Folic acid conjugated and Ag-carrying organoclay nanoparticles and their response to L929 fibroblast and DLD-1 cancer cells.

This work presents the synthesis and characterisation of intercalated nanocomposites (NCs) from dispersed water solution blends of octadecyl amine-montmorillonite (ODA-MMT) (NC-0), folic acid (FA) conjugated ODA-MMT (NC-1) and Ag-MMT clay as a stable silver carrying agent (NC-2). The composition, chemical/physical and morphology of NCs with in situ intercalating nanostructures were investigated. Effect of organoclay, FA and Ag-MMT on L929 fibroblast (control), human colon carcinoma (DLD-1) cell lines, and the cytotoxicity, apoptosis and necrosis degree were estimated via WST-1/hemocytometric, double staining (as a ribonuclease A enzyme based method) and fluorescence microscopy methods in a dose-dependent manner. The mentioned cell lines integrated with NCs resulted in remarkable change in both morphology and nuclei of DLD-1 and fibroblast cells by apoptosis analysis. The number of necrotic cells were remarkably increased, as the toxic effects of nanocomposite nanoparticles were applied to both cell lines. Finally, the molecular mechanism of anticancer action of functionalised organoclays was elucidated.

Bioengineering functional copolymers. XXI. Synthesis of a novel end carboxyl-trithiocarbonate functionalized poly(maleic anhydride) and its interaction with cancer cells.

A novel carboxyl-trithiocarbonate functionalized polymer with a highly selective antitumor activity was synthesized by a reversible addition-fragmentation chain transfer (RAFT) polymerization of maleic anhydride (MA) with benzoyl peroxide as an initiator and S-1-dodecyl-S-(α,α'-dimethyl-α"-acetic acid)trithiocarbonate as a RAFT agent with the aim to design and synthesize an effective anticancer agent with minimum side effects. The structure, molecular weights and composition of synthesized polymers were investigated by (1)H ((13)C) NMR, MALDI-TOF-MS and GPC analyzes. It was demonstrated that RAFT polymerization of MA was accompanied by a partially controlled decarboxylation of anhydride units and the formation of conjugated double bond fragments in backbone macromolecular chains. The mechanism of interaction of pristine RAFT agent and PMA-RAFT polymer with cancer (HeLa human cervix carcinoma) and normal (L929 Fibroblast) cells was investigated by using a combination of chemical, biochemical, statistical, spectroscopic (SEM and fluorescence inverted microscope) and real-time analysis (RTCA) methods. PMA-RAFT exhibited higher and selective cytotoxicity, apoptotic and necrotic effects toward HeLa cells at relatively low concentrations (around 7.5-75 µg mL(-1), IC(50) = 11.183 µg mL(-1)) and toward Fibroblast cells at high concentrations (IC(50) > 100 µg mL(-1)). The observed highly selective antitumor activity render PMA-RAFT polymers as promising candidates for the utilization in cancer chemotherapy.

Occurrence and removal of microbial indicators from municipal wastewaters by nine different MBR systems.

Nine different membrane bioreactor (MBR) systems with different process configurations (submerged and external), membrane geometries (hollow-fiber, flat-sheet, and tubular), membrane materials (polyethersulfone (PES), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE)) and membrane nominal pore sizes (0.03-0.2 µm) were evaluated to assess the impact of influent microbial concentration, membrane pore size and membrane material and geometries on removal of microbial indicators by MBR technology. The log removal values (LRVs) for microbial indicators increased as the influent concentrations increased. Among the wide range of MBR systems evaluated, the total and fecal coliform bacteria and indigenous MS-2 coliphage were detected in 32, 9 and 15% of the samples, respectively; the 50th percentile LRVs were measured at 6.6, 5.9 and 4.5 logs, respectively. The nominal pore sizes of the membranes, membrane materials and geometries did not show a strong correlation with the LRVs.

