Electrostatic assembly of nanoparticles and biomacromolecules

The controlled assembly of nanoparticles in thin film form on solid supports, both as monolayers and as superlattice structures, is a problem of considerable topical interest. Among the many interactions used to program the assembly of nanoparticles, electrostatic forces are particularly interesting for many reasons. This Account deals with assembling surface-modified nanoparticles in thin film form using electrostatic interactions at the air-water interface and in thermally evaporated lipid films. The generality of the electrostatic assembly protocol is demonstrated in the immobilization of DNA and proteins in lipid films.     

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

In this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g^?1s^?1over 10 min as compared to 1.2, 7.5 J g^?1s^?1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46381.     

Formation of BaCrO4 NanoCrystallites within Thermally Evaporated Sodium Bis-2-Ethylhexyl-Sulfosuccinate and Stearic Acid Thin Films

This paper describes the growth of barium chromate (BaCrO₄) nanocrystallites within thermally evaporated thin films of stearic acid (StA) and sodium bis-2-ethylhexyl-sulfosuccinate by a process of Ba²⁺ ion entrapment followed by in situ reaction with CrO₄²⁻ ions. Dense spherical assemblies of BaCrO₄ nanocrystallites of very uniform size (∼50 nm) were obtained within the two different host matrices. The spherical assemblies were composed of smaller (ca. 5–10 nm size) BaCrO₄ crystals indicating that efficient size control over crystal size may be exercised by the matrix. Contact angle measurements of the BaCrO₄–StA and BaCrO₄–sodium bis-2-ethylhexyl-sulfosuccinate films indicated that they were hydrophobic, thus pointing to the possible role of hydrophobic interaction between the StA and sodium bis-2-ethylhexyl-sulfosuccinate monolayer-covered BaCrO₄ crystals in the assembly process.     

Effect of Trace Additions (Be,Cr, Mn and Co) on the Mechanical Properties and Fracture Toughness of Fe-containing Al-7Si-0.3Mg Alloy

Abstract

The detrimental effect of iron impurity on the mechanical properties and fracture toughness of Al-7Si-0.3Mg alloy has been widely reported. It is also quite evident that Fe forms the intermetallic compound β-FeSiAl₅, which exists as needles/plates in the interdendritic regions, thereby lowering the mechanical properties. However, very little is known about the methods of counteracting this detrimental effect. The present study has shown that trace additions of Be, Cr, Mn and Co, individually or combined, tie up the iron to form new phases with altered morphology which significantly influence the mechanical properties. Among the trace additions, Be is found to be most effective in neutralising the detrimental effect of Fe on tensile properties. Hardness, tensile and yield strengths, ductility, dynamic fracture toughness (K_d and, K_jd remain constant with an increase in Fe from 0.1 to 0.93% where Be additions are present. Be additions in combination with Mn and/or Cr are also found to nullify the detrimental effect of Fe. However, Be and Mn, when added together, seem to be most effective in providing better tensile properties, than does a Be addition alone or with other additions. The probable reason for good mechanical properties, even in the case of higher-Fe-containing alloys containing a Be addition can be explained as follows: The Be-Fe phases are present inside the α-Al dendrites and act as a preferential site for crack nucleation rather than the Si particles. However, these nucleated cracks are arrested when they approach the α-Al dendrites.     

Radiation-Induced Senescence Reprograms Secretory and Metabolic Pathways in Colon Cancer HCT-116 Cells

Understanding the global metabolic changes during the senescence of tumor cells can have implications for developing effective anti-cancer treatment strategies. Ionizing radiation (IR) was used to induce senescence in a human colon cancer cell line HCT-116 to examine secretome and metabolome profiles. Control proliferating and senescent cancer cells (SCC) exhibited distinct morphological differences and expression of senescent markers. Enhanced secretion of pro-inflammatory chemokines and IL-1, anti-inflammatory IL-27, and TGF-β1 was observed in SCC. Significantly reduced levels of VEGF-A indicated anti-angiogenic activities of SCC. Elevated levels of tissue inhibitors of matrix metalloproteinases from SCC support the maintenance of the extracellular matrix. Adenylate and guanylate energy charge levels and redox components NAD and NADP and glutathione were maintained at near optimal levels indicating the viability of SCC. Significant accumulation of pyruvate, lactate, and suppression of the TCA cycle in SCC indicated aerobic glycolysis as the predominant energy source for SCC. Levels of several key amino acids decreased significantly, suggesting augmented utilization for protein synthesis and for use as intermediates for energy metabolism in SCC. These observations may provide a better understanding of cellular senescence basic mechanisms in tumor tissues and provide opportunities to improve cancer treatment.     

A study on the sealing performance of bolted flange joints with gaskets using finite element analysis

Gaskets play an important role in the sealing performance of bolted flange joints, and their behaviour is complex due to nonlinear material properties combined with permanent deformation. The variation of contact stresses due to the rotation of the flange and the material properties of the gasket play important roles in achieving a leak proof joint. In this paper, a three-dimensional finite element analysis (FEA) of bolted flange joints has been carried out by taking experimentally obtained loading and unloading characteristics of the gaskets. Analysis shows that the distribution of contact stress has a more dominant effect on sealing performance than the limit on flange rotation specified by ASME.     

Reduced graphene oxide/tin oxide composite as an enhanced anode material for lithium ion batteries prepared by homogenous coprecipitation

Reduced graphene oxide/tin oxide composite is prepared by homogenous coprecipitation. Characterizations show that tin oxide particles are anchored uniformly on the surface of reduced graphene oxide platelets. As an anode material for Li ion batteries, it has 2140 mAh g⁻¹ and 1080 mAh g⁻¹ capacities for the first discharge and charge, respectively, which is more than the theoretical capacity of tin oxide, and has good capacity retention with a capacity of 649 mAh g⁻¹ after 30 cycles. The simple synthesis method can be readily adapted to prepare other composites containing reduced graphene oxide as a conducting additive that, in addition to supporting metal oxide nanoparticles, can also provide additional Li binding sites to, perhaps, further enhance capacity.     

Synthesis,Characterization, and Evaluation of Mesoporous MCM-41-supported Molybdenum Hydrotreating Catalysts

Abstract

Mesoporous MCM-41 material with high surface area and narrow pore size distribution was synthesized and used as a support for Mo, CoMo, and NiMo catalysts. The molybdenum loading was varied from 2–14 wt% on MCM-41. On 10 wt% Mo/MCM-41, the promoter Co or Ni concentration was varied from 1–5 wt%. All the catalyst samples were characterized by surface area, low temperature oxygen chemisorption, x-ray diffraction (XRD), and temperature programmed reduction methods. Characterization results show that Mo is well dispersed on MCM-41 up to 10 wt%. The catalytic activities were evaluated for thiophene hydrodesulphurization (HDS), cyclohexene hydrogenation (HYD), and furan hydrodeoxygenation (HDO). All three catalytic functionalities vary in a similar manner to that of oxygen chemisorption as a function of Mo loading, indicating that there is a correlation between oxygen uptake and catalytic sites. The activities of these catalysts were compared with γ-Al₂O₃- and amorphous SiO₂-supported catalysts. It was found that MCM-41-supported Mo catalysts displayed superior activities.