Effects of functionalization conditions of sulfonic acid grafted SBA-15 on catalytic activity in the esterification of glycerol to monoglyceride: a factorial design approach

A series of propyl sulfonic acid-modified SBA-15 catalysts (SBA-15SO₃H) was prepared under various conditions using post-functionalization approach. A factorial design coupled with response surface analysis were employed to evaluate the effects of the preparation conditions on the catalyst activity. Optimization of the conditions to find the most active SBA-15SO₃H catalyst with the highest activity in glycerol esterification with lauric acid at 160?°C for 6?h was also made. Amount of 3-(mercaptopropyl)trimethoxysilane (MPTMS) and reflux time were chosen as parameters of the preparation conditions. The presence of propyl sulfonic acid groups in SBA-15SO₃H catalysts was confirmed by FT-TIR method. The catalysts were also characterized by means of surface analysis, XRD, TEM and TGA. The results obtained from the statistical models suggested that the amount of MPTMS was more important parameter to influence the activity compared to the reflux time. The optimum preparation condition was achieved at a reflux time of 20?h and an MPTMS amount of 1?mL/gram SBA-15 to obtain the SBA-15SO₃H(1) with the highest monoglyceride selectivity (70.2%) and corresponding lauric acid conversion (95%) in the esterification process.     

Improvement of the production of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) terpolyester by manipulating the culture condition

BACKGROUND: The aim of this work is to enhance the production of terpolyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐3HV‐co‐4HB)) produced by a locally isolated bacterium, Cupriavidus sp. USMAA2‐4. The monomer composition was varied by supplementing different carbon precursors and by manipulating the culture condition through one‐stage cultivation. The effect of C/N ratio and different concentrations of carbon source and precursors were investigated in order to produce higher content of this terpolyester. Although research on this biodegradable polyester is abundant, studies on terpolyester P(3HB‐co‐3HV‐co‐4HB) are still limited. RESULTS: Supplementation of oleic acid in accumulation medium increased the bacterial growth and polyhydroxyalkanoate (PHA) accumulation. It was also shown that medium consisting of assorted carbon precursors at C/N 20 gave relatively high dry cell weight and P(3HB‐co‐3HV‐co‐4HB) content. Various compositions of terpolyester were obtained when the concentration of oleic acid and 4HB precursors were manipulated. The combination of oleic acid with γ‐butyrolactone and 1‐pentanol was found to be the best combination to produce high PHA content (81 wt%). The composition of monomer in P(3HB‐co‐3HV‐co‐4HB) was produced in the range 8–13 mol% for 3HV and 9–24 mol% for 4HB, respectively. CONCLUSIONS: The production of P(3HB‐co‐3HV‐co‐4HB) in shake‐flasks successfully produced 81 wt% of PHA content. This manipulated culture condition can be used at larger scale to provide modeling for the production of terpolyester in a bioreactor. Copyright © 2012 Society of Chemical Industry     

Hollow micro-mesoporous carbon polyhedra produced by selective removal of skeletal scaffolds

An approach has been demonstrated for fabricating hollow micro-mesoporous carbon polyhedra by selective removal of the skeletal scaffolds of polyurethane (PU) foam in monolithic mesostructured resin/PU composites. Hollow micro-mesoporous carbon polyhedra with an irregular shape molded from the cellular cavities of PU foam were synthesized by using phenolic resol as a precursor, triblock copolymer Pluronic F127 as a template, PU foam as a skeletal scaffold and triethyl phosphate as a reaction agent. By a reaction with triethyl phosphate, the PU foam in resin/PU composites can be degraded, simultaneously leading to the disassembly of the monolithic structure into separated polyhedral particles. The method can also be used for synthesizing hollow micro-mesoporous carbon–silica polyhedra, using tetraethyl orthosilicate as a silica source. Moreover, after etching the silica away, hollow micro-mesoporous carbon polyhedra with an ordered hexagonal mesostructure (space group p6mm), large particle sizes of 65–500 μm, a large surface area of 1384 m² g^?1, a uniform pore size of 3.2 nm and a high pore volume of 1.15 cm³ g^?1 as well as a high mesoporosity of 81% can be obtained, which exhibits excellent adsorption performance toward methylene blue compared with the active carbon having a similar surface area.     

Easy access to pharmaceutically relevant heterocycles by catalytic reactions involving α-imino gold carbene intermediates

This review summarizes recent advances in the field of gold-catalyzed synthesis of pharmaceutically relevant aza-heterocycles via in situ generated α-imino gold carbene complexes as intermediates.     

Ubiquitin C-Terminal Hydrolase L1: Biochemical and Cellular Characterization of a Covalent Cyanopyrrolidine-Based Inhibitor

The deubiquitinase (DUB) ubiquitin C-terminal hydrolase L1 (UCHL1) is expressed primarily in the central nervous system under normal physiological conditions. However, UCHL1 is overexpressed in various aggressive forms of cancer with strong evidence supporting UCHL1 as an oncogene in lung, glioma, and blood cancers. In particular, the level of UCHL1 expression in these cancers correlates with increased invasiveness and metastatic behavior, as well as poor patient prognosis. Although UCHL1 is considered an oncogene with potential as a therapeutic target, there remains a significant lack of useful small-molecule probes to pharmacologically validate in vivo targeting of the enzyme. Herein, we describe the characterization of a new covalent cyanopyrrolidine-based UCHL1 inhibitory scaffold in biochemical and cellular studies to better understand the utility of this inhibitor in elucidating the role of UCHL1 in cancer biology.     

