Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T_g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T_g and T_m of the polymers.     

Selecting green suppliers based on GSCM practices: Using fuzzy TOPSIS applied to a Brazilian electronics company

Due to an increased awareness and significant environmental pressures from various stakeholders, companies have begun to realize the significance of incorporating green practices into their daily activities. This paper proposes a framework using Fuzzy TOPSIS to select green suppliers for a Brazilian electronics company; our framework is built on the criteria of green supply chain management (GSCM) practices. An empirical analysis is made, and the data are collected from a set of 12 available suppliers. We use a fuzzy TOPSIS approach to rank the suppliers, and the results of the proposed framework are compared with the ranks obtained by both the geometric mean and the graded mean methods of fuzzy TOPSIS methodology. Then a Spearman rank correlation coefficient is used to find the statistical difference between the ranks obtained by the three methods. Finally, a sensitivity analysis has been performed to examine the influence of the preferences given by the decision makers for the chosen GSCM practices on the selection of green suppliers. Results indicate that the four dominant criteria are Commitment of senior management to GSCM; Product designs that reduce, reuse, recycle, or reclaim materials, components, or energy; Compliance with legal environmental requirements and auditing programs; and Product designs that avoid or reduce toxic or hazardous material use.     

Investigation of clay modifier effects on the structure and rheology of supercritical carbon dioxide‐processed polymer nanocomposites

Superior property enhancements in polymer–clay nanocomposites can be achieved if one can significantly enhance the nanoclay dispersion and polymer–clay interactions. Recent studies have shown that nanoclays can be dispersed in polymers using supercritical carbon dioxide (scCO₂). However, there is need for a better understanding of how changing the clay modifier affects the clay dispersability by scCO₂ and the resultant nanocomposite rheology. To address this, the polystyrene (PS)/clay nanocomposites with “weak” interaction (Cloisite 93A clay) and “strong” interaction (Cloisite 15A clay) have been prepared using the supercritical CO₂ method in the presence of a co‐solvent. Transmission electron microscopy images and small‐angle X‐ray diffraction illustrate that composites using 15A and 93A clays show similar magnitude of reduction in the average tactoid size, and dispersion upon processing with scCO₂. When PS and the clays are coprocessed in scCO₂, the “dispersion” of clays appears to be independent of modifier or polymer–clay interaction. However, the low‐frequency storage modulus in the scCO₂‐processed 15A nanocomposites is two orders of magnitude higher than that of 93A nanocomposites. It is postulated that below percolation (solution blended composites), the strength of polymer–clay interaction is not a significant contributor to rheological enhancement. In the scCO₂‐processed nanocomposites the enhanced dispersion passes the percolation threshold and the interactions dictate the reinforcement potential of the clay–polymer–clay network. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 823–831, 2010     

FTIR spectroscopic investigation of thermal effects in semi‐syndiotactic polypropylene

The temperature‐dependent behavior of individual components within metallocene‐catalyzed semisyndiotactic polypropylenes (semi‐sPP) with a wide range of stereoregular content (26 to 96% rr) is studied using Fourier transform infrared (FTIR) spectroscopy and temperature‐modulated differential scanning calorimetry (DSC). Changes in sensitive, high‐resolution absorbance spectra are observed as melt‐slow‐cooled thin films are subjected to stepwise temperature increases. In general, spectral bands previously identified as being sensitive to ordered structures (e.g., conformed chains, crystal morphs) appear to follow overall trends of shifting to lower wavenumbers (energies), broadening, and decreasing in peak area intensity as temperature increases. Peaks that appear due to “splitting” (observed in more stereoregular materials) show a trend toward coalescence as temperature increases; this corresponds to a gradual loss of chain conformational order. Gauche‐gauche‐trans‐trans (ggtt)_n helical and all‐trans (tttt)_n planar zigzag‐conformed chains that participate in the crystalline‐amorphous interfacial region (“mesophase”) appear to be more stable (i.e., they do not lose their conformational order as easily) with increasing temperature in materials with a greater degree of syndiotacticity. Moreover, IR data correspond well with modulated DSC endotherms located near 50 °C and 70 °C. At each transition temperature—thought to represent, respectively, a thermally driven chain conformation from planar zigzags to helices, and a dynamic disorder of helices marked by rapid gauche ? trans isomerization—the IR absorbance ratio, A₉₇₈/A₉₆₃, which represents the relative population of helical chains, undergoes an accelerated decrease. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 439–461, 2005     

Assessment of Physical Process Conditions for Enhanced Production of Novel Glutaminase-Free L-Asparaginase from <Emphasis Type="BoldItalic">Pectobacterium carotovorum</Emphasis> MTCC 1428

Statistically based experimental design was applied to maximize the production of glutaminase-free L-asparaginase from Pectobacterium carotovorum MTCC 1428. The effect of physical process parameters (initial pH of the medium, temperature, rpm of the shaking incubator, and inoculum size) on the production of L-asparaginase from P. carotovorum MTCC 1428 was studied using central composite design technique. The individual optimum levels of initial pH of the medium, temperature, rpm of shaking incubator, and inoculum size were found to be 6.90, 29.8 °C, 157 rpm, and 2.61% (v/v), respectively, for the production of L-asparaginase. After physical process parameters optimization, the production and productivity of L-asparaginase was enhanced by 26.39% (specific activity) and 10.19%, respectively. Maximization of L-asparaginase production was achieved at 12 h under optimal levels of physical process parameters in shake flask level.     

