Cu(II), Co(II) and Ni(II) Complexes Installed on Functionalized Silica Surface for Hydrogen Peroxide Assisted Cyclohexane Oxidation

In this work, Cu(II), Co(II) and Ni(II) complexes of the Schiff base ((S,E)-2-(3,4-dimethoxybenzylideneamino)-3-(1H-imidazol-4-yl)propionic acid) were synthesized and subsequently anchored onto amine functionalized silica. They were characterized by FT-IR, UV–vis., ²⁹Si NMR, TG-DTG, ESR, FE-SEM and AFM techniques, and employed as catalysts in cyclohexane oxidation using hydrogen peroxide oxidant. Silica supported Cu(II) catalyst was shown the highest catalytic activity (70%) than rest of the catalysts used. On the other hand, all the complexes were selective as they yield only cyclohexanol and cyclohexanone. Silica supported catalysts were maintained their catalytic activity over five successive catalytic run. As these catalysts are selective, reusable and functioning well with hydrogen peroxide, they could design the environment friendly catalytic system for effective cyclohexane oxidation.     

First Application of Newly Developed FT-NIR Spectroscopic Methodology to Predict Authenticity of Extra Virgin Olive Oil Retail Products in the USA

Economically motivated adulteration (EMA) of extra virgin olive oils (EVOO) has been a worldwide problem and a concern for government regulators for a long time. The US Food and Drug Administration (FDA) is mandated to protect the US public against intentional adulteration of foods and has jurisdiction over deceptive label declarations. To detect EMA of olive oil and address food safety vulnerabilities, we used a previously developed rapid screening methodology to authenticate EVOO. For the first time, a recently developed FT-NIR spectroscopic methodology in conjunction with partial least squares analysis was applied to commercial products labeled EVOO purchased in College Park, MD, USA to rapidly predict whether they are authentic, potentially mixed with refined olive oil (RO) or other vegetable oil(s), or are of lower quality. Of the 88 commercial products labeled EVOO that were assessed according to published specified ranges, 33 (37.5%) satisfied the three published FT-NIR requirements identified for authentic EVOO products which included the purity test. This test was based on limits established for the contents of three potential adulterants, oils high in linoleic acid (OH-LNA), oils high in oleic acid (OH-OLA), palm olein (PO), and/or RO. The remaining 55 samples (62.5%) did not meet one or more of the criteria established for authentic EVOO. The breakdown of the 55 products was EVOO potentially mixed with OH-LNA (25.5%), OH-OLA (10.9%), PO (5.4%), RO (25.5%), or a combination of any of these four (32.7%). If assessments had been based strictly on whether the fatty acid composition was within the established ranges set by the International Olive Council (IOC), less than 10% would have been identified as non-EVOO. These findings are significant not only because they were consistent with previously published data based on the results of two sensory panels that were accredited by IOC but more importantly each measurement/analysis was accomplished in less than 5 min.     

Ewma charts for multivariate time series

In this paper a muIt,ivariat.e EWMA chart for time series is introduced. In principle, it is a generalization of the control scheme of Lowry et al. (I992) for multivarite indendent observations.

The autocovariances of the EWMA recursion are derived for stationary multivariate time series. IYsing tllese reslllts a co11t.rol chart hased or1 t11 illt.ivariate EWMA recursion is proposed. For a multivariate autoregressive process of order 1, a sufficient. condition is given such that the in-control average run length (ARL) is invariant, withrespect to the covariance of the White Noise process. This scheme is compared with the MEWMA control chart of Lowry et al. (1992) applied to the residuals.

By an extensive Monte carlo study the ARL of both charts are determined for several multivariate autoregressive processses.     

Fabrication and characterization of planar and channel polymer waveguides. III. Compositional distribution and solute loss in polymer thin films

For many microelectronic and optoelectronic applications, polymer thin films require the addition of small molecules. However, the thin‐film geometry and associated processing techniques will influence the final morphology and compositional distribution of the constituents. It is therefore important that these be examined directly rather than inferred from bulk measurements. As an example system, the concentration and distribution of Disperse Red 1 (DR1) molecules in poly(methyl methacrylate) thin films were examined. Ultraviolet visibility spectroscopy and dynamic secondary ion mass spectrometry indicate that the composition of the molecules decreased dramatically with thermal treatment of the film. The sublimation of the chromophore was observed to occur at temperatures well below the melting point of the small molecule and the glass transition of the pure polymer; this solute loss manifested itself in changes in the glass transition temperature of the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2021–2024, 2002     

Molecularly Targeted Agents as Radiosensitizers in Cancer Therapy—Focus on Prostate Cancer

As our understanding of the molecular pathways driving tumorigenesis improves and more druggable targets are identified, we have witnessed a concomitant increase in the development and production of novel molecularly targeted agents. Radiotherapy is commonly used in the treatment of various malignancies with a prominent role in the care of prostate cancer patients, and efforts to improve the therapeutic ratio of radiation by technologic and pharmacologic means have led to important advances in cancer care. One promising approach is to combine molecularly targeted systemic agents with radiotherapy to improve tumor response rates and likelihood of durable control. This review first explores the limitations of preclinical studies as well as barriers to successful implementation of clinical trials with radiosensitizers. Special considerations related to and recommendations for the design of preclinical studies and clinical trials involving molecularly targeted agents combined with radiotherapy are provided. We then apply these concepts by reviewing a representative set of targeted therapies that show promise as radiosensitizers in the treatment of prostate cancer.     

N‐Arylsulfonyl Indolines as Retinoic Acid Receptor‐Related Orphan Receptor γ (RORγ) Agonists

The nuclear retinoic acid receptor‐related orphan receptor γ (RORγ; NR1F3) is a key regulator of inflammatory gene programs involved in T helper 17 (T_H17) cell proliferation. As such, synthetic small‐molecule repressors (inverse agonists) targeting RORγ have been extensively studied for their potential as therapeutic agents for various autoimmune diseases. Alternatively, enhancing T_H17 cell proliferation through activation (agonism) of RORγ may boost an immune response, thereby offering a potentially new approach in cancer immunotherapy. Herein we describe the development of N‐arylsulfonyl indolines as RORγ agonists. Structure–activity studies reveal a critical linker region in these molecules as the major determinant for agonism. Hydrogen/deuterium exchange coupled to mass spectrometry (HDX‐MS) analysis of RORγ–ligand complexes help rationalize the observed results.     

Formation of quasicrystals in Zr–Pd–(Cu) melt spun ribbons and mechanically milled powders

Amorphous Zr₇₀Pd₃₀ and Zr₇₀Pd₂₀Cu₁₀ alloys were prepared by mechanical milling and melt spinnng to compare their devitrification behaviors. The devitrification of mechanically milled Zr₇₀Pd₃₀ and Zr₇₀Pd₂₀Cu₁₀ powders occurs via a single-step, first-order transformation to a stable Zr₂Pd tetragonal structure. This is in sharp contrast to the devitrification of the same amorphous alloys prepared by melt spinning, in which a primary meta-stable quasicrystalline phase forms. Since the mechanical milling process does not involve direct liquid phase formation of an amorphous structure, it is inferred that the short-range order in the solid state derived amorphous powder is different from that in the melt spun ribbon. During mechanical milling of an amorphous melt spun ribbon, crystallization of the quasicrystalline phase appears to precede disordering into an amorphous structure having an different short range order. Deformation of an amorphous melt spun ribbon by repetitive rolling at ambient temperature crystallizes the meta-stable quasicrystalline phase.