Carbon quantum dots derived from rice straw doped with N and S and its nanocomposites with hydroxypropyl cellulose nanocomposite.

As biomass, rice straw (RS) is often valorized as a precursor of green products. In this respect, the RS-based carbon quantum dots (CQDs) are synthesized doped with N and S during the preparation. Synergistic doping with lipoic acid and ethylenediamine can vastly increase the yield of CQD from rice straw from 6.14 % to 62.8 %, and sulfur doping plays a more important role on the surface functional groups of the quantum dots. Further assessment is achieved toward the performance of SN-CQDs-hydroxypropyl cellulose nanocomposites. The optical behavior of synthesized SN-CQDs, and the critical concentration of its liquid crystal behaviors, at which the anisotropic phase begins to emerge, is approximately 1 %. Incorporating it into HPC, especially at 5 %, provided nanocomposite films with effective liquid crystal, tensile strength, and thermal stability. This sample's texture reveals a planar structure with colors ranging from yellow to red. The synergistic effect of incorporating SN-CQDs is shown by improving the strength to ~282.1 %, and the activation energy increased from 583.6 kJ.mol-1 to 615.1 kJ/mol. HPC-SN-CQDs can be assembled into an LED device, emitting warm light, of which CIE coordinate is (0.34,0.43).

Opportunity for valorization of pulping by-product in production high performance sustaining release lignin-based gel.

This study focuses on optimizing the pulping by-product to produce effective hydrogels for controlling the release of salicylic acid (SA). In this regard, two routes are achieved: the first involves preparing black liquor (BL) composite hydrogels with various polymer macromolecules [polyacrylamide (PAM), polyvinyl alcohol (PVA), and chitosan (Cs), and the second involves carboxymethylation of BL and grafting with acrylamide. Hydrogels are evaluated using spectral analysis (ATR-FTIR), thermal analysis (TGA and DTG), and swelling measures. Encapsulation, release profile, SA release kinetics, as well as ATR-FTIR and SEM measurements, were used to evaluate the behavior of loaded hydrogels. According to the results, grafted carboxymethylated BL-gel had the maximum SA release (98.7 %), followed by PAM-BL (51.7 %) and PAM/PVA-BL (43.1 %). Over a 48-hour period, the hydrogels demonstrated a prolonged SA release pattern. The Ritger-Peppas and Higuchi models fitted to all examined hydrogels showed that SA release followed both Fickian and non-Fickian diffusion pathways.

Enhancing the valorization of pulping black liquors in production effective aerogel-carbon nanostructure as adsorbents toward cationic and ionic dyes.

This work deals with promoting the efficiency of removing the cationic and ionic dyes by new aerogel-carbon nanostructures. For cleaner production the rice straw-pulping black liquors, which regards serious environmental risk during routine disposing, is used in preparing the aerogel precursors. These aerogels (AGBs) depend on using pulping black liquor in hybrid with resorcinol and the less carcinogenic formaldehyde butyraldehyde. Black liquors from five pulping processes are used, Elemental, thermogravimetric (TGA and DTG), and FTIR-ATR analyses are used to characterize the carbon precursors. While their adsorption behavior toward cationic and anionic dyes are accessed via iodine-value, adsorption capacity and kinetic models, textural characterization, and SEM. The TGA measurements reveal that AGBs from BLs of neutral sulfite and soda-borohydride pulping reagents have higher activation and degradation energies than other aerogels. In terms of cationic and anionic dyes adsorption as well as textural characterization, the AGB-CNSs surpass that made from BLs. The discarded KOH/NH4OH black liquor is used to synthesize the best aerogel precursor for producing cationic methylene blue dye (MB) adsorbent, where it provides an adsorption capacity 242.1 mg/g. The maximum anionic brilliant blue dye (BB) adsorption capacity, 162.6 mg/g, is noticed by Kraft BL-aerogel-CNSs. These finding data overcome the literature carbon adsorbents based on lignin precursors. All examined CNSs toward MB dye follow the Langmuir adsorption equilibrium; while primarily the Freundlich model for BB dye. The pseudo-second-order kinetic model well fits the adsorption kinetics of investigated AGB-CNSs. The textural characterization and SEM revealed a mixture of mesoporous and micro porous features in the CNSs.

Performance effectiveness of nano-lignin in production of gel with nano-chitosan for controlling release of salicylic acid.

