Hybrid palm-oil/styrene-maleimide nanoparticles synthesized in aqueous dispersion under different conditions.

Poly(styrene-co-maleic anhydride) was imidized with ammonium hydroxide and palm oil, resulting in an aqueous dispersion of hybrid nanoparticles with diameters 85-180 nm (dispersed) or 20-50 nm (dried). The reaction conditions were optimized for different precursors by evaluating the relative amount ammonium hydroxide and maximizing the incorporated palm oil up to 70 wt.%. The interactions between palm oil and polymer phase have been studied by TEM, IR, Raman spectroscopy and thermal analysis (TGA, [TM] DSC). From Raman spectra, the amount of imide and reacted oil were quantified. Through concurring effects of imidization and coupling of fatty acids, the imidization needs a slight excess of NH3 relatively to maleic anhydride. The oxidative stability highly depends on oxidative crosslinking of free or non-reacted oil. Comparing the imide content from spectroscopic and thermal analysis suggests that a complex rigid imide phase without strong relaxation behavior has formed in combination with oil.

Mitigating iodomethane emissions and iodide residues in fumigated soils.

Although long-regarded as an excellent soil fumigant for killing plant pests, methyl bromide (MeBr) was phased out in 2005 in the USA, because it can deplete the stratospheric ozone layer. Iodomethane (MeI) has been identified as an effective alternative to MeBr and is used in a number of countries for preplant pest control. However, MeI is highly volatile and potentially carcinogenic to humans if inhaled. In addition, iodide anions, a breakdown product of MeI, can build up in fumigated soils and potentially cause plant toxicity and contaminate groundwater via leaching. In order to overcome the above two obstacles in MeI application, a method is proposed to place reactive bags containing ammonium hydroxide solution (NH4OH) on the soil surface underneath an impermeable plastic film covering the fumigated area. Our research showed that using this approach, over 99% of the applied MeI was quantitatively transferred to iodide. Of all the resulting iodide, only 2.7% remained in the fumigated soil, and 97.3% was contained in the reactive bag that can be easily removed after fumigation.

Preparation of carbon dots from waste cellulose diacetate as a sensor for tetracycline detection and fluorescence ink.

As one type of the solid wastes, the increasing contamination of waste cellulose diacetate (CDA) from discarded cigarette filters is a growing problem worldwide. Finding a facile and suitable approach to convert the CDA into value-added materials is of significance. Herein, we reported a green, simple and effective method to reuse CDA as precursor for preparing fluorescence N-doped carbon dots (N-CDs) via one-pot hydrothermal carbonization in aqueous solution with low-cost ammonium hydroxide as the passivation agent. The N-CDs showed a quantum yield up to 22.4% with a maximum emission at 415 nm and excitation at 320 nm. Interestingly, the N-CDs exhibited high selectivity toward tetracycline (TC) as their fluorescence was obviously quenched by TC as a result of inner-filter effect. A linear relationship was fabricated over concentration range of 0-80 µM with a detection limit of 0.06 µM. Moreover, the N-CDs could also be applied as fluorescent ink for anti-forgery.

Valorization of sugarcane bagasse by chemical pretreatment and enzyme mediated deconstruction.

After chemical pretreatment, improved amenability of agrowaste biomass for enzymatic saccharification needs an understanding of the effect exerted by pretreatments on biomass for enzymatic deconstruction. In present studies, NaOH, NH4OH and H2SO4 pretreatments effectively changed visible morphology imparting distinct fibrous appearance to sugarcane bagasse (SCB). Filtrate analysis after NaOH, NH4OH and H2SO4 pretreatments yielded release of soluble reducing sugars (SRS) in range of ~0.17-0.44%, ~0.38-0.75% and ~2.9-8.4% respectively. Gravimetric analysis of pretreated SCB (PSCB) biomass also revealed dry weight loss in range of ~25.8-44.8%, ~11.1-16.0% and ~28.3-38.0% by the three pretreatments in the same order. Release of soluble components other than SRS, majorly reported to be soluble lignins, were observed highest for NaOH followed by H2SO4 and NH4OH pretreatments. Decrease or absence of peaks attributed to lignin and loosened fibrous appearance of biomass during FTIR and SEM studies respectively further corroborated with our observations of lignin removal. Application of commercial cellulase increased raw SCB saccharification from 1.93% to 38.84%, 25.56% and 9.61% after NaOH, H2SO4 and NH4OH pretreatments. Structural changes brought by cell wall degrading enzymes were first time shown visually confirming the cell wall disintegration under brightfield, darkfield and fluorescence microscopy. The microscopic evidence and saccharification results proved that the chemical treatment valorized the SCB by making it amenable for enzymatic saccharification.

