synthesis temperatures of 65 and 95 degrees C. It is confirmed from X-ray diffraction (XRD) studies that in the high-temperature-synthesized samples, cubic and BCT phases coexist, in contrast to the room-temperature-synthesized sample, which consists of only cubic phase with sizes of the particles lying between 2 and 3 nm. The sizes of BCT phase nanocrystals are bigger than those of cubic phase of ZnS. The presence of BCT phase of ZnS in the samples is increased from 40 to 90% when the temperature of synthesis is increased from 65 to 95 degrees C. The nanocrystalline nature and UV-Vis absorption characteristics of the prepared samples have been studied with a transmission electron microscope (TEM) and a UV-Visible pectrophotometer, respectively. The room-temperature-synthesized ZnS sample shows photoluminescence (PL) emission in the blue region with multiple peaks, whereas the high-temperature-synthesized samples show PL emissions in the visible region. The Gaussian fittings of the measured PL spectra shows that three PL peaks at 429, 477, and 525 nm are appeared in the 65 degrees C sample and two peaks at 491 and 540 nm appear in the 95 degrees C sample with the enhanced PL intensity of the green peak at 540 nm. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Synthesis and characterization of metal substituted AlxCr1-x(acetylacetonate)(3) single-source precursors for their application to MOCVD of thin films

A detailed study, involving the synthesis of a single-source precursor containing two metal ions sharing the same crystallographic site, has been undertaken to elucidate the use of such a single-source precursor in a CVD process for growing thin films of oxides comprising these two metals, ensuring a uniform composition and distribution of metal ions. The substituted complexes Cr1-xAlx(acac)(3), where acac = acetyl-acetonate, have been prepared by a co-synthesis method, and characterized using UV-Vis spectroscopy. TGA/DTA measurements, and single crystal X-ray diffraction at low temperature. All the studied compositions crystallize in the monoclinic space group P2(1)/c with Z = 4 in the unit cell. It was observed that the ratio (Al:Cr) of the site occupancy for the metal ions, obtained from single crystal refinement, is in agreement with the results obtained from complexometric titrations. All the solid state structures have the metal in an octahedral environment forming six-membered chelate rings. M-O acac bond lengths and disorder in the terminal carbon have been studied in detail for these substituted metal-organic complexes. One composition among these was chosen to evaluate their suitability as a single-source precursor in a LPMOCVD process (low-pressure metal-organic chemical vapour deposition) for the deposition of a substituted binary metal oxide thin film. The resulting thin films were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. (C) 2010 Elsevier Ltd. All rights reserved.

An accurate numerical integration scheme for finite rotations using rotation vector parametrization

A numerical integration procedure for rotational motion using a rotation vector parametrization is explored from an engineering perspective by using rudimentary vector analysis. The incremental rotation vector, angular velocity and acceleration correspond to different tangent spaces of the rotation manifold at different times and have a non-vectorial character. We rewrite the equation of motion in terms of vectors lying in the same tangent space, facilitating vector space operations consistent with the underlying geometric structure. While any integration algorithm (that works within a vector space setting) may be used, we presently employ a family of explicit Runge-Kutta algorithms to solve this equation. While this work is primarily motivated out of a need for highly accurate numerical solutions of dissipative rotational systems of engineering interest, we also compare the numerical performance of the present scheme with some of the invariant preserving schemes, namely ALGO-C1, STW, LIEMIDEA] and SUBCYC-M. Numerical results show better local accuracy via the present approach vis-a-vis the preserving algorithms. It is also noted that the preserving algorithms do not simultaneously preserve all constants of motion. We incorporate adaptive time-stepping within the present scheme and this in turn enables still higher accuracy and a `near preservation' of constants of motion over significantly longer intervals. (C) 2010 The Franklin Institute. Published by Elsevier Ltd. All rights reserved.

Graphene analogue BCN: Femtosecond nonlinear optical susceptibility and hot carrier dynamics

Third-order nonlinear absorption and refraction coefficients of a few-layer boron carbon nitride (BCN) and reduced graphene oxide (RGO) suspensions have been measured at 3.2 eV in the femtosecond regime. Optical limiting behavior is exhibited by BCN as compared to saturable absorption in RGO. Nondegenerate time-resolved differential transmissions from BCN and RGO show different relaxation times. These differences in the optical nonlinearity and carrier dynamics are discussed in the light of semiconducting electronic band structure of BCN vis-a-vis the Dirac linear band structure of graphene. (C) 2010 Elsevier B.V. All rights reserved.

