Self-Assembled Aminated and TEMPO Cellulose Nanofibers (Am/TEMPO-CNF) Aerogel for Adsorptive Removal of Oxytetracycline and Chloramphenicol Antibiotics from Water.

Antibiotics are used for the well-being of human beings and other animals. Detectable levels of antibiotics can be found in pharmaceutical, municipal, and animal effluents. Therefore, the treatment of antibiotic contaminated water is of great concern. In this study, we fabricated a sustainable aminated/TEMPO cellulose nanofiber (Am/TEMPO-CNF) aerogel to remove oxytetracycline (OTC) and chloramphenicol (CAP) from synthetic wastewater. The prepared aerogel was characterized using different analytical techniques such as elemental analysis, FTIR, TGA, SEM-EDS, and N2 adsorption-desorption isotherms. The characterization techniques confirmed the presence and interaction of quaternary amine -[NR3]+ and -COOH groups on Am/TEMPO-CNF with OTC and CAP, which validates the successful modification of Am/TEMPO-CNF. The adsorption process of the pollutants was examined as a function of solution pH, concentrations, reaction time, and temperatures. The maximum adsorption capacity was 153.13 and 150.15 mg/g for OTC and CAP, respectively. The pseudo-second order (PSO-2) was well fitted to both OTC and CAP, confirming the removal is via chemisorption. Hydrogen bonding and electrostatic attraction have been postulated as key factors in facilitating OTC and CAP adsorption according to spectroscopic studies. Energetically, the adsorption was spontaneous and endothermic for both pollutants. In conclusion, the efficient removal rate and excellent reusability of Am/TEMPO-CNF indicate the strong potential of the adsorbent for antibiotics' removal.

Cellulose Nanofibril Stabilized Pickering Emulsion Templated Aerogel with High Oil Absorption Capacity.

Nanocellulose-based aerogels, featuring a three-dimensional porous structure, are considered as a desirable green absorbent because of their exceptional absorption performance as well as the abundance and renewability of the raw material. However, these aerogels often require hydrophobic modification or carbonization, which is often environmentally harmful and energy-intensive. In this study, we introduce a Pickering-emulsion-templating approach to fabricate a cellulose nanofibril (CNF) aerogel with a hierarchical pore structure, allowing for high oil absorption capacity. n-Hexane-CNF oil-in-water Pickering emulsions are prepared as an emulsion template, which is further lyophilized to create a hollow microcapsule-based CNF (HM-CNF) aerogel with a density ranging from 1.3 to 6.1 mg/cm3 and a porosity of ≥99.6%. Scanning electron microscopy and Brunauer-Emmett-Teller analyses reveal the HM-CNF aerogel's hierarchical pore structure, originating from the CNF Pickering emulsion template, and also confirm the aerogel's very high surface area of 216.6 m2/g with an average pore diameter of 8.6 nm. Furthermore, the aerogel exhibits a maximum absorption capacity of 354 g/g and 166 g/g for chloroform and n-hexadecane, respectively, without requiring any surface modification or chemical treatment. These combined findings highlight the potential of the Pickering-emulsion-templated CNF aerogel as an environmentally sustainable and high-performance oil absorbent.

Microwave-Prepared Quantum Dots and Their Potential Applications as Adsorbents and Chemosensors.

A combination of different eco-friendly materials prepared promising fluorescent quantum dots (QDs) through the one-step process using the microwave heating of urea with cellulose, chitosan, and biochar. Characterizations of the prepared QDs, including the investigation of their structure by infrared spectroscopy, Raman analysis, X-ray diffraction, thermal gravimetric analysis, morphology, and optical properties, were performed. The results showed that QDs possess a small size, high UV absorption, and excitation wavelength-dependent fluorescence. The prepared QDs were also tested for metal ions removal from aqueous solutions. The adsorption at different contact times was investigated to optimize the adsorption efficiency of the prepared QDs. All QDs were found to be an ideal sorbent for Cr(II), Cu(II), Mn(II), and Pb(II). From the data, Cr(II) was more highly adsorbed than other metal ions. The results of the kinetic investigation showed that the pseudo-second-order kinetic model fit the adsorption process effectively. In addition, the fluorescence spectra of QDs were changed after the adsorption of metal ions; hence, the prepared QDs could be utilized in environmental sectors such as wastewater pollution detection, adsorption, and chemical sensing applications.