This work deals with assessing the performance of lignin nanoparticles (LNPs) in solving the problem of using salicylic acid as an agrochemical compound, via controlling its release. LNPs, obtained from black liquor, have been used to develop new delivery systems. Gels from chelating of LNPs with chitosan or chitosan nanoparticles (Cs-NPs) in presence or absence of cationic starch are investigated to achieve this essential aim. The nanoparticles are examined by TEM, ATR-FTIR, and XRD techniques. Based on measurements of swelling, encapsulation, release profile, release kinetic modeling of salicylic acid (SA), infrared spectroscopy, thermo-gravimetric analysis and scanning electron microscope the behavior of the investigated nanocomposite gels is assessed. The results show that the SA release profile of Cs-NPs and its nanocomposite with LNPs in phosphate-buffered saline (PBS) (7.4) (51.5-69.4 %) is higher than that of the mixture of water and ethanol (34.9-50.4 %). The release profile in PBS (7.4) demonstrates a trend of prolonged SA release over a 48-hour period. Best control of the SA-release can be achieved by CsNPs-LNPs nanocomposite. Comparing the results with previous literature demonstrates the promising characteristics of these examined gel nanocomposites. The release of SA from nanocomposites is regulated by a diffusion mechanism and follows the Ritger-Peppas and Higuchi models for kinetic release.

Assessment of the effect of different pulping by-products on enhancing the reuse of rubber waste in producing of cement-mortar.

This work deals with avoiding the pollution risks from paper pulping liquors and rubber wastes that result from routine disposal tools; moreover, finding an approach to minimize the drawback of incorporating the rubber waste in weakening the strength of building materials. In this respect, pulping black liquors (BLs) is assessed as a treating agent for rubber waste and substituting the water in cement mortar formulation. The assessment was achieved by testing the mechanical properties, water resistance (reduction in water absorption and dimensional change against water), and morphology. The results showed that all BLs from different pulping agents, used in mixtures with water, provided improvements in both strength and water resistance properties. Kraft black liquor is most effective in providing improvements in compressive strength and flexural strength, as well as resistance to water absorption and change in dimension after exposure to water for 24 h, where the improvements were 688.2 %, 494.3 %, 27 %, and 65.3 %, respectively. It is interesting to note that this investigated route provided improvements in the impact resistance property of mortar. This last property is essential for minimizing accidents on the highway.

Toward pulping process for enhancing the RS-black liquors as precursor of activated carbons for aqueous adsorbent purposes.

This work deals with providing a green pulping process of rice straw with zero waste discharged, via valorization of its by-product as a promising precursor for production of carbon nanostructures. The carbon nanostructures (BL-CNSs) from rice straw pulping liquors (BLs) are prepared in one step with phosphoric acid activation. The carbon nanostructures (BL-CNSs) from rice straw pulping liquors (BLs) are prepared in one step with phosphoric acid activation. The optimal pulping approach for achieving effective adsorbent (BL-CNSs) of cationic and anionic dyes is recommended from using different BLs precursors resulting from different reagents (alkaline, neutral, and acidic reagents). The carbon precursors are characterized by elemental, thermal (TGA and DTG) and ATR FTIR analyses. While the impact of pulping route on performance of CNSs is evaluated by their adsorption of iodine, cationic dye and anionic dye, as well as ATR-FTIR, textural characterization, and SEM. The data of elemental analysis displayed a high Carbon content ranges from 57.85 to 66.69% suitable for CNSs preparation, while the TGA showed that Sulphur-containing BLs (Kraft, neutral sulfite and acidic sulfite) have higher degradation temperature and activation energies as compared with other BLs. The optimum BL-CNSs adsorbent is prepared from the disposed neutral sulfite black liquor, with the following characteristics: cationic dye adsorption capacity 163.9 mg/g, iodine value 336.9 mg/g and SBET 310.6 m2/g. While the Kraft-CNSs provided highest anionic adsorption (70.52 mg/g). The studies of equilibrium and kinetic adsorption of dyes showed that the adsorption equilibrium of all investigated BL-CNSs toward MB follow the Langmuir and mainly Freundlich models for BB adoption. Their adsorption kinetics are a good fit with the pseudo-second-order model. The textural characterization and SEM revealed the CNSs exhibit a mixture of mesoporous and microporous structure.

Upcycling polyethylene terephthalate wastes for enhancing the performance of polyester from rice straw polyol in HDPE-composites.