Antimicrobial activity of highly stable silver nano particles embedded in agar-agar matrix as a thin film

Highly stable silver nanoparticles (Ag NPs) in agar-agar (Ag/agar) as inorganic-organic hybrid were obtained as free-standing film by in situ reduction of silver nitrate by ethanol. The antimicrobial activity of Ag/agar film on Escherichia coli (E. coil), Staphylococcus aureus (S. aureus), and Candida albicans (C albicans) was evaluated in a nutrient broth and also in saline solution. In particular, films were repeatedly tested for antimicrobial activity after recycling. UV-vis absorption and TEM studies were carried out on films at different stages and morphological studies on microbes were carried out by SEM. Results showed spherical Ag NPs of size 15-25 nm, having sharp surface plasmon resonance (SPR) band. The antimicrobial activity of Ag/agar film was found to be in the order, C. albicans > E. coil > S. aureus, and antimicrobial activity against C. albicans was almost maintained even after the third cycle. Whereas, in case of E. coil and S. aureus there was a sharp decline in antimicrobial activity after the second cycle. Agglomeration of Ag NPs in Ag/agar film on exposure to microbes was observed by TEM studies. Cytotoxic experiments carried out on HeLa cells showed a threshold Ag NPs concentration of 60 mu g/mL, much higher than the minimum inhibition concentration of Ag NPs (25.8 mu g/mL) for E. coli. The mechanical strength of the film determined by nanoindentation technique showed almost retention of the strength even after repeated cycle. (C) 2010 Elsevier Ltd. All rights reserved.

Protein Kinase C and Anaplastic Lymphoma Kinase Targeted Compounds

The protein kinases (PKs) belong to the largest single family of enzymes, phosphotransferases, which catalyze the phosphorylation of other enzymes and proteins and function primarily in signal transduction. Consequently, PKs regulate cell mechanisms such as growth, differentiation, and proliferation. Dysfunction of these cellular mechanisms may lead to cancer, a major predicament in health care. Even though there is a range of clinically available cancer-fighting drugs, increasing number of cancer cases and setbacks such as drug resistance, constantly keep cancer research active. At the commencement of this study an isophthalic acid derivative had been suggested to bind to the regulatory domain of protein kinase C (PKC). In order to investigate the biological effects and structure-activity relationships (SARs) of this new chemical entity, a library of compounds was synthesized. The best compounds induced apoptosis in human leukemia HL-60 cells and were not cytotoxic in Swiss 3T3 fibroblasts. In addition, the best apoptosis inducers were neither cytotoxic nor mutagenic. Furthermore, results from binding affinity assays of PKC isoforms revealed the pharmacophores of these isophthalic acid derivatives. The best inhibition constants of the tested compounds were measured to 210 nM for PKCα and to 530 nM for PKCδ. Among natural compounds targeting the regulatory domain of PKC, the target of bistramide A has been a matter of debate. It was initially found to activate PKCδ; however, actin was recently reported as the main target. In order to clarify and to further study the biological effects of bistramide A, the total syntheses of the natural compound and two isomers were performed. Biological assays of the compounds revealed accumulation of 4n polyploid cells as the primary mode of action and the compounds showed similar overall antiproliferative activities. However, each compound showed a distinct distribution of antimitotic effect presumably via actin binding, proapoptotic effect presumably via PKCδ, and pro-differentiation effect as evidenced by CD11b expression. Furthermore, it was shown that the antimitotic and proapoptotic effects of bistramide A were not secondary effects of actin binding but independent effects. The third aim in this study was to synthesize a library of a new class of urea-based type II inhibitors targeted at the kinase domain of anaplastic lymphoma kinase (ALK). The best compounds in this library showed IC50 values as low as 390 nM for ALK while the initial low cellular activities were successfully increased even by more than 70 times for NPM-ALK- positive BaF3 cells. More importantly, selective antiproliferative activity on ALK-positive cell lines was achieved; while the best compound affected the BaF3 and SU-DHL-1 cells with IC50 values of 0.5 and 0.8 μM, respectively, they were less toxic to the NPM-ALK-negative human leukemic cells U937 (IC50 = 3.2 μM) and BaF3 parental cells (IC50 = 5.4 μM). Furthermore, SAR studies of the synthesized compounds revealed functional groups and positions of the scaffold, which enhanced the enzymatic and cellular activities.