Amino-Functionalized Cellulose Nanofiber/Lignosulfonate New Aerogel Adsorbent for the Removal of Dyes and Heavy Metals from Wastewater.

Due to the increasingly widespread water pollutants and the high cost of treatment methods, there is a demand for new, inexpensive, renewable, and biodegradable adsorbent materials for the purification of wastewater contaminants. In this study, a new biocomposite aerogel (Amf-CNF/LS) was prepared using a chemically cross-linking method between the amino-functionalized cellulose nanofibers (Amf-CNF) and lignosulfonates (LS). The physical and chemical properties of the prepared aerogel were investigated using several techniques including elemental analysis, scanning electron microscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and N2 adsorption-desorption analysis. The Amf-CNF/LS aerogel was then applied for the removal of methylene blue (MB), rhodamine B dye (RhB), and the heavy metal cadmium ion (Cd2+) from synthetic wastewater solutions. The adsorption parameters controlling the adsorption process including the pH, contact time, adsorbent dosage, and adsorbate concen-tration were optimized. High adsorption kinetics and isotherms were observed, with the adsorption isotherms of the Amf-CNF/LS aerogel fitting the Langmuir model with maximum adsorption capacities of 170.94, 147.28, and 129.87 mg/g for MB, RhB, and Cd2+, respectively. These results show that Amf-CNF/LS aerogel is a promising green and inexpensive adsorbent for MB, RhB, and Cd2+ removal from wastewater.

Lignite, thermally-modified and Ca/Mg-modified lignite for phosphate remediation.

Aqueous phosphate uptake is needed to reduce global eutrophication. Negatively charged adsorbent surfaces usually give poor phosphate sorption. Chemically- and thermally-modified lignite (CTL) was prepared by impregnating low-cost lignite (RL) with Ca2+ and Mg2+ cations, basified with KOH (pH Ì´ 13.9), followed by a 1 h 600 °C pyrolysis under nitrogen. CTL has a positive surface (PZC = 13) due to basic surface Ca and Mg compounds, facilitating the aqueous phosphate uptake. CaCO3, MgO, Ca(OH)2, and Mg(OH)2 surface phases with 0.22 µm particle sizes were verified by XRD, XPS, SEM, TEM, and EDX before and after phosphate uptake. Higher amounts of these mineral phases promoted more CTL phosphate uptake than raw lignite (RL) and thermally treated lignite (TL) without Ca/Mg modification. Phosphorous uptake by Ca2+/Mg2+ occurs not by classic adsorption but by stochiometric precipitation of Mg3(PO4)2, MgHPO4, Ca3(PO4)2, and CaHPO4. This offers the potential of substantial uptake capacities. CTL's phosphate removal is pH-dependent; the optimum pH was 2.2. Water-washed CTL exhibited a maximum Langmuir phosphate uptake capacity of 15.5 mg/g at pH 7, 6 and 14 times higher than that of TL and RL, respectively (particle size <150 µm, adsorbent dose 50 mg, 25 mL of 25-1000 ppm phosphate concentration, 24 h, 25 °C). The unwashed CTL exhibited a maximum Langmuir phosphate removal capacity (80.6 mg/g), 5.2-times greater than the washed CTL (15.5 mg/g). Insoluble Ca2+ and Mg2+ phosphates/hydrophosphate particles dominated CTL's phosphate removal. Phosphates were recovered from both exhausted unwashed and washed CTL better in HCl than in NaOH. P-laden washed CTL exhibited a slow phosphate leaching rate under initial pH of 6.5-7.5 (52-57% over 20 days) after phosphate uptake, indicating it could serve as a slow-release fertilizer. Unwashed CTL retained more phosphates than washed CTL (cumulative qe for 4 cycles = 391.8 mg/g vs 374.7 mg/g) and potentially improves soil fertility more.

Characterization of graphene/pine wood biochar hybrids: Potential to remove aqueous Cu2.