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine of MMT clay in interlamellar copolymerization. This simple and versatile method can be applied to a wide range of functional monomer/comonomer systems and mono- and bifunctional RAFT compounds for preparation new generation of nanomaterials.

Bioengineering functional copolymers. XIV. Synthesis and interaction of poly(N-isopropylacrylamide-co-3,4-dihydro-2H-pyran-alt-maleic anhydride)s with SCLC cancer cells.

Novel antitumor active functional polymers with supramacromolecular structures were synthesized by a complex-radical terpolymerization of N-isopropylacrylamide (NIPAm), 3,4-dihydro-2H-pyran (DHP), and maleic anhydride (MA) with 2,2'-azoisobisbutyronitrile as a radical initiator in 1,4-dioxane at 65°C under nitrogen atmosphere. The structure and composition of terpolymers were investigated by (1)H ((13)C) NMR spectroscopy. Interaction of terpolymers with human lung small cell carcinoma (SCLC) were investigated by using different methods such as cytotoxicity, statistical, apoptotic and necrotic cell indexes, double staining and caspase-3 immunostaining, light and fluorescence inverted microscopy analyses. Investigations into structure, composition, and antitumor activity relationships revealed that terpolymers containing a combination of ionisable amide-pyran linkages and H-bonded carboxylic groups exhibited higher cytotoxicity. It was observed that terpolymer with nearly alternating structure provides a maximum concentration of ionisable and H-bonded antitumor sites, and therefore, exhibits higher in vitro cytotoxicity, apoptotic and necrotic effects towards SCLC cancer cells.

Novel compound from Trachyspermum ammi (Ajowan caraway) seeds with antibiofilm and antiadherence activities against Streptococcus mutans: a potential chemotherapeutic agent against dental caries.

AIM: The objective of this study was to isolate and characterize the active compound from Trachyspermum ammi seeds, exhibiting antibiofilm activity against Streptococcus mutans, a major causal organism of dental caries. METHODS AND RESULTS: Purification of the active compound from the seeds was performed by silica gel chromatography, and spectroscopic methods (FTIR, NMR and MS) were employed for its identification and structure determination. Antibiofilm and antiadherence activities of the active compound against S. mutans were analysed. Confocal microscopy was performed to visualize the effect of the compound on biofilm structure of S. mutans. Around 50% reduction was observed in adherence at 39·06 µg ml(-1) and in biofilm at 78·13 µg ml(-1) . It was found effective against adherent cells of S. mutans, reduced water-insoluble glucan synthesis and inhibited the reduction in pH. Confocal microscopy revealed scattered cells at sub-MIC concentration of the compound, resulting in distorted biofilm architecture in contrast to clustered cells seen in control. CONCLUSION: This study revealed a novel compound, a naphthalene derivative, isolated first time from T. ammi seeds with antibiofilm activity against S. mutans. SIGNIFICANCE AND IMPACT OF THE STUDY: Trachyspermum ammi represents an interesting source of a novel compound, (4aS, 5R, 8aS) 5, 8a-di-1-propyl-octahydronaphthalen-1-(2H)-one, with a great potential to be used as a therapeutic agent against dental caries.

Ag-carried CMC/functional copolymer/ODA-Mt wLED-treated NC and their responses to brain cancer cells.