Fly Ash-based Geopolymer Lightweight Concrete Using Foaming Agent

In this paper, we report the results of our investigation on the possibility of producing foam concrete by using a geopolymer system. Class C fly ash was mixed with an alkaline activator solution (a mixture of sodium silicate and NaOH), and foam was added to the geopolymeric mixture to produce lightweight concrete. The NaOH solution was prepared by dilute NaOH pellets with distilled water. The reactives were mixed to produce a homogeneous mixture, which was placed into a 50 mm mold and cured at two different curing temperatures (60 °C and room temperature), for 24 hours. After the curing process, the strengths of the samples were tested on days 1, 7, and 28. The water absorption, porosity, chemical composition, microstructure, XRD and FTIR analyses were studied. The results showed that the sample which was cured at 60 °C (LW2) produced the maximum compressive strength for all tests, (11.03 MPa, 17.59 MPa, and 18.19 MPa) for days 1, 7, and 28, respectively. Also, the water absorption and porosity of LW2 were reduced by 6.78% and 1.22% after 28 days, respectively. The SEM showed that the LW2 sample had a denser matrix than LW1. This was because LW2 was heat cured, which caused the geopolymerization rate to increase, producing a denser matrix. However for LW1, microcracks were present on the surface, which reduced the compressive strength and increased water absorption and porosity.     

Comprehensive and Facile Synthesis of Some Functionalized Bis-Heterocyclic Compounds Containing a Thieno[2,3-b]thiophene Motif

A comprehensive and facile method for the synthesis of new functionalized bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif is described. The hitherto unknown bis-pyrazolothieno[2,3-b]thiophene derivatives 2a-c, bis-pyridazin othieno[2,3-b]thiophene derivatives 4, bis-pyridinothieno[2,3-b]thiophene derivatives 6a,b, and to an analogous bis-pyridinothieno[2,3-b]thiophene nitrile derivatives 7 are obtained. Additionally, the novel bis-pyradazinonothieno[2,3-b]thiophene derivatives 9, and nicotinic acid derivatives 10, 11 are obtained via bis-dienamide 8. The structures of all newly synthesized compounds have been elucidated by (1)H, (13)C NMR, GCMS, and IR spectrometry. These compounds represent a new class of sulfur and Nitrogen containing heterocycles that should also be of interest as new materials.     

Synthesis and Characterization of Privileged Monodentate Phosphoramidite Ligands and Chiral Brønsted Acids Derived from d-Mannitol

The synthesis of several novel chiral phosphoramidite ligands (L1–L8) with C₂ symmetric, pseudo C₂ symmetric secondary amines and chiral Brønsted acids 1a,b has been achieved. These chiral auxiliaries were obtained from commercially available d-mannitol, and secondary amines in moderate to excellent yields. Excellent diastereoselectivites of ten chiral auxiliaries were obtained. The chiral phosphoramidite ligands and chiral Brønsted acids were fully characterized by spectroscopic methods.     

A New Potent and Selective Monoamine Oxidase-B Inhibitor with Extended Conjugation in a Chalcone Framework: 1-[4-(Morpholin-4-yl)phenyl]-5-phenylpenta-2,4-dien-1-one

The general blueprint for the design of monoamine oxidase-B (MAO-B) inhibitors has been based on two phenyl or heteronuclei linked via a spacer of appropriate length. In this study, 1-[4-(morpholin-4-yl)phenyl]-5-phenylpenta-2,4-dien-1-one (MO10) was prepared by the condensation of 4′-morpholinoacetophenone and cinnamaldehyde in basic alcoholic medium. MO10 was assessed for inhibitory activity against two human MAO isoforms, MAO-A and MAO-B. Interestingly, MO10 showed a remarkable inhibition against MAO-B with an IC₅₀ value of 0.044 μM along with a selectivity index of 366.13. The IC₅₀ value was better than that of lazabemide (IC₅₀ value of 0.063 μM), which was used as a reference. Kinetics studies revealed that MO10 acted as a competitive inhibitor of MAO-B, with a K_i value of 0.0080 μM. The observation of recovery of MAO-B inhibition, compared to reference levels showed MO10 to be a reversible inhibitor. MTT assays showed that MO10 was nontoxic to normal VERO cells with an IC₅₀ value of 195.44 μg/mL. SwissADME predicted that MO10 provided advantageous pharmacokinetics profiles for developing agents acting on the central nervous system, that is, high passive human gastrointestinal absorption and blood–brain barrier permeability. Molecular docking simulations showed that MO10 properly entered the aromatic cage formed by Y435, Y398, and FAD of the active site of MAO-B. On the basis of these results, MO10 can be considered a promising starting compound in development of agents for the treatment of various neurodegenerative disorders.     

Gold-Nanoparticle-Decorated Metal-Organic Frameworks for Anticancer Therapy

Confinement of Au nanoparticles (NPs) within the porous materials with few nanometers (2-3 nm) has been a well established research area in the past decades in heterogeneous catalysis mainly due to the unique behaviour of Au NPs than its bulk counterpart. In this aspect, Au NPs encapsulated within the pore volumes of metal−organic frameworks (MOFs) have been intensively explored as heterogeneous solid catalysts for wide range of reactions. In recent years, Au NPs confined within the porous MOFs along with the photosensitizer or drug have been effectively used for the treatment of tumor cells through the generation of reactive oxygen species via cascade reactions. This work highlights the benefits of MOFs pores in the preparation of nanomedicine with high efficiency by assembling Au NPs, photosensitizer/drug with the combination of laser either for imaging or treatment of tumor cells. Further, the existing literature is grouped based on the nature of porous materials employed in the preparation of nanomedicine. The final section comments on our view on future developments in the field.