Biochar-based hybrid composites containing added nano-sized phases are emerging adsorbents. Biochar, when functionalized with nanomaterials, can enhance pollutant removal when both the nanophase and the biochar surface act as adsorbents. Three different pine wood wastes (particle size < 0.5 mm, 10 g) were preblended with 1 wt% of three different graphenes in aqueous suspensions, designated as G1, G2, and G3. G1 (SBET, 8.1 m2/g) was prepared by sonicating graphite made from commercial synthetic graphite powder (particle size 7-11 µm). G2 (312.0 m2/g) and G3 (712.0 m2/g) were purchased commercial graphene nanoplatelets (100 mg in 100 mL deionized water). These three pine wood-graphene mixtures were pyrolyzed at 600 °C for 1 h to generate three graphene-biochar adsorbents, GPBC-1, GPBC-2, and GPBC-3 containing 4.4, 4.9, and 5.0 wt% of G1, G2, and G3 respectively. Aqueous Cu2+ adsorption capacities were 10.6 mg/g (GPBC-1), 4.7 mg/g (GPBC-2), and 5.5 mg/g (GPBC-3) versus 7.2 mg/g for raw pine wood biochar (PBC) (0.05 g adsorbent dose, Cu2+ 75 mg/L, 25 mL, pH 6, 24 h, 25 ± 0.5 °C). Increased graphene surface areas did not result in adsorption increases. GPBC-1, containing the lowest nanophase surface area with the highest Cu2+ capacity, was chosen to evaluate its Cu2+ adsorption characteristics further. Results from XPS showed that the surface concentration of oxygenated functional groups on the GPBC-1 is greater than that on the PBC, possibly contributing to its greater Cu2+ removal versus PBC. GPBC-1 and PBC uptake of Cu2+ followed the pseudo-second-order kinetic model. Langmuir maximum adsorption capacities and BET surface areas were 18.4 mg/g, 484.0 m2/g (GPBC-1) and 9.2 mg/g, 378.0 m2/g (PBC). This corresponds to 3.8 × 10-2 versus 2.4 × 10-2 mg/m2 of Cu2+ removed on GPBC-1 (58% more Cu2+ per m2) versus PBC. Cu2+ adsorption on both these adsorbents was spontaneous and endothermic.

Eucalyptus Globulus protects against diclofenac sodium induced hepatorenal and testicular toxicity in male rats.

The current study was conducted to investigate the protective properties of Eucalyptus globulus leaves methanolic extract (EGLME) against diclofenac sodium (DS) induced hepatorenal and testicular toxicity in male rats. A total of 40 rats were equally divided into 4 groups, Control, Diclofenac sodium (DS), EGLME and DS + EGLME groups, respectively. DS and EGLME were administered orally at dose rate 2.5 and 100 mg/kg BW, 4 times/week for 8 weeks, respectively. Administration of DS distorted hepatorenal functions manifested by alteration of serum levels of ALT, AST, total protein and albumin, creatinine and urea with changes of histological architectures. DS caused reproductive toxicity represented by minimized sperm count, individual sperm motility and viability; depleted concentration of reduced glutathione (GSH) in testicular tissue; and decreased testosterone level with alteration in testicular histological features. In contrast, co-treatment of DS intoxicated rats with EGLME protected rats against the adverse effects of DS revealing enhancing properties of EGLME on rats' liver, kidney and testes. In conclusion, we demonstrated that EGLME had a potent protecting property against DS induced hepatic, renal and testicular toxicity in male rats, with special concern to testicular tissue via modulation of GSH as an oxidant marker. TAXONOMY: (classification by EVISE): Diclofenac sodium toxicity (hepatorenal and testicular toxicity), co-treatment with natural herbal extract, blood biochemical assays, tissue anti-oxidants assay, histopathology and reproductive indices analyses.

Microporous carbon nanoflakes derived from biomass cork waste for CO2 capture.

Porous structure design is considered to be a promising strategy for the development of effective sorbents for CO2 capture. Herein, a series of carbon nanoflakes with large surface area (up to 2380 m2/g) and high micropore volume (up to 0.896 m3/g) were synthesized from a renewable precursor, cork dust waste, to capture CO2 at atmospheric pressure. The nanoflakes exhibited superior CO2 uptake performance at 1 bar with the maximum capacity of 7.82 and 4.27 mmol/g at 0 and 25 °C, respectively, in sharp contrast to previously reported porous carbon materials. The existence of large numbers of narrow micropores with the pore width less than 0.86 nm and 0.70 nm play a critical role in the CO2 uptake at 0 and 25 °C, respectively. Moreover, the CNFs exhibited good recyclability and high selectivity for CO2 uptake from the mixture of CO2 and N2. By taking advantage of the unique hollow honeycomb cell, the three-layered cell wall structure, as well as the unique chemical composition of a cork precursor, such delicate microporous carbon nanoflakes were able to be achieved by simple thermal pretreatment combined with chemical activation. This bioinspired precursor-synthesis route poses a great potential for the facile production of porous carbons for a variety of diverse applications including CO2 capture.