The subject of this work is synthesis and characterization of novel multifunctional nanocomposite (8/2A-NC) consisting (1) carboxymethyl cellulose (CMC) as a matrix biopolymer and poly (maleic acid-alt-acrylic acid) as a reactive synthetic partner matrix polymer; (2) octadecyl amine montmorillonite (ODA-MMT) reactive organoclay provide intercalated silicate layers structures and aqueous colloidal dispersing medium, and MMT as carriers and targeting agents for anticancer agents in drug delivery systems, respectively. ODA as a intercalated surfactant finely dispersed 8/2A NC and its compatibility with matrix polymers via the interfacial polarization (complexing) and functionalization of matrix polymers by amine (ODA) and carboxylic acids from both the CMC and copolymer; (3) silver nanoparticles (AgNPs) as in-situ generated onto matrix polymers with unique nano-size and morphology parameters was synthesized. Important material science and bioengineering aspects of these investigations included (a) novel approach in synthetic pathways; (b) effects of physical and chemical structural rearrangements; (c) effects of Light Emitting Dioda (LED)-treatment on the FT-IR spectra, XRD reflection parameters, SEM-TEM morphology and nano-size and diameter distribution of AgNPs onto matrix polymers; (d) positive effect of LED-treatment of 8/2A nanocomposite and its response to the MIAPaCa-2 and U87 human brain cancer cell lines were evaluated. Novel 8/2A-NC multifunctional drug consisting unique positive, intercalating and encapsulated core-shell morphology structures, nano-size (5.6 nm) and narrow diameter distribution (94%) of AgNPs onto matrix polymers [silver NPs (0.25%) in 8/2A NC (25%)] with highest volume of contact area compared with used cancer micro-cells show lowest cell viability as an excellent anticancer platform. 8/2A-NC is a novel multifunctional drug with intercalating and encapsulated core-shell morphology structures consisting of positively charged, non-randomly distributed AgNPs with a large contact area and low diameters (5-6 nm). The anticancer properties of (This factor is not conformed experimentally in work) this drug can be explained by the following structural factors: 8/2A-NC contains a combination of active sites from protonated hydroxyl, carboxyl and amine groups; Ag+-cations and ODA-MMT with high physical and chemical surface areas. We suggest this material be further explored for anti-cancer testing.

Multifunctional colloidal nanofiber composites including dextran and folic acid as electro-active platforms.

This work presents the fabrication and characterization of novel colloidal multifunctional polymer nanofiber composites (NFCs) from water dispersion blends of intercalated silicate layered nanocomposites of poly (2-vinyl-N-pyrrolidone)/octadecyl amine-montmorillonite (ODA-MMT) and dextran/ODA-MMT as matrix and partner polymer intercalated nanocomposites in the presence of NaOH and folic acid (FA) as doping agents by green reactive electrospinning. Chemical and physical structures, surface morphology and electrical properties were investigated. Effects of matrix/partner polymer ratios, doping agents, absorption time of NaOH, and temperature on electrical parameters of NFCs were evaluated. The presence of FA and increasing dextran fraction in NFCs resulted in reducing fiber diameter and improving diameter distribution. High complexing behaviors of matrix/partner polymer chains, organoclay, FA, and NaOH significantly improved conductivity parameters, especially 5-min of absorption time (≈10-2-10-3Sm-1). The conductivity of the samples decreased with increasing temperature. NFCs fabricated for the first time are promising candidates for various biomedical, electrochemical and electronic applications as electro-active platforms.

Emx2 and Pax6 function in cooperation with Otx2 and Otx1 to develop caudal forebrain primordium that includes future archipallium.

One of the central issues in developmental neurobiology is how the forebrain is organized ontogenetically. The traditional view is that the anterior neuroectoderm first develops into mesencephalic and prosencephalic vesicles; the latter vesicle subsequently develops into the diencephalon and secondary prosencephalon, of which dorsal parts protrude to generate the telencephalon. The diencephalon yields the pretectum, thalamus, and prethalamus, and the telencephalon produces the archipallium, neopallium, and ganglionic eminences. By identifying cell descendants that once expressed Emx2 with use of the Cre knock-in mutant into the Emx2 locus and analyzing phenotypes of double mutants between Emx2 and Otx2/Otx1 and between Emx2 and Pax6, we propose that at the 3-6 somite stage, the anterior neuroectoderm develops into three primordia: midbrain, caudal forebrain, and rostral forebrain. The caudal forebrain primordium generates not only the pretectum, thalamus, and prethalamus but also the archipallium, cortical hem, choroid plexus, choroidal roof, and eminentia thalami. The primordium corresponds to the Emx2- or Pax6-positive region at the 3-6 somite stage that most probably does not include the future neopallium or commissural plate. Otx2 and Otx1 that are expressed in the entire future forebrain and midbrain cooperate with this Emx2 and Pax6 expression in the development of the caudal forebrain primordium; Emx2 and Pax6 functions are redundant. In the embryonic day 9.5 Emx2-/-Pax6-/- double mutant, the caudal forebrain remained unspecified and subsequently transformed into tectum in a mirror image of the endogenous one.

