Toward a reversible consolidation of paper materials using cellulose nanocrystals

An innovative consolidation strategy for degraded paper is presented based on the reversible application of cellulose nanocrystals as sustainable fillers to reinforce mechanical properties and resistance to further degradation. The compatibility and efficacy of the proposed consolidation treatment are assessed first on pure cellulose paper, used as a model, by reliable techniques such as field emission scanning electron microscopy, atomic force microscopy, tensile tests, X-ray powder diffraction, and Fourier transform infrared spectroscopy, evidencing the influence of the surface functionalization of nanocellulose on the consolidation and protection effects. Then, the consolidation technique is applied to real aged paper samples fromBreviarium romanum ad usum Fratrum Minorum S.P.(1738), demonstrating the promising potential of the suggested approach. Amperometric measurements, carried out with a smart electrochemical tool developed in our laboratory, demonstrate the reversibility of the proposed treatment by removal of the nanocrystalline cellulose from the paper surface with a suitable cleaning hydrogel. This completely new feature of the consolidation treatment proposed here satisfies a pivotal requisite in cultural heritage conservation because the methodological requirement for the ″reversibility″ of any conservation measure is a fundamental goal for restorers. A paper artifact, in fact, is subject to a number of natural and man-made hazards, inducing continuous degradation. With time, monitoring and consolidation actions need to be often performed to ensure conservation, and this tends to modify the status quo and compromise the artifact integrity. Removable treatments can potentially avoid erosion of the artifact integrity

Tailoring the chemical structure of cellulose nanocrystals by amine functionalization

The surface functionalization of cellulose nanocrystals is presently considered a useful and straightforward tool for accessing very reliable biocompatible and biodegradable nanostructures with tailored physical and chemical properties. However, to date the fine characterization of the chemical appendages introduced onto cellulose nanocrystals remains a challenge, due to the low sensitivity displayed by the most common techniques towards surface functionalization. In this paper, we demonstrate the easy functionalization of cellulose nanocrystals with aliphatic and aromatic amines, demonstrating the tunability of their properties in dependence on the selected functionality. Then, we apply to colloidal suspensions of modified nanocrystals 1H NMR analysis to elucidate their surface structure. To the best of our knowledge, this is the first report where such investigation was performed on cellulose nanocrystals presenting both surface and reducing end modification. These results involve interesting implications for the fields of cultural heritage and of materials chemistry

Nanocellulose/fullerene hybrid films assembled at the air/water interface as promising functional materials for photo-electrocatalysis

Cellulose nanomaterials have been widely investigated in the last decade, unveiling attractive properties for emerging applications. The ability of sulfated cellulose nanocrystals (CNCs) to guide the supramolecular organization of amphiphilic fullerene derivatives at the air/water interface has been recently highlighted. Here, we further investigated the assembly of Langmuir hybrid films that are based on the electrostatic interaction between cationic fulleropyrrolidines deposited at the air/water interface and anionic CNCs dispersed in the subphase, assessing the influence of additional negatively charged species that are dissolved in the water phase. By means of isotherm acquisition and spectroscopic measurements, we demonstrated that a tetra-sulfonated porphyrin, which was introduced in the subphase as anionic competitor, strongly inhibited the binding of CNCs to the floating fullerene layer. Nevertheless, despite the strong inhibition by anionic molecules, the mutual interaction between fulleropyrrolidines at the interface and the CNCs led to the assembly of robust hybrid films, which could be efficiently transferred onto solid substrates. Interestingly, ITO-electrodes that were modified with five-layer hybrid films exhibited enhanced electrical capacitance and produced anodic photocurrents at 0.4 V vs Ag/AgCl, whose intensity (230 nA/cm2) proved to be four times higher than the one that was observed with the sole fullerene derivative (60 nA/cm2)

Molecular and Supramolecular Architectures of Organic Semiconductors for Field Effect Transistor Devices and Sensors: a Synthetic Chemical Perspective

Organic field-effect transistors (OFETs) are key devices in organic electronics, and their performances largely depend on molecular structure and solid-state organization of the π-conjugated compounds used as semiconductors. This microreview reports several examples of materials for OFET devices and sensors, which have been selected to highlight the basic criteria of molecular design together with the synthetic logic driving the development of organic semiconductors. Versatile synthetic methodologies enable to optimize properties by tailoring molecular structures and functionalization, thus playing a key role in the progress of OFET technology, and more in general of organic electronics, which is emphasized in the discussion

High Yield Synthesis of Cellulose Nanocrystals From Avicel by Mechano-Enzymatic Approach

Cellulose nanocrystals are an important class of bio-based crystalline nanostructures, finding application in several technological fields, including paper and textile coating, biocomposite engineering, biocatalysts immobilization, etc. This study explores enzymatic hydrolysis of Avicel, using endoglucanase from Aspergillus niger, to find an environmentally friendly method to extract cellulose nanocrystals from cellulose sources. Enzymatic hydrolysis has the advantage of reduced energy consumption and higher environmental friendliness compared to acid hydrolysis. In this work, we report for the first time very high nanocrystals yield by combining mechanical pretreatment of the cellulose starting material with a ball miller and endoglucanase hydrolysis, as a result of an extensive optimization of reaction conditions. In particular, a ball milling pretreatment carried out for 50 minutes at 3 Hz, allowed to isolate enzymatic CNCs with 76 % yield and with crystallinity as high as 75 %. The materials were characterized by X-Ray diffractometry, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, dynamic light scattering, zeta potential and field emission scanning electron microscopy (FE-SEM). Their characteristics were compared with the properties of sulfated CNCs, prepared from Avicel by sulfuric acid hydrolysis. Our results are technologically relevant, as they contribute to the accessibility and sustainability of CNCs for a wide range of applications in various industries

Synthesis of electroluminescent conjugated polymers for OLEDs

This chapter discusses the most important synthetic routes to the main classes of electroluminescent -conjugated polymers, highlighting advantages and limitations of the different methods in terms of versatility, stereo- and regioselectivity, efficiency. The discussion covers not only the synthesis of basic classes of polymers such as polyarylenes, poly(arylenevinylene)s, poly(aryleneethynylene)s, but describes routes to systems with more complex structures, including multifunctional copolymers and coordination polymers

Synthesis of electroluminescent conjugated polymers for OLEDs

This chapter discusses the most important synthetic routes to the main classes of electroluminescent -conjugated polymers, highlighting advantages and limitations of the different methods in terms of versatility, stereo- and regioselectivity, efficiency. The discussion covers not only the synthesis of basic classes of polymers such as polyarylenes, poly(arylenevinylene)s, poly(aryleneethynylene)s, but describes routes to systems with more complex structures, including multifunctional copolymers and coordination polymers

Iron-catalyzed cross-coupling reaction of aryl Grignard reagents with bis(2-bromovinyl)benzenes

Fe(acac)3 has been used as the catalyst in cross-coupling reactions of aryl Grignard reagents with 1,4-bis(2- bromovinyl)benzenes affording bis(2-arylvinyl)benzenes. Effects of alkoxy substituents on both reactants and of the temperature on the reaction outcome are investigated

Synthesis of organic semiconductors functionalized with biological molecules

Organic polymeric and molecular semiconductors functionalized with biological molecules represent a very interesting class of materials for highly selective electrical and optical sensors. Molecular design and synthetic approaches to several bio-substituted conjugated oligomers and polymers are discussed, highlighting the impact of synthetic pathways on the properties of the materials