Novel oxone treated hydrochar for the removal of Pb(II) and methylene blue (MB) dye from aqueous solutions.

This study represents the first ever work on a novel oxone treated hydrochar as an adsorbent for the efficient removal of different contaminants from aqueous solutions. Pine wood hydrochar (HC) was prepared by hydrothermal treatment at 300 °C and oxidized with oxone to produce oxidized pine wood hydrochar (OHC). Different analytical tools such as elemental analysis, FTIR, TGA, FE-SEM, and BET were used for the characterization of the OHC. Conductometric titration of OHC showed a substantial increase from 22 µmol/g to 600 µmol/g in the hydrochar carboxylic content. The OHC sorption performance was assessed by using Pb(II) ions and methylene blue (MB) dye as two models of contaminants. Sorption benchmarks were performed by varying the contaminant initial concentration, time, and temperatures. Sorption kinetic data was fitted well to the pseudo-second order kinetic model with high correlation coefficients (R2 > 0.99) and isothermal data was fitted to the Langmuir model. The highest adsorption capacities for MB and Pb(II) were 86.7 mg/g and 46.7 mg/g, respectively. This study proves that oxone treatment could be a potential sustainable oxidation method to tune the hydrochar surface to increase selectivity towards heavy metal ions and dye sorption.

Biochar Adsorbents with Enhanced Hydrophobicity for Oil Spill Removal.

Oil spills cause massive loss of aquatic life. Oil spill cleanup can be very expensive, have secondary environmental impacts, or be difficult to implement. This study employed five different adsorbents: (1) commercially available byproduct Douglas fir biochar (BC) (SA ∼ 695 m2/g, pore volume ∼ 0.26 cm3/g, and pore diameter ∼ 13-19.5 Å); (2) BC modified with lauric acid (LBC); (3) iron oxide-modified biochar (MBC); (4) LBC modified with iron oxide (LMBC); and (5) MBC modified with lauric acid (MLBC) for oil recovery. Transmission, engine, machine, and crude oils were used to simulate oil spills and perform adsorption experiments. All five adsorbents adsorbed large quantities of each oil in fresh and simulated seawater with only a slight pH dependence, fast kinetics (sorptive equilibrium reached before 15 min), and high regression fits to the pseudo-second-order kinetic model. The Sips isotherm model oil sorption capacities for these sorbents were in the range ∼3-11 g oil/1 g adsorbent. Lauric acid-decorated (60-2 wt %) biochars gave higher oil adsorption capacities than the undecorated biochar. Lauric acid enhances biochar hydrophobicity and its water contact angle and reduces water influx into biochar's porosity preventing it from sinking in water for 3 weeks. These features were observed even at 2% wt of lauric acid (sinks only after 2 weeks). Magnetization by magnetite nanoparticle deposition onto BC and LBC allows the recovery of the exhausted adsorbent by a magnetic field as an alternative to filtration. Oil sorption was endothermic. Recycling was demonstrated after toluene stripping. The oil-laden adsorbents' heating values were obtained, suggesting an alternative use of these spent adsorbents as a low-cost fuel after recovery, avoiding waste disposal costs. The initial and oil-laden adsorbents were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmet-Teller surface area, contact angle, thermogravimetric analyses, differential scanning calorimetry, vibrating sample magnetometry, elemental analysis, and X-ray photoelectron spectroscopy.

Assessing South American Guadua chacoensis bamboo biochar and Fe3O4 nanoparticle dispersed analogues for aqueous arsenic(V) remediation.

