Microcrystalline Cellulose (MCC) is an isolated, colloidal crystalline portion of cellulose fibers, and it is a valuable alternative to non-renewable fossil-based materials. It is used for a large ...plethora of different fields, such as composites, food applications, pharmaceutical and medical developments, and cosmetic and material industries. The interest of MCC has also been driven by its economic value. In the last decade, particular attention has been driven to the functionalization of its hydroxyl groups to expand the field of applications of such biopolymer. Herein, we report and describe several pre-treatment methods that have been developed to increase the accessibility of MCC by breaking its dense structure allowing further functionalization. This review also collects the results that have appeared in the literature during the last two decades on the utilization of functionalized MCC as adsorbents (dyes, heavy metals, and carbon dioxide), flame retardants, reinforcing agents, energetic materials, such as azide- and azidodeoxy-modified, and nitrate-based cellulose and biomedical applications.
Cover boxes with inspection glass are generally used outdoors for photovoltaic systems. Sometimes these boxes break, during normal use. High temperature, thermal stress, cyclic stress, and cracking ...contribute to weakening the polymeric inspection “glass”. The study presents an interdisciplinary analysis to discover the mode of occurrence and causes of the failure. First, the material is accurately characterized. Then its mechanical behavior is characterized in a virtual scenario that reconstructs the real external environment. The goal is to build a new cover with inspection boxes that exhibits superior life cycle behavior when exposed to harsh weather conditions and atmospheric agents. The breaking phenomena of solar panels covering boxes in PMMA (Poly Methyl Methacrylate) are examined. Environmental stress is the main responsible for cracking. Styrene is employed in the polymerization process of Sheet Molding Compound (SMC); the diffusion of this material is the main responsible for cracking. Comprehensive engineering analysis shows how the thermoplastic component fails after being exposed to atmospheric agents. The PMMA “glass” is one of the polymers most sensible to the crazing phenomena.
SEM micrograph of PMMA composite.
•Salting out agents able to improve HS–SPME of the FFAs from C2 to C10 were evaluated.•A combination of (NH4)2SO4 and NaH2PO4 improves HS–SPME of the FFAs from C2 to C10.•The effect of ...(NH4)2SO4/NaH2PO4 was also assessed on food and biological samples.•Up to 4-fold increases in extraction compared to extraction with NaCl were obtained.
Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace–SPME–gas chromatographic (HS–SPME–GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2–C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl.
Composite anode material based on Fe3O4 and reduced graphene oxide is prepared by base-catalysed co-precipitation and sonochemical dispersion. Structural and morphological characterizations ...demonstrate an effective and homogeneous embedding of Fe3O4 nanoparticles in the carbonaceous matrix. Electrochemical characterization highlights specific capacities higher than 1000 mAh g−1 at 1C, while a capacity of 980 mAhg−1 is retained at 4C, with outstanding cycling stability. These results demonstrate a synergistic effect by nanosize morphology of Fe3O4 and inter-particle conductivity of graphene nanosheets, which also contribute to enhancing the mechanical and cycling stability of the electrode. The outstanding capacity delivered at high rates suggests a possible application of the anode material for high-power systems.
A new dimeric copper(II) bromide complex, Cu(LOHex)Br(μ-Br)2 (1), was prepared by a reaction of CuBr2 with the hexyl bis(pyrazol-1-yl)acetate ligand (LOHex) in acetonitrile solution and fully ...characterized in the solid state and in solution. The crystal structure of 1 was also determined: the complex is interlinked by two bridging bromide ligands and possesses terminal bromide ligands on each copper atom. The two pyrazolyl ligands in 1 coordinate with the nitrogen atoms to complete the Cu coordination sphere, resulting in a five-coordinated geometry—away from idealized trigonal bipyramidal and square pyramidal geometries—which can better be described as distorted square pyramidal, as measured by the τ and χ structural parameters. The pendant hexyloxy chain is disordered over two arrangements, with final site occupancies refined to 0.705 and 0.295. The newly synthesized complex was evaluated as a catalyst in copper-catalyzed C–H oxidation for allylic functionalization through a Kharasch–Sosnovsky reaction without any external reducing agent. Using 0.5 mol% of this catalyst, and tert-butyl peroxybenzoate (Luperox) as an oxidant, allylic benzoates were obtained with up to 90% yield. The general reaction time was only slightly decreased to 24 h but a very significant decrease in the alkene:Luperox ratio to 3:1 was achieved. These factors show relevant improvements with respect to classical Kharasch–Sosnovsky reactions in terms of rate and amount of reagents. The present study highlights the potential of copper(II) complexes containing functionalized bis(pyrazol-1-yl)acetate ligands as efficient catalysts for allylic oxidations.