Crystal Chemistry of the Noncentrosymmetric Eulytites: A(3)Bi(XO4)(3) (X = V, A = Pb; X = P, A = Ca, Cd, Sr, Pb)

Eulytite compounds, A(3)Bi(XO4)(3) (X = P, A = Ca, Cd, Sr, Pb), belong to the noncentrosymmetric space group l (4) over bar 3d (No. 220) as determined by single-crystal X-ray diffraction studies. The crystals were grown from the melt-cool technique with considerable difficulty as the compounds melt incongruently at their melting temperature, except for the compound Pb3Bi(PO4)(3). The unit cell parameter a is 9.984(5), 9.8611(3), 10.2035(3), and 10.3722(2) angstrom for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), Sr3Bi(PO4)(3), and Pb3Bi(PO4)(3) respectively, and there are four formula units in the unit cell. The structure of Pb3Bi(VO4)(3), a unique eulytite with vanadium substitution, is compared with all these phosphorus substituted eulytites. The A(2+) and Bi3+ cations occupy the special position (16c) while the O anions occupy the general Wyckoff position (48e) in the crystal structure. Only one O position has been identified for Pb3Bi(PO4)(3) and Pb3Bi(VO4)(3), whereas two O atom sites were identified for Ca3Bi(PO4)(3), Cd3Bi(PO4)(3), and Sr3Bi(PO4)(3). The UV-vis diffuse reflectance spectra indicate large band gaps for all the phosphate eulytites while a lower band gap is observed for the vanadate eulytite. The feasibility of the use of these compounds in optoelectronic devices has been tested by measuring the second-harmonic generation (SHG) values which have been found to be of a magnitude equivalent to the commercially used KDP (KH2PO4).

Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modified neodymium doped TiO2 hybrid nanoparticles. For the first time, surface modification of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modifier under mild hydrothermal conditions. The modified nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modified neodymium doped TiO2 nanoparticles was more compared to pure TiO2, which can be attributed to the doping and modification with n-butylamine.

Enhancement of fatigue life of Ni-Ti-Fe shape memory alloys by thermal cycling

The effect of thermal cycling on the load-controlled tension-tension fatigue behavior of a Ni-Ti-Fe shape memory alloy (SMA) at room temperature was studied. Considerable strain accumulation was observed to occur in this alloy under both quasi-static and cyclic loading conditions. Though, in all cases, steady-state is reached within the first 50-100 cycles, the accumulated steady-state strain, epsilon(p.ss), is much smaller in thermally cycled alloy. As a result, the fatigue performance of them was found to be significantly enhanced vis-a-vis the as-solutionized alloy. Furthermore, under load-controlled conditions, the fatigue life of Ni-Ti-Fe alloys was found to be exclusively dependent on epsilon(p.ss). Observations made by profilometry and differential scanning calorimetry (DSC) indicate that the 200-500% enhancement in fatigue life of thermally cycled alloy is due to the homogeneous distribution of the accumulated fatigue strain. (C) 2010 Elsevier B.V. All rights reserved.

Calorimetry In Vapor Absorption And Binary Mixture Vapor Compression Refrigeration And Heatpump Systems

The use of binary fluid systems in thermally driven vapour absorption and mechanically driven vapour compression refrigeration and heatpump cycles has provided an impetus for obtaining experimental date on caloric properties of such fluid mixtures. However, direct measurements of these properties are somewhat scarce in spite of the calorimetric techniques described in the literature being quite adequate. Most of the design data are derived through calculations using theoretical models and vapour-liquid equilibrium data. This article addresses the choice of working fluids and the current status on the data availability vis-a-vis engineering applications. Particular emphasis is on organic working fluid pairs.

Trade Blocs and the Cold War : The CMEA and the EC challenge, 1969-1976

The coherence of the Soviet bloc was seriously tested at the turn of the 1970s, as the Soviet Union and its allies engaged in intensive negotiations over their relations with the European Communities (EC). In an effort to secure their own national economic interests many East European countries began independent manoeuvres against the wishes of their bloc leader. However, much of the intra-bloc controversy was kept out of the public eye, as the battle largely took place behind the scenes, within the organisation for economic cooperation, the Council for Mutual Economic Assistance (CMEA). The CMEA policy-making process vis-à-vis the EC is described in this study with reference to primary archival materials. This study investigates the negotiating positions and powers of the CMEA member states in their efforts to deal with the economic challenge created by the progress of the EC, as it advanced towards the customs union. This entails an analysis of the functioning principles and performance of the CMEA machinery. The study traces the CMEA negotiations that began in 1970 over its policy toward the EC. The policy was finally adopted in 1974, and was followed by the first official meeting between the two organisations in early 1975. The story ends in 1976, when the CMEA s efforts to enter into working relations with the EC were seemingly frustrated by the latter. The first major finding of the study is that, contrary to much of the prior research, the Soviet Union was not in a hegemonic position vis-à-vis its allies. It had to use a lot of its resources to tame the independent manoeuvring of its smaller allies. Thus, the USSR was not the kind of bloc leader that the totalitarian literature has described. Because the Soviet Union had to spend so much attention on its own bloc-politics, it was not able to concentrate on formulating a policy vis-à-vis the EC. Thus, the Soviet leadership was dependent on its allies in those instances when the socialist countries needed to act as a bloc. This consequently opened up the possibility for the USSR s allies to manoeuvre. This study also argues that when the CMEA did manage to find a united position, it was a force that the EC had to reckon with in its policy-making. This was particularly the case in the implementation of the EC Common Commercial Policy. The other main finding of the study is that, although it has been largely neglected in the previous literature on the history of West European integration, the CMEA did in fact have an effect on EC decision-making. This study shows how for political and ideological reasons the CMEA members did not acknowledge the EC s supranational authority. Therefore the EC had no choice but to refrain from implementing its Common Commercial Policy in full.