Discarded bamboo culms of Guadua chacoensis were used for biochar remediation of aqueous As(V). Raw biochar (BC), activated biochar (BCA), raw Fe3O4 nanoparticle-covered biochar (BC-Fe), and activated biochar covered with Fe3O4 nanoparticles (BCA-Fe) were prepared, characterized and tested for As(V) aqueous adsorption. The goal is to develop an economic, viable, and sustainable adsorbent to provide safe arsenic-free water. Adsorbents were characterized using scanning electron microscopy (SEM) and energy dispersive analysis by X-ray (SEM-EDX), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (TEM-EDS), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller surface area measurements (SBET), point of zero charge determinations (PZC), and elemental analysis. Activation with KOH increased the O/C ratio and the surface area of BC from 6.7 m2/g to 1239.7 m2/g (BCA). As(V) sorption equilibrium was achieved within <2 h for all four adsorbents and kinetics followed the pseudo-second-order model. At a 10 mg/L initial As(V) concentration, BC-Fe achieved a 100% removal (5 mg/g) over a pH 5 to 9 window. Sorption was endothermic on all four adsorbents and the capacities rose with the increasing temperature. Langmuir capacities at 40 °C for BC, BCA, BC-Fe, and BCA-Fe were 256, 217, 457, and 868 mg/g, respectively, and capacities were compared with other sorbents. Breakthrough fixed-bed column sorption was carried out for BC and BC-Fe producing 6.6 mg/g and 13.9 mg/g bed capacities, respectively. Potassium phosphate was a better As stripping agent than sodium bicarbonate. Performance of the adsorbents in an As(V)-spiked natural water and a naturally As(V)-contaminated domestic water were assessed. Robust arsenate sequestration occurred generating As-safe water (As <0.01 mg/L), despite the presence of competing ions. Stoichiometric precipitation of iron-arsenate complexes triggered by iron dissolution was also established.

Optimization of microbial cell disruption using pressurized CO2 for improving lipid recovery from wet biomass.

Microbial cell disruption using pressurized gases (e.g., CO2) is a promising approach to improve the lipid recovery from wet oleaginous microorganisms by eliminating the energy-intensive drying required for conventional methods. In this study, we perform cell disruption of Rhodotorula glutinis using pressurized CH4, N2, and Ar where we find the efficacy of these gases on cell viability is minimal. Since CO2 is found to be the only viable gas for microbial cell disruption among these four gases, we use a combination of Box-Behnken design and response surface methodology (RSM) to find the optimal cell disruption by tuning different parameters such as pressure (P), temperature (T), exposure time (t), and agitation (a). From RSM, we find 6 log reduction of viable cells at optimized conditions, which corresponds to more than 99% cell death at P = 4000 kPa, T = 296.5 K, t = 360 min, and a = 325 rpm. Furthermore, from the scanning electron microscope (SEM), we find a complete morphological change in the cell structure when treated with pressurized CO2 compared to the untreated cells. Finally, we find that up to 85% of total lipid can be recovered using optimized pressurized CO2 from wet biomass compared to the untreated wet cells where up to 73% lipid can be recovered.

The influence of three acid modifications on the physicochemical characteristics of tea-waste biochar pyrolyzed at different temperatures: a comparative study.

Tea-waste is an abundant feedstock for producing biochar (BC) which is considered to be a cost effective carbonaceous adsorbent useful for water remediation and soil amendment purposes. In the present study, tea-waste BC (TWBC) produced at three different temperatures were subjected to nitric, sulfuric and hydrochloric acid modifications (abbreviated as NM, SM and HM respectively). Characteristics of the raw and modified BC such as ultimate and proximate analyses, surface morphology, surface acidity and functionality, point of zero charge, cation exchange capacity (CEC) and thermal stability were compared to evaluate the influence of pyrolysis temperature and of modifications incorporated. The amount of carboxylic and phenolic surface functionalities on TWBC was seen to decrease by 93.44% and 81.06% respectively when the pyrolysis temperature was increased from 300 to 700 °C. Additionally, the yield of BC was seen to decrease by 46% upon the latter temperature increment. The elemental analysis results provided justification for high-temperature BC being more hydrophobic as was observed by the 61% increase in H/C ratio which is an indication of augmented aromatization. The CEC was the highest for the low-temperature BC and was seen to further increase by NM which is attributed to the 81.89% increase in carboxylic functionalities. The surface area was seen to significantly increase for BC700 upon NM (∼27 times). The SM led to pore wall destruction which was observed in scanning electron microscopy images. Findings would enable the rational use of these particular modifications in relevant remediation and soil amendment applications.