Isolation and Purification of Pyrazines Produced by Reaction of Cellulosic-Derived Sugars with NH4OH and Selected Amino Acids.

Various pyrazines have been synthesized via reaction of selected cellulosic-derived sugars, ammonium hydroxide and amino acids at 110°C for 2 hours. Different methods of sample cleanup such as liquid-liquid extraction (LLE), liquid-solid extraction, column chromatography and distillation were employed to isolate pyrazines from the reaction mixture. Effective LLE of pyrazines from aqueous solution using either hexane, methyl-t-butyl ether (MTBE) or ethyl acetate required multiple extraction steps with fresh solvent each time. When hexane was used as the extraction solvent, no imidazole derivatives were extracted with the pyrazines. However, when MTBE or ethyl acetate was employed, 4-methyl imidazole was co-extracted and further cleanup was required. Passing the organic solvent extracts through a column of silica revealed that the silica retained the undesirable imidazoles, such as 4-methyl imidazole. A mixture of 90/10 hexane/ethyl acetate as eluting solvent provided the desirable pyrazines, but it also provided a desirable separation of pyrazines as a function of total alkyl substituent content. Distillation of the aqueous reaction mixture was also used to isolate the pyrazines, leaving the undesirable imidazoles in the undistilled portion of the reaction. Additional chromatographic methods were used to isolate pyrazines from the aqueous distillate including a column packed with C18-bonded silica.

Combined dilute hydrochloric acid and alkaline wet oxidation pretreatment to improve sugar recovery of corn stover.

Two-stage dilute hydrochloric acid (DA)/aqueous ammonia wet oxidation (AWO) pretreatment was used to recover the sugars of corn stover. The morphology characterizations of samples were detected by SEM, BET and SXT. The results showed that DA-AWO process demonstrated a positive effect on sugar recovery compared to AWO-DA. 82.8% of xylan was recovered in the first stage of DA-AWO process at 120 °C for 40 min with 1 wt% HCl. The second stage was performed under relative mild reaction conditions (130 °C, 12.6 wt% ammonium hydroxide, 3.0 MPa O2, 40 min), and 86.1% lignin could be removed. 71.5% of glucan was achieved with a low enzyme dosage (3 FPU·g-1) in the following enzymatic hydrolysis. DA-AWO pretreatment was effective due to its sufficient hydrolysis of hemicellulose in the first stage and remarkably removal of the lignin in the second stage, resulting in high sugar recovery with a low enzyme dosage.

Development of a micro-solid-phase extraction molecularly imprinted polymer technique for synthetic cannabinoids assessment in urine followed by liquid chromatography-tandem mass spectrometry.

Several molecularly imprinted polymers (MIPs) have been synthesized for the first time using various synthetic cannabinoids (JWH007, JWH015 and JWH098) as template molecules. Ethylene dimethacrylate (EDMA) was used as a functional monomer for all cases. Similarly, divinylbenzene (DVB) and 2,2'-azobisisobutyronitrile (AIBN) were used as cross-linker and initiator, respectively. The prepared MIPs have been fully characterized and evaluated as new selective adsorbents for micro-solid phase extraction (µ-SPE) of synthetic cannabinoids in urine. The developed MIP-µ-SPE devices consisted of a polypropylene (PP) porous membrane containing the adsorbent (novel porous membrane protected micro-solid phase extraction based on a cone-shaped device) for operating in batch mode, which allowed a fast and integrated extraction-cleanup procedure. High performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used for quantifying the analytes after MIP-µ-SPE. The best performances were obtained for MIPs prepared from JWH015 as a template. Optimum loading conditions were found to be urine pH of 5.0 and adsorption time of 8.0 min under mechanical (orbital-horizontal) stirring at 100 rpm. The composition of the eluting solution consisted of 75:20:5 heptane/2-propanol/ammonium hydroxide. The elution was assisted by ultrasounds (37 kHz, 325 W) for 8.0 min. In addition, studies regarding selectivity have also been addressed for several drugs of abuse under optimized loading/adsorption conditions. Validation of the method showed good precision and analytical recovery by intra-day and inter-day assays (RSD values lower than 7 and 10% for intra-day and inter-day precision, and within the 83-100% range for intra-day and inter-day analytical recovery).