Upscaling the utilization of polymer wastes together with the valorization of undesirable waste rice straw (RS) will minimize the environmental impact of waste disposal by traditional tools. This present work assesses the utilization of polyethylene terephthalate wastes in enhancing the production of polyester-(high density polyethylene) HDPE from Rice straw polyol composites. In this respect, the polyester from rice straw polyol in hybrid with glycolysis polyethylene terephthalate wastes (Gly-WPET) was assessed in comparison with that resulted from RS-polyol, using FTIR, non-isothermal analysis, and mechanical tests. The data showed the positive role of Gly-WPET in hybrid with RS-polyol in production polyester with high thermal stability and mechanical properties. It provided an increase in activation energy of degradation, elongation, Young's Modulus, and modulus of toughness from 184.5 to 1201 kJ/mole, from 4.7 to 9.8%, from 47.5 to 66.5 MPa, and from ~ 4.0 to 23 J/m3, respectively. This behavior was reflected in the properties of HDPE-polyester polyol (PEPO) composites, especially in improving elongation (from 55.4 to 72%). These promising data persuade us to recommend the influential role of Gly-WPET in using PEPO from liquefied RS as a plasticizer.

Synthesis and evaluation of protein-based biopolymer in production of silver nanoparticles as bioactive compound versus carbohydrates-based biopolymers.

This overall process deals with evaluating the performance of silver nanoparticles, synthesized from sodium caseinate (SC) as green biological active agent, in comparison with widely produced from carboxymethyl cellulose, other carbohydrates (oxidized nanocellulose fibres (OC) and starch (St)). The TGA, FTIR and TEM, as well as its antimicrobial activities toward pathogenic Gram-positive and Gram-negative bacteria in addition to the yeast strain Candida albicans NRRL Y-477 were examined. In addition, with regard to their anti-tumour activity, the evaluation was studied via many cancer cell lines against RPE1 (normal retina cell line). The results revealed that the SC-Ag(I) and CMC-Ag(I) complexes were formed in six- and five-membered chelate rings, respectively, as nanoparticles, while linear chelation structure was formed in case of OC-Ag(I) and St-Ag(I) complexes. The complexation of SC with Ag(I) ions was recommended as promising stable and antimicrobial agent, with lower free Ag(I) ions and particle size than other Ag-complexes. Moreover, it provided anti-tumour activity of most tested cell lines (in vitro), with the following sequence HCT116 > PC3 > HePG 2 > MCF-7 > A549 with IC50 and IC90 values of 25.8 and 54.73 µg ml-1, 45.1 and 66.7 µg ml-1, 64.3 and 110.7 µgml-1, 71.4 and 114.8 µgml-1 and 80.1 and 127.7 µgml-1, respectively. The promising effect of SC-Ag complex was also clear from its selective index versus RPE1 (normal retina cell line).

Optimizing the chitosan-cellulose based drug delivery system for controlling the ciprofloxacin release versus organic/inorganic crosslinker, characterization and kinetic study.

This work was done to optimize the drug delivery system based on N-trimethyl chitosan (TMC) and carboxylate-containing cellulose derivatives, as well as assessment the effective role of organic and inorganic cross-linkers for controlling release of ciprofloxacin (CPX) drug. Organic crosslinking of oxidized cellulose nanoparticle or CMC with TMC for preparing the hydrogel and their CPX drug loading were characterized by FTIR, swelling behaviour, DSC and SEM. Parallel tests were carried out on using Cu (II) ions as inorganic cross-linker. The FTIR and DSC data confirmed the formation of crosslinked delivery systems incorporated with CPX drug and candidate the TMC-CMC as the most stable delivery system. The SEM micrographs evidence the compatibility of cross-linked delivery systems with the incorporated of CPX drug through the hydrogel matrix. In vitro drug release study showed the effectiveness of organic crosslinking of TMC with CMC and OC to control the release of CPX than TMC, individually. Sustained and controlled drug releases were observed for organic crosslinked CMC (TMC-CMC) with maximum release (~75%) exceeded the TMC-OC and inorganic crosslinked CMC (Cu (II)-CMC). The release kinetics of all examined hydrogels followed Ritger-Peppas and Higuchi models, that indicating Fickian and the release of CPX was primarily controlled by diffusion process. The cell viability of human normal fibroplast cell line (BJ1) was positively correlated with the type of cellulose derivative-hydrogels and crosslinker. The TMC-CMC was recommended as promising safety and control drug release hydrogel.

Comparative evaluation for controlling release of niacin from protein- and cellulose-chitosan based hydrogels.