Catalytic upgrading of bio-oil produced from hydrothermal liquefaction of Nannochloropsis sp.

Upgrading of bio-oil obtained from hydrothermal liquefaction (HTL) of algae is necessary for it to be used as a fuel. In this study, bio-oil obtained from HTL of Nannochloropsis sp. was upgraded using five different catalysts (Ni/C, ZSM-5, Ni/ZSM-5, Ru/C and Pt/C) at 300 °C and 350 °C. The upgraded bio-oil yields were higher at 300 °C; however, higher quality upgraded bio-oils were obtained at 350 °C. Ni/C gave the maximum upgraded bio-oil yield (61 wt%) at 350 °C. However, noble metal catalysts (Ru/C and Pt/C) gave the better upgraded bio-oils in terms of acidity, heating values, and nitrogen values. The higher heating value of the upgraded bio-oils ranged from 40 to 44 MJ/kg, and the nitrogen content decreased from 5.37 to 1.29 wt%. Most of the upgraded bio-oils (35-40 wt%) were in the diesel range. The major components present in the gaseous products were CH4, CO, CO2 and lower alkanes.

Influence of biochemical composition during hydrothermal liquefaction of algae on product yields and fuel properties.

Hydrothermal liquefaction (HTL) of nine algae species were performed at two reaction temperatures (280 and 320°C) to compare the effect of their biomass composition on product yields and properties. Results obtained after HTL indicate large variations in terms of bio-oil yields and its properties. The maximum bio-oil yield (66wt%) was obtained at 320°C with a high lipid containing algae Nannochloropsis. The higher heating value of bio-oils ranged from 31 to 36MJ/kg and around 50% of the bio-oils was in the vacuum gas oil range while high lipid containing algae Nannochloropsis contained a significant portion (33-42%) in the diesel range. A predictive relationship between bio-oil yields and biochemical compositions was developed and showed a broad agreement between predictive and experimental yields. The aqueous phases obtained had high amount of TOC (12-43g/L), COD (35-160g/L), TN (1-18g/L), ammonium (0.34-12g/L) and phosphate (0.7-12g/L).

Carbon Nanostructure of Kraft Lignin Thermally Treated at 500 to 1000 °C.

Kraft lignin (KL) was thermally treated at 500 to 1000 °C in an inert atmosphere. Carbon nanostructure parameters of thermally treated KL in terms of amorphous carbon fraction, aromaticity, and carbon nanocrystallites lateral size (La), thickness (Lc), and interlayer space (d002) were analyzed quantitatively using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy. Experimental results indicated that increasing temperature reduced amorphous carbon but increased aromaticity in thermally treated KL materials. The Lc value of thermally treated KL materials averaged 0.85 nm and did not change with temperature. The d002 value decreased from 3.56 Å at 500 °C to 3.49 Å at 1000 °C. The La value increased from 0.7 to 1.4 nm as temperature increased from 500 to 1000 °C. A nanostructure model was proposed to describe thermally treated KL under 1000 °C. The thermal stability of heat treated KL increased with temperature rising from 500 to 800 °C.

Transparent bionanocomposite films based on chitosan and TEMPO-oxidized cellulose nanofibers with enhanced mechanical and barrier properties.

The development of biobased active films for use in food packaging is increasing due to low cost, environmental appeal, renewability and availability. The objective of this research was to develop an effective and complete green approach for the production of bionanocomposite films with enhanced mechanical and barrier properties. This was accomplished by incorporating TEMPO-oxidized cellulose nanofibers (2,2,6,6-tetramethylpiperidine-1-oxyl radical) into a chitosan matrix. An aqueous suspension of chitosan (100-75wt%), sorbitol (25wt%) and TEMPO-oxidized cellulose nanofibers (TEMPO-CNFs, 0-25wt%) were cast in an oven at 40°C for 2-4days. Films were preconditioned at 25°C and 50% RH for characterization. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermogravimetric analysis (TGA-DTG) and X-ray diffraction (XRD). Incorporation of TEMPO-CNFs enhanced the mechanical strength of the films due to the high aspect ratio (3-20nm width, and 10-100nm length) of TEMPO-CNFs and strong interactions with the chitosan matrix. Oxygen and water vapor transmission rates for films that are prepared with chitosan and TEMPO-CNFs (15-25wt%) were significantly reduced. Furthermore, these bionanocomposite films had good thermal stability. Use of TEMPO-CNFs in this method makes it possible to produce bionanocomposite films that are flexible, transparent, and thus have potential in food packaging applications.