Exploring the first steps in core-shell electrocatalyst preparation: in situ characterization of the underpotential deposition of Cu on supported Au nanoparticles

The underpotential deposition (upd) of a Cu shell on a non-Pt nanoparticle core followed by galvanic displacement of the Cu template shell to form core-shell electrocatalyst materials is one means by which the Pt-based mass activity targets required for commercialization of PEM fuel cells may be reached. In situ EXAFS measurements were conducted at both the Au L(3) and the Cu K absorption edges during deposition of Cu onto a carbon-supported Au electrocatalyst to study the initial stages of formation of such a core-shell electrocatalyst. The Au L(3) EXAFS data obtained in 0.5 mol dm(-3) H(2)SO(4) show that the shape of the Au core is potential dependent, from a flattened to a round spherical shape as the Cu upd potential is approached. Following the addition of 2 mmol dm(-3) Cu, the structure was also measured as a function of the applied potential. At +0.2 V vs Hg/Hg(2)SO(4), the Cu(2+) species was found to be a hydrated octahedron. As the potential was made more negative, single-crystal studies predict an ordered bilayer of sulfate anions and partially discharged Cu ions, followed by a complete/uniform layer of Cu atoms. In contrast, the model obtained by fitting the Au L(3) and Cu K EXAFS data corresponds first to partially discharged Cu ions deposited at the defect sites in the outer shell of the Au nanoparticles at -0.42 V, followed by the growth of clusters of Cu atoms at -0.51 V. The absence of a uniform/complete Cu shell, even at the most negative potentials investigated, has implications for the structure, and the activity and/or stability, of the core-shell catalyst that would be subsequently formed following galvanic displacement of the Cu shell.     

Some robust objectives of FCM for data analyzing

There are many data clustering techniques available to extract meaningful information from real world data, but the obtained clustering results of the available techniques, running time for the performance of clustering techniques in clustering real world data are highly important. This work is strongly felt that fuzzy clustering technique is suitable one to find meaningful information and appropriate groups into real world datasets. In fuzzy clustering the objective function controls the groups or clusters and computation parts of clustering. Hence researchers in fuzzy clustering algorithm aim is to minimize the objective function that usually has number of computation parts, like calculation of cluster prototypes, degree of membership for objects, computation part for updating and stopping algorithms. This paper introduces some new effective fuzzy objective functions with effective fuzzy parameters that can help to minimize the running time and to obtain strong meaningful information or clusters into the real world datasets. Further this paper tries to introduce new way for predicting membership, centres by minimizing the proposed new fuzzy objective functions. And experimental results of proposed algorithms are given to illustrate the effectiveness of proposed methods.     

Green synthesis of biogenic metal nanoparticles by terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible agents

The size, shape and controlled dispersity of nanoparticles play a vital role in determining the physical, chemical, optical and electronic properties attributing its applications in environmental, biotechnological and biomedical fields. Various physical and chemical processes have been exploited in the synthesis of several inorganic metal nanoparticles by wet and dry approaches viz., ultraviolet irradiation, aerosol technologies, lithography, laser ablation, ultrasonic fields, and photochemical reduction techniques. However, these methodologies remain expensive and involve the use of hazardous chemicals. Therefore, there is a growing concern for the development of alternative environment friendly and sustainable methods. Increasing awareness towards green chemistry and biological processes has led to a necessity to develop simple, cost-effective and eco-friendly procedures. Phototrophic eukaryotes such as plants, algae, and diatoms and heterotrophic human cell lines and some biocompatible agents have been reported to synthesize greener nanoparticles like cobalt, copper, silver, gold, bimetallic alloys, silica, palladium, platinum, iridium, magnetite and quantum dots. Owing to the diversity and sustainability, the use of phototrophic and heterotrophic eukaryotes and biocompatible agents for the synthesis of nanomaterials is yet to be fully explored. This review describes the recent advancements in the green synthesis and applications of metal nanoparticles by plants, aquatic autotrophs, human cell lines, biocompatible agents and biomolecules.     

Synthesis of N2-alkyl-8-oxo-7,8-dihydro-2'-deoxyguanosine derivatives and effects of these modifications on RNA duplex stability

N(2)-alkyl analogues of 8-oxo-7,8-dihydro-2'-deoxyguanosine (OG) were synthesized (alkyl = propyl, benzyl) via reductive amination of the protected OG nucleoside and incorporated into various positions of an RNA strand. Thermal stability studies of duplexes containing A or C opposite a single modified base revealed only moderate destabilization. Both OG as well as its N(2)-alkyl analogues can pair opposite A or C with nearly equal stability, potentially offering a new means of modulating RNA-protein interactions in the minor vs major grooves.