Elämää keskustassa ja kaupunkiseudun reunoilla. Urbaani ja jälkiesikaupungillinen elämäntyyli asumisen valinnoissa ja arkiliikkumisessa Helsingin seudulla.

The lifestyles of people living in single-family housing areas on the outskirts of the Greater Helsinki Region (GHR) are different from those living in inner city area. The urban structure of the GHR is concentrated in the capital on the one hand, and spread out across the outskirts on the other. Socioeconomic spatial divisions are evident as well-paid and educated residents move to the inner city or the single-family house dominated suburban neighbourhoods depending on their housing preferences and life situations. The following thesis explores how these lifestyles have emerged through the housing choices and daily mobility of the residents living in the new single-family housing areas on the outskirts of the GHR and the inner city. The study shows that, when it comes to lifestyles, residents on the outskirts of the region have different housing preferences and daily mobility patterns when compared with their inner city counterparts. Based on five different case study areas my results show that these differences are related to residents values, preferences and attitudes towards the neighbourhood, on the one hand, and limited by urban structure on the other. This also confirms earlier theoretical analyses and findings from the GHR. Residents who moved to the outskirts of Greater Helsinki Region and the apartment buildings of the inner city were similar in the basic elements of their housing preferences: they sought a safe and peaceful neighbourhood close to the natural environment. However, where housing choices, daily mobility and activities vary different lifestyles develop in both the outskirts and the inner city. More specifically, lifestyles in the city apartment blocks were inherently urban. Liveliness and highest order facilities were appreciated and daily mobility patterns were supported by diverse modes of transportation for the purposes of work, shopping and leisure time. On the outskirts, by contrast, lifestyles were largely post-suburban and child-friendliness appreciated. Due to the heterachical urban structure, daily mobility was more car-dependent since work, shopping and free time activities of the residents are more spread around the region. The urban structure frames the daily mobility on the outskirts of the region, but this is not to say that short local trips replace longer regional ones. This comparative case study was carried out in the single-family housing areas of Sundsberg in Kirkkonummi, Landbo in Helsinki and Ylästö in Vantaa, as well as in the inner city apartment building areas of Punavuori and Katajanokka in Helsinki. The data is comprised of residential surveys, interviews, and statistics and GIS data sets that illustrate regional daily mobility, socio-economic structure and vis-à-vis housing stock.

The Reproducing Kernel DMS-FEM: 3D Shape Functions and Applications to Linear Solid Mechanics

We propose a family of 3D versions of a smooth finite element method (Sunilkumar and Roy 2010), wherein the globally smooth shape functions are derivable through the condition of polynomial reproduction with the tetrahedral B-splines (DMS-splines) or tensor-product forms of triangular B-splines and ID NURBS bases acting as the kernel functions. While the domain decomposition is accomplished through tetrahedral or triangular prism elements, an additional requirement here is an appropriate generation of knotclouds around the element vertices or corners. The possibility of sensitive dependence of numerical solutions to the placements of knotclouds is largely arrested by enforcing the condition of polynomial reproduction whilst deriving the shape functions. Nevertheless, given the higher complexity in forming the knotclouds for tetrahedral elements especially when higher demand is placed on the order of continuity of the shape functions across inter-element boundaries, we presently emphasize an exploration of the triangular prism based formulation in the context of several benchmark problems of interest in linear solid mechanics. In the absence of a more rigorous study on the convergence analyses, the numerical exercise, reported herein, helps establish the method as one of remarkable accuracy and robust performance against numerical ill-conditioning (such as locking of different kinds) vis-a-vis the conventional FEM.