Bioengineering Functional Copolymers. IX. Poly[(maleic anhydride-co-hexene-1)-g-poly(ethylene oxide)].

Amphiphilic bioengineering copolymers having a combination of hydrophilic/hydrophobic linkages and polyelectrolyte behavior, along with an ability to interact with biomacromolecules, in particular with the invertase enzyme, have been synthesized by (a) complex-radical copolymerization of maleic anhydride (MA, the acceptor) and hexene-1 (H-1, the donor) monomers with benzoyl peroxide as the initiator in 1,4-dioxane at 65 degrees C under high-conversion conditions and (b) subsequent grafting (polyesterification) of synthesized poly(MA-alt-H-1) with alpha-methoxy-omega-hydroxy-poly(ethylene oxide) (PEO). Copolymerizations were also carried out in the steady state, in order to essentially reduce the effect of copolymer composition drift. The values of the monomer reactivity ratios (r(1) and r(2)) determined by using the known terminal models of Fineman-Ross (FR) and Kelen-Tüdös (KT), as well as by nonlinear regression (NLR) analysis, are: r(1) = 0.16 and r(2) = 0.30 (FR), r(1) = 0.14 and r(2) = 0.27 (KT), and r(1) = 0.15 and r(2) = 0.29 (NLR), respectively. All the copolymers and graft copolymers were characterized by FTIR spectroscopy, (1)H{(13)C} NMR spectroscopy, viscometric measurements, and chemical (acid number), thermal (DSC and TGA), and X-ray diffraction analyses. Unlike poly(MA-alt-H-1)s, PEO macrobranched graft copolymers exhibit expressed polyelectrolyte and swelling behavior in diluted and concentrated dioxane solutions, respectively. The copolymer and its PEO hyperbranched derivatives can be used as carriers for enzyme immobilization.

Fabrication and characterization of novel starch-grafted poly l-lactic acid/montmorillonite organoclay nanocomposites.

In this work, poly(L-lactic acid)-g-starch layered silicate nanocomposites (NCs) (PLLA-g-starch/MMT) were fabricated by intercalative bulk graft copolymerization of LA with starch, in the presence of either stannous octoate acting as a catalyst or LA-MMT organoclay acting as a cocatalyst-nanofiller. This procedure was performed inside a custom vacuum micro-reactor. To better understand the graft copolymerization mechanism, in situ processing types, interfacial interactions and nanostructure formation of PLLA-g-starch/MMT NCs, methods such as FT-IR, XRD, (1)H NMR, (13)C CP/MAS-NMR, DSC/TGA, TEM and SEM were utilized. The morphology and thermal behaviors of nanocomposites were found to be strongly dependent on the loading mass fraction of LA-MMT within the nanocomposite structure and the type of in situ processing such as interfacial, physical and chemical interactions. Preintercalated LA-MMT organoclay exhibited dual functions. It demonstrated the ability to act as a catalyst, essentially accelerating in situ graft copolymerization via esterification of LA carboxyl groups with hydroxyl groups of starch macromolecules, whilst also acting as a nananofiller-compatibilizer.

Fabrication and characterization of PVA/ODA-MMT-poly(MA-alt-1-octadecene)-g-graphene oxide e-spun nanofiber electrolytes and their response to bone cancer cells.