This work deals with assessing the efficient performance of sodium caseinate (SC) as protein-based drug delivery system of niacin (NA) than carboxymethyl cellulose (CMC). In this respect the hydrogels from complexation of chitosan with sodium caseinate (SC/Ch) or sodium carboxymethyl cellulose (CMC/Ch) were prepared. The Synthesized NA free and loaded hydrogels were characterized by many techniques for examining the interaction, morphology, swelling, encapsulation efficiency (EE) and loading (L) % of niacin, as well as cytotoxicity study. The finding data showed the promising behavior of SC/Ch hydrogel than CMC/Ch hydrogel, toward the amount of loaded NA (95.6%) and in vitro slow sustained release up to 24 h. Whereas, the entrapment efficiency of the CMC/Ch to nicotinic acid was reached 85.6%, and it possessed highly initial burst release followed by a slower release up to 24 h. At pH 7.4 (simulated intestinal fluid) both hydrogels provided higher level of releasing profile to NA than pH 2.1 (gastric fluid). The NA release from hydrogels followed Fickian and non-Fickian diffusion mechanism according to pH 7.4 and 2.1, respectively. It is interesting to note that, the data obtained are higher than those obtained from literature reported hydrogel, e.g., poly (2-hydroxyethyl methacrylate). Neutral red uptake and lactate dehydrogenase assays confirmed both hydrogels have good biocompatibility and could be used as nontoxic drug delivery system. So, we recommended SC/Ch hydrogel as an effective controlled niacin drug delivery system with reducing systemic side effects and improved intestinal targeting efficiency.

Role of pulping process as synergistic treatment on performance of agro-based activated carbons.

To recommend the beneficial effect of the pulping process on enhancing agro-wastes as precursors for the production of high-performance activated carbons (ACs), different pulping methods (alkali, sulfite and neutral sulfite) were applied on two available Egyptian agriculture by-products (rice straw and sugar cane bagasse), using the one-step pyrolysis method and H3PO4 activating agent. The adsorption performance of the different prepared ACs was evaluated in terms of Iodine Numbers and their sorption properties for removing the methylene blue (MB) from aqueous solutions. The corresponding sorption processes were also analysed using Lagergren first order, pseudo-second order and intraparticle diffusion models. Data revealed that the applied pulping conditions were effective for removing the non-cellulosic constituents of agro-residues. This was demonstrated by the hydrogen/carbon and oxygen/carbon ratios, thermal stability and IR-measurements of the final pulps. These data were effective on the particular sorption properties of RS and SCB-based ACs. Interestingly, the pulping process is a profound modification of the SCB-based fibres, on which it induced a clear increase of the specific surface areas of the corresponding ACs even though they had an impact on the sorption of MB and iodine. These values are superior to the reported data on agro-based ACs with H3PO4 activators. Pulping processes therefore play a dual role in the sorption properties of ACs. The first important role is the impact on the specific surface areas and the second impact is a profound modification of the surface chemistry of the ACs. Therefore, SCB-based ACs can be seen as an economical breakthrough product, and an alternative to the high-cost commercial ACs for the purification of industrial wastewaters.

Electiveness of agro-pulping process in the sustainable production of black liquor-based activated carbons.

During the production of paper pulp, the waste water loaded with organic materials from pulping process is discharged. Therefore, water treatment should be performed before disposing of such effluent. The use of such effluent for production of activated carbon will be effective in omitting the wastewater treatment and in obtaining the product required in many industries. In this respect, this paper deals with evaluating the performance of activated carbons (ACs) produced from black liquors (BLs) as by-products from three pulping processes of rice straw (RS) and sugar-cane bagasse (SCB), namely: alkaline, sulfite and neutral sulfite, which are coded SP, SSP and NSP, respectively. Elemental analysis and thermal analysis (TGA and DTGA) are carried out on the BLs, while the surface area (S BET), micro-/mesoporous distribution, adsorption capacity of methylene blue (MB) and iodine (I2-value), as well as Fourier transform infrared spectra (FT-IR) and scanning electron micrograph (SEM) are studied on synthesizing ACs. The optimal pulping approach for achieving BL-based AC, with the following characteristics: specific surface area (S BET) ∼ 921 and 545 m2 g-1, MB adsorption capacity 238 and 370 mg g-1, and I2-value 928 and 1255 mg g-1 of BL-based ACs, are from neutral sulfite pulping of SCB (B-NSP) and RS (RS-NSP), respectively. These finding data are ascribed to the carbon content of BL, as well as greatest total volume (VT 0.786 and 0.701 cm3 g-1) together with decreasing the volume of micropores/total (38 and 48%) of BL-NSP-ACs. It is interesting to note that the AC provided from RS-NSP has greater adsorption capacity for I2 and MB than the AC produced from RS-pulp fibres.