A poly(urethane-acrylate) polymer (PUA) was synthesized, and a sufficiently high molecular weight starting from urethane-acrylate oligomer (UAO) was obtained. PUA was then loaded with two types of ...powdered ligno-cellulosic waste, namely from licorice root and palm leaf, in amounts of 1, 5 and 10%, and the obtained composites were chemically and mechanically characterized. FTIR analysis of final PUA synthesized used for the composite production confirmed the new bonds formed during the polymerization process. The degradation temperatures of the two types of waste used were in line with what observed in most common natural fibers with an onset at 270 °C for licorice waste, and at 290 °C for palm leaf one. The former was more abundant in cellulose (44% vs. 12% lignin), whilst the latter was richer in lignin (30% vs. 26% cellulose). In the composites, only a limited reduction of degradation temperature was observed for palm leaf waste addition and some dispersion issues are observed for licorice root, leading to fluctuating results. Tensile performance of the composites indicates some reduction with respect to the pure polymer in terms of tensile strength, though stabilizing between data with 5 and 10% filler. In contrast, Shore A hardness of both composites slightly increases with higher filler content, while in stiffness-driven applications licorice-based composites showed potential due to an increase up to 50% compared to neat PUA. In general terms, the fracture surfaces tend to become rougher with filler introduction, which indicates the need for optimizing interfacial adhesion.
Sodium‐ion batteries (SIBs) represent a potential alternative to lithium‐ion batteries in large‐scale energy storage applications. To improve the sustainability of SIBs, the utilization of anode ...carbonaceous materials produced from biomass and the selection of a bio‐based binder allowing an aqueous electrode processing are fundamental. Herein, corncobs are used as raw material for the preparation of hard carbon and it is also used as cellulose sources for the synthesis of carboxymethyl cellulose (CMC) binder. The corncob‐derived electrodes deliver a high discharge capacity of around 264 mAhg−1 at 1 C (300 mAg−1), with promising capacity retention (84 % after 100 cycles) and good rate capability. Additionally, this work expands the fundamental insight of the sodium storage behavior of Hard Carbons through an electrochemical approach, suggesting that the reaction mechanism is controlled by capacitive process in the sloping voltage region, while the diffusion‐controlled intercalation is the predominant process in the low‐voltage plateau.
Hard carbon for sodium‐ion batteries: Corncobs are used for the preparation of bio‐based electrode with hard carbon as active material and carboxymethyl cellulose as binder. The electrodes deliver a high discharge capacity and good rate capability. Additionally, the sodium storage behavior of Hard Carbons was investigated.
Quinoline-2-carboxylates are an important subclass of quinoline derivatives largely present in a variety of biologically active molecules, as well as useful ligands in metal-catalyzed reactions. ...Herein, we present a new one-pot protocol for synthesizing this class of derivatives starting from β-nitroacrylates and 2-aminobenzaldehydes. In order to optimize the protocol, we investigated several reaction conditions, obtaining the best results using the 2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as solid base, in acetonitrile. Finally, we demonstrated the generality of our approach over several substrates which led to synthesize a plethora of functionalized quinolines-2-carboxylate derivatives in good overall yields.
The nitroaldol reaction of ketal-functionalized nitroalkanes with alpha-oxoaldehydes, promoted by Amberlyst A21, followed by acidic treatment (Amberlyst 15) of the obtained nitroalkanol, leads to the ...formation of 2,5-disubstituted furans in good yields. The procedure was successfully applied to the total synthesis of 1-benzyl-3-(5'-hydroxymethyl-2'-furyl)-indazole (YC-1), an important pharmaceutical target.
In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted ...polymers were created using sol-gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents,
packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. Finally, the device was applied to a real urine sample to check the method feasibility on a very complex matrix. The new paraben imprinted SPE sorbents, not yet present in the literature, potentially encourage the development of novel molecularly imprinted polymers (MIPs) to enhance the extraction efficiency, and consequently the overall analytical performances, when the trace quantification is required.
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