This work presents a new approach to fabrication and characterization of novel polymer nanofiber electrolytes from intercalated PVA/ODA-MMT nanocomposite as a matrix polymer and encapsulated graphene oxide (GO) nanosheets with amphiphilic reactive copolymer as partner polymers using electrospinning method. The chemical and physical structures, surface morphology, thermal behaviors and electric conductivity of nanocomposites and nanofibers were investigated using analyses methods including FTIR, XRD, SEM, DSC-TGA and conductivity analysis. Significant improvements in nanofiber morphology and size distribution were observed when GO and reactive organoclay were incorporated as reinforcement fillers into various matrix/partner solution blends. The structural factors of matrix-partner polymer nanocomposite particles with higher zeta-potential play important roles in both chemical and physical interfacial interactions and phase separation processing and also lead to the formation of nanofibers with unique surface morphologies and good conductivities. The cytotoxic, necrotic and apoptotic effects of chosen nanofibers on osteocarcinoma cells were also investigated. These multifunctional, self-assembled, nanofibrous surfaces can serve as semi-conductive and bioactive platforms in various electrochemical and bio-engineering processes, as well as reactive matrices used for the immobilization of various biopolymer precursors.

Novel multifunctional colloidal carbohydrate nanofiber electrolytes with excellent conductivity and responses to bone cancer cells.

This work presents a new approach to fabricating novel polymer nanofiber composites (NFCs) from water solution blends of PVA (hydrolyzed 89%)/ODA-MMT and Na-CMC/ODA-MMT nanocomposites as well as their folic acid (FA) incorporated modifications (NC-3-FA and NC-4-FA) through green electrospinning nanotechnology. The chemical and physical structures and surface morphology of the nanofiber composites were confirmed. Significant improvements in nanofiber morphology and size distribution of the NFC-3-FA and NFC-4-FA nanofibers with lower average means 110 and 113nm compared with those of NFC-1/NFC-2 nanofibers (270 and 323nm) were observed. The structural elements of polymer NFCs, particularly loaded partner NC-2, plays an important role in chemical and physical interfacial interactions, phase separation processing and enables the formation of nanofibers with unique morphology and excellent conductivity (NFC-3-FA 3.25×10(-9)S/cm and NFC-4-FA 8.33×10(-4)S/cm). This is attributed to the higher surface contact areas and multifunctional self-assembled supramacromolecular nanostructures of amorphous colloidal electrolytes. The anticancer activity of FA-containing nanofibers against osteocarcinoma cells were evaluated by cytotoxicity, apoptotic and necrotic analysis methods.

Cross-striolar and commissural inhibition in the otolith system.

Neural connections from the saccular and utricular nerves to the ipsilateral vestibular neurons and the commissural effects were studied by using intracellular recordings of excitatory (E) and inhibitory (I) postsynaptic potentials (PSPs) in vestibular neurons of cats after focal stimulation of the saccular and the utricular maculae. Neural circuits from the maculae to vestibular neurons, termed cross-striolar inhibition, may provide a mechanism for increasing the sensitivity to linear acceleration and tilt of the head. It was examined whether secondary vestibular neurons activated by an ipsilateral otolith organ received a commissural inhibition from a contralateral otolith organ that occupied the same geometric plane. Results suggest that utricular-activated vestibular neurons receiving commissural inhibition may provide a mechanism for increasing the sensitivity to horizontal linear acceleration and tilt of the head. The commissural inhibition of the saccular system was much weaker than that of the utricular system.

Neuronal organization of the utricular macula concerned with innervation of single vestibular neurons in the cat.