Simple and Quick Method to Obtain a Decellularized, Functional Liver Bioscaffold.

The development of new approaches for organ transplantation has become crucial in the last years. In particular, organ engineering, involving the preparation of acellular matrices that provide a natural habitat for reseeding with an appropriate population of cells, is an attractive although technically demanding approach. We here describe a method that allows for the derivation of functional in vitro hepatic organoids and that does not require a previous selection of all the parenchymal hepatocytes and non-parenchymal cells, namely, Kupffer cells, liver endothelial cells, and hepatic stellate cells. The procedure also replaces the costly standard collagenase perfusion step with a trypsin-based enzymatic digestion that results in high-yield decellularization. A combination of physical and chemical treatments through deep immersion and intraluminal infusion of two different consecutive solutions is used: (1) deionized water (DI) and (2) DI + Triton X 1% + ammonium hydroxide (NH4OH) 0.1%. This ensures the isolation of the hepatic constructs that reliably maintain original architecture and ECM components while completely removing cellular DNA and RNA. The procedure is fast, simple, and cheap and warrants an optimal organoid functionality that may find applications in both toxicological and transplantation studies.

Adsorption of Cu2+ and Zn2+ by extracellular polymeric substances (EPS) in different sludges: Effect of EPS fractional polarity on binding mechanism.

Extracellular polymeric substances (EPS) in sludge samples played a major role in heavy metals removal during wastewater treatment. In this study, the binding quality, adsorption mechanism, as well as the chemical fractional contribution of the sludge EPS from activated sludge, anaerobic granular sludge and anaerobic flocculent sludge to the adsorption of Zn2+ and Cu2+ was investigated. For all three sludge samples, Cu2+ could be more easily adsorbed than Zn2+, and EPS extracted from the anaerobic granular sludge exhibited a relatively higher adsorption capacity than that of anaerobic flocculent sludge and activated sludge. Specifically, hydrophobic EPS of the activated sludge and anaerobic flocculent sludge was more efficient in adsorbing Cu2+ and Zn2+ than that of the hydrophilic EPS. However, hydrophilic EPS in anaerobic granular sludge played a greater role in heavy metals removal. The adsorption of those two heavy metals onto the unfractionated and hydrophobic EPS could be better described by the Langmuir isotherm, while Freundlich models fitted hydrophilic EPS. In addition, the effect of the heavy metals adsorption on the spectrum characteristics of the sludge EPS was also explored by analysis of FT-IR and fluorescent spectra.

Preparation of micro-porous bioceramic containing silicon-substituted hydroxyapatite and beta-tricalcium phosphate.

Dimensional instability caused by sintering shrinkage is an inevitable drawback for conventional processing of hydroxyapatite (HA). A new preparation method for biphasic calcium phosphates was developed to increase micro pores and biodegradation without significant dimensional change. Powder pressed HA discs, under 100MPa, were immersed in a colloidal mixture of tetraethoxysilane (TEOS) and ammonium hydroxide for 10min, followed by drying, and then were sintered at 900°C, 1050°C, and 1200°C, respectively. Comparing with pure HA discs, the newly prepared product sintered up to 1200°C contained silicon substituted HA, beta-tricalcium phosphate, and calcium silicate with better micro-porosity, high specific surface area, less sintering shrinkage and the strength maintained. The cytocompatibility test demonstrated a better viability for D1 mice stem cells cultured on TEOS treated HA for 14days compared to the pure HA. This simple TEOS sol-gel pretreatment has the potential to be applied to any existing manufacturing process of HA scaffold for better control of sintering shrinkage, create micropores, and increase biodegradation.