Chemical isolation and characterization of different cellulose nanofibers from cotton stalks.

Recently, cellulose nanofibers (CNFs) have received wide attention in green nanomaterial technologies. Production of CNFs from agricultural residues has many economic and environmental advantages. In this study, four different CNFs were prepared from cotton stalks by different chemical treatments followed by ultrasonication. CNFs were prepared from untreated bleached pulp, sulfuric acid hydrolysis, and TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl) oxy radical]-mediated oxidation process. Physical and chemical properties of the prepared CNFs such as morphological (FE-SEM, AFM), structural (FTIR), and thermal gravimetric analysis (TGA) were investigated. Characterization results clearly showed that the method of preparation results in a significant difference in the structure, thermal stability, shape and dimensions of the produced CNFs. TEMPO-mediated oxidation produced brighter and higher yields (>90%) of CNFs compared to other methods. FE-SEM and AFM analysis clearly indicated that, TEMPO-mediated oxidation produced uniform nano-sized fibers with a very small diameter (3-15 nm width) and very small length (10-100 nm). This was the first time uniform and very small nanofibers were produced.

Microbial conversion of pyrolytic products to biofuels: a novel and sustainable approach toward second-generation biofuels.

This review highlights the potential of the pyrolysis-based biofuels production, bio-ethanol in particular, and lipid in general as an alternative and sustainable solution for the rising environmental concerns and rapidly depleting natural fuel resources. Levoglucosan (1,6-anhydrous-ß-D-glucopyranose) is the major anhydrosugar compound resulting from the degradation of cellulose during the fast pyrolysis process of biomass and thus the most attractive fermentation substrate in the bio-oil. The challenges for pyrolysis-based biorefineries are the inefficient detoxification strategies, and the lack of naturally available efficient and suitable fermentation organisms that could ferment the levoglucosan directly into bio-ethanol. In case of indirect fermentation, acid hydrolysis is used to convert levoglucosan into glucose and subsequently to ethanol and lipids via fermentation biocatalysts, however the presence of fermentation inhibitors poses a big hurdle to successful fermentation relative to pure glucose. Among the detoxification strategies studied so far, over-liming, extraction with solvents like (n-butanol, ethyl acetate), and activated carbon seem very promising, but still further research is required for the optimization of existing detoxification strategies as well as developing new ones. In order to make the pyrolysis-based biofuel production a more efficient as well as cost-effective process, direct fermentation of pyrolysis oil-associated fermentable sugars, especially levoglucosan is highlly desirable. This can be achieved either by expanding the search to identify naturally available direct levoglusoan utilizers or modify the existing fermentation biocatalysts (yeasts and bacteria) with direct levoglucosan pathway coupled with tolerance engineering could significantly improve the overall performance of these microorganisms.

Inhibitors removal from bio-oil aqueous fraction for increased ethanol production.

Utilization of 1,6-anhydro-ß-d-glucopyranose (levoglucosan) present (11% w/v) in the water fraction of bio-oil for ethanol production will facilitate improvement in comprehensive utilization of total carbon in biomass. One of the major challenges for conversion of anhydrous sugars from the bio-oil water fraction to bio-ethanol is the presence of inhibitory compounds that slow or impede the microbial fermentation process. Removal of inhibitory compounds was first approached by n-butanol extraction. Optimal ratio of n-butanol and bio-oil water fraction was 1.8:1. Removal of dissolved n-butanol was completed by evaporation. Concentration of sugars in the bio-oil water fraction was performed by membrane filtration and freeze drying. Fermentability of the pyrolytic sugars was tested by fermentation of hydrolyzed sugars with Saccharomyces pastorianus lager yeast. The yield of ethanol produced from pyrolytic sugars in the bio-oil water fraction reached a maximum of 98% of the theoretical yield.