We investigated whether cross-striolar inhibition, which may increase sensitivity to linear acceleration, contributed to utricular (UT) afferent innervation of single vestibular neurons (VNs). Excitatory and inhibitory postsynaptic potentials (EPSPs, IPSPs, respectively) were recorded from VNs after focal stimulation of the UT macula (M). From a total of 83 VNs, 25 (30%) neurons received inputs from both sides of the UTM, and the response patterns were opposite, i.e. cross-striolar inhibition was observed. In roughly 2/3 of these neurons, stimulation of the medial side of the UTM evoked EPSPs, while stimulation of the lateral side evoked IPSPs. In the remaining 1/3 neurons, the response patterns were opposite. Thirty-two (39%) of the 83 neurons received the identical pattern of inputs from both sides of the UTM: EPSPs in 26 neurons and IPSPs in six neurons. Twenty-six (31%) of the 83 neurons received inputs from either the medial or the lateral side of the UTM. These findings suggest that cross-striolar inhibition existed in the UT system, although it was not a dominant circuit that increased the sensitivity as in the saccular system [15].

A novel approach of dose mapping using a humanoid breast phantom in radiotherapy.

A study of dose mapping techniques to investigate the dose distribution throughout a planned target volume (PTV) in a humanoid breast phantom exposed to a 6 MV photon beam similar to that of treatment conditions is described. For tangential breast irradiation using a 6 MV accelerator beam, the dose is mapped at various locations within the PTV using thermoluminescent dosemeters (TLDs) and radiographic films. An average size perspex breast phantom with the ability to hold the dosemeters was made. TLDs were exposed after packing them in various locations in a particular slice, as planned by the treatment planning system (TPS). To map the dose relative to the isocenter, films were exposed after tightly packing them in between phantom slices, parallel to the central axis of the beam. The dose received at every location was compared with the given dose as generated by the TPS. The mapped dose in each location in the isocentric slice from superficial to deep region was found to be in close agreement with the TPS generated dose to within +/-2%. Doses at greater depths and distant medial and lateral ends, however, were found to be lower by as much as 9.4% at some points. The mapped dose towards the superior region and closest inferior region from the isocenter was found to agree with those for TPS. Conversely, results for the farthest inferior region were found to be significantly different with a variance as much as 17.4% at some points, which is believed to be owing to the variation in size and shape of the contour. Results obtained from films confirmed this, showing similar trends in dose mapping. Considering the importance of accurate doses in radiotherapy, evaluating dose distribution using this technique and tool was found to be useful. This provides the opportunity to choose a technique and plan to provide optimum dose delivery for radiotherapy to the breast.

Canal and otolith inputs to single vestibular neurons in cats.

Convergence of both afferents from the PC and saccular macula, and those from the PC and utricular macula on single vestibular neurons was noted by use of intercellular recording from vestibular neurons. Vestibular neurons were classified VO neurons (vestibulo-ocular proper neurons), VOS (Vestibulo-oculo-spinal neurons sending axon collaterals both to the extraocular motoneuron pools and to the spinal cord), VS neurons (vestibulospinal proper neurons) and V neurons (vestibular neurons without axons to the oculomotor nuclei or the spinal cord) on the basis of whether or not they responded antidromically to stimulation of the oculomotor nuclei and the spinal cord. Of the total 143 vestibular neurons recorded in the series of experiments on convergence of the PC and saccular afferents, 47 neurons (33%) were received inputs from both the PC and saccular nerves. Twenty-six of the 47 convergent neurons were identified as having the nature of VS neurons. Half (13/26) of those were activated monosynaptically from both the PC and saccular nerves. Only one saccular-activated neuron without PC inputs sent an axon to the oculomotor nuclei. In the other series of experiments on the convergence of the PC and utricular afferents, 41 (37%) of 111 vestibular neurons were proved to converge on inputs from both nerves. The majority (35/41) of the neurons received monosynaptic inputs from the PC nerve and polysynaptic EPSP-IPSP sequences from the utricular nerve, or vice versa. The ratio of PC-otolith convergent neurons among utricular-activated neurons (41/54, 76%) was higher than that among saccular activated neurons (47/88, 53%). The percentage of utricular alone neurons without PC inputs (13/111, 12%) was less than that of the saccular alone without PC inputs (41/145, 28%). In conclusion, the convergence of canal and otolith inputs likely contribute mainly to vestibulospinal reflexes including the vestibulocollic reflex, by sending inputs to the neck and other muscles during head inclination which creates the combined stimuli of angular and linear acceleration.