Macromolecular changes and nano-structural arrangements in gliadin and glutenin films upon chemical modification: Relation to functionality.

Protein macromolecules adopted for biological and bio-based material functions are known to develop a structured protein network upon chemical modification. In this study, we aimed to evaluate the impact of chemical additives such as, NaOH, NH4OH and salicylic acid (SA), on the secondary and nano-structural transitions of wheat proteins. Further, the effect of chemically induced modifications in protein macromolecular structure was anticipated in relation to functional properties. The gliadin-NH4OH-SA film showed a supramolecular protein organization into hexagonal structures with 65 Å lattice parameter, and other not previously observed structural entities having a characteristic distance of 50 Å. Proteins in gliadin-NH4OH-SA films were highly polymerized, with increased amount of disulfide crosslinks and ß-sheets, causing improved strength and stiffness. Glutenin and WG proteins with NH4OH-SA showed extensive aggregation and an increase in ß-sheet content together with irreversible crosslinks. Irreversible crosslinks hindered a high order structure formation in glutenins, and this resulted in films with only moderately improved stiffness. Thus, formation of nano-hierarchical structures based on ß-sheets and disulfide crosslinks are the major reasons of high strength and stiffness in wheat protein based films.

Decellularized periodontal ligament cell sheets with recellularization potential.

The periodontal ligament is the key tissue facilitating periodontal regeneration. This study aimed to fabricate decellularized human periodontal ligament cell sheets for subsequent periodontal tissue engineering applications. The decellularization protocol involved the transfer of intact human periodontal ligament cell sheets onto melt electrospun polycaprolactone membranes and subsequent bi-directional perfusion with NH4OH/Triton X-100 and DNase solutions. The protocol was shown to remove 92% of DNA content. The structural integrity of the decellularized cell sheets was confirmed by a collagen quantification assay, immunostaining of human collagen type I and fibronectin, and scanning electron microscopy. ELISA was used to demonstrate the presence of residual basic fibroblast growth factor (bFGF), vascular endothelial growth factor (VEGF), and hepatocyte growth factor (HGF) in the decellularized cell sheet constructs. The decellularized cell sheets were shown to have the ability to support recellularization by allogenic human periodontal ligament cells. This study describes the fabrication of decellularized periodontal ligament cell sheets that retain an intact extracellular matrix and resident growth factors and can support repopulation by allogenic cells. The decellularized hPDL cell sheet concept has the potential to be utilized in future "off-the-shelf" periodontal tissue engineering strategies.

Determining the optimal decellularization and sterilization protocol for preparing a tissue scaffold of a human-sized liver tissue.

Attaining a well-qualified whole decellularized organ applicable for an enduring and successful transplantation, decellularization protocols should be organ specific in terms of decellularizing agents and time of tissue exposure. Since a bioscaffold resulting from a large solid organ should have the potential to preserve its three-dimensional architecture and consistency for at least several months in the site of transplantation, evaluating the mechanical properties of the bioscaffold is mandatory before transplantation. In the current study, we compared five different decellularization protocols and also two main decellularization techniques (perfusion vs. diffusion) to decellularize the sheep liver, which is similar to the human liver in terms of size and anatomy. Moreover, we assessed the retaining of vascular network by dye injection and angiography. We also determined the most proper sterilization method by comparing six different sterilization methods. The mechanical properties of the scaffolds were assessed by applying tensile strength, suture retention, and compressive strength tests. The perfusion technique showed better results compared to the diffusion technique. The protocol containing ammonium hydroxide and triton X-100 was the most proper decellularization protocol leading to completely decellularized livers along with intact vascular network. Furthermore, we noted that application of streptokinase in washing step facilitates decellularization. Our results also showed that a combination of two sterilization methods is necessary for complete sterilization of a sheep liver and peracetic acid or ethylene oxide+gamma irradiation was associated with the best outcome. Determining the most appropriate decellularization and sterilization method for each organ along with assessing the mechanical properties of the resulting bioscaffold are principal steps before fabricating efficient artificial organs in the foreseeable future.