Controlled graft copolymerization of lactic acid onto starch in a supercritical carbon dioxide medium.

This work presents a new approach for the synthesis of a starch-g-poly L-lactic acid (St-g-PLA) copolymer via the graft copolymerization of LA onto starch using stannous 2-ethyl hexanoate (Sn(Oct)2) as a catalyst in a supercritical carbon dioxide (scCO2) medium. The effects of several process parameters, including the pressure, temperature, scCO2 flow rate and reaction time, on the polymerization yield and grafting degree were studied. Amorphous graft St-g-PLA copolymers with increased thermal stability and processability were produced with a high efficiency. The maximum grafting degree (i.e., 52% PLA) was achieved with the following reaction conditions: 6h, 100°C, 200 bar and a 1:3 (w/w) ratio of St/LA. It was concluded that these low cost biobased graft biopolymers are potential candidates for several environment-friendly applications.

Impact of MBR cleaning and breaching on passage of selected microorganisms and subsequent inactivation by free chlorine.

Membrane bioreactors (MBRs) produce better quality effluent compared to conventional treatment processes but they are still subjected to the same disinfection requirements as conventional processes by many regulatory agencies. A research study consisting of bench-, pilot- and full-scale studies was conducted to characterize effluents produced from an MBR system operating under routine and challenged conditions and to assess the disinfection requirements for these effluents. Membrane cleaning did not seem to pose a substantial risk with respect to passage of target microorganisms; however, the membrane under breached conditions (turbidity > 0.5 NTU) resulted in an increase in a total coliform bacterial concentration up to 8500 CFU/100 mL. Adenoviruses were always detected in MBR filtrate samples by PCR (method detection limit of 10(3) genome copies per 25 µL reaction) irrespective of the membrane cleaning or breaching status. Passage of MS-2 bacteriophage through a breached membrane was lower compared to total coliform bacteria potentially due to their lower densities in the mixed liquor. Despite an increase in microbial concentration, a free chlorine CT of 30 mg-min/L was sufficient to achieve greater than 5-log removal of seeded MS-2 bacteriophage and removal of total coliform bacteria at or below the method detection limit (2 CFU/100 mL) for samples with a filtrate turbidity of 1.0 NTU. If such lower CT were to be employed, a significant decrease in plant footprint and operational costs could be realized.

Characterization of effluent water qualities from satellite membrane bioreactor facilities.

Membrane bioreactors (MBRs) are often a preferred treatment technology for satellite water recycling facilities since they produce consistent effluent water quality with a small footprint and require little or no supervision. While the water quality produced from centralized MBRs has been widely reported, there is no study in the literature addressing the effluent quality from a broad range of satellite facilities. Thus, a study was conducted to characterize effluent water qualities produced by satellite MBRs with respect to organic, inorganic, physical and microbial parameters. Results from sampling 38 satellite MBR facilities across the U.S. demonstrated that 90% of these facilities produced nitrified (NH4-N <0.4 mg/L-N) effluents that have low organic carbon (TOC <8.1 mg/L), turbidities of <0.7 NTU, total coliform bacterial concentrations <100 CFU/100 mL and indigenous MS-2 bacteriophage concentrations <21 PFU/100 mL. Multiple sampling events from selected satellite facilities demonstrated process capability to consistently produce effluent with low concentrations of ammonia, TOC and turbidity. UV-254 transmittance values varied substantially during multiple sampling events indicating a need for attention in designing downstream UV disinfection systems. Although enteroviruses, rotaviruses and hepatitis A viruses (HAV) were absent in all samples, adenoviruses were detected in effluents of all nine MBR facilities sampled. The presence of Giardia cysts in filtrate samples of two of nine MBR facilities sampled demonstrated the need for an appropriate disinfection process at these facilities.