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.     

A New Strong-Acid Free Route to Produce Xanthan Gum-PANI Composite Scaffold Supporting Bioelectricity

Conductive hybrid xanthan gum (XG)–polyaniline (PANI) biocomposites forming 3D structures able to mimic electrical biological functions are synthesized by a strong-acid free medium. In situ aniline oxidative chemical polymerizations are performed in XG water dispersions to produce stable XG–PANI pseudoplastic fluids. XG–PANI composites with 3D architectures are obtained by subsequent freeze-drying processes. The morphological investigation highlights the formation of porous structures; UV–vis and Raman spectroscopy characterizations assess the chemical structure of the produced composites. I–V measurements evidence electrical conductivity of the samples, while electrochemical analyses point out their capability to respond to electric stimuli with electron and ion exchanges in physiological-like environment. Trial tests on prostate cancer cells evaluate biocompatibility of the XG–PANI composite. Obtained results demonstrate that a strong acid-free route produces an electrically conductive and electrochemically active XG–PANI polymer composite. The investigation of charge transport and transfer, as well as of biocompatibility properties of composite materials produced in aqueous environments, brings new perspective for exploitation of such materials in biomedical applications. In particular, the developed strategy can be used to realize biomaterials working as scaffolds that require electrical stimulations for inducing cell growth and communication or for biosignals monitoring and analysis.     

Yoichiro Nambu and the Concept of Apparent Vacuum: A Stepping Stone to Spontaneous Symmetry Breaking

The processes of discovery and concept formation are as mysterious as they are intriguing. In this article, they give a sketch of Yoichiro Nambu's long path toward the concept of spontaneous symmetry breaking focusing on the pivotal role played by his notion of “apparent vacuum”. This is instrumental to draw the original analogical correspondence between the vacuum of quantum field theory and solid matter, which, transforming over time in its use and purpose, enables Nambu to arrive at the concept of spontaneous symmetry breaking. From this historical episode they draw a methodological lesson and emphasise the broad cultural influences that conditioned the conceptual development.     

On the determination of the average molecular weight,radius of gyration,and mass/length ratio of polydisperse solutions of polymerizing rod‐like macromolecular monomers by multi‐angle static light scattering

The angular dependence of the light scattered from polydisperse solutions of rod‐like or worm‐like linear polymers formed by the polymerization of rod‐like macromolecular monomers was studied with the aid of computer simulations. Except at very low conversion degrees, these ensembles are characterized by curved Zimm‐like plots. An appraisal of the use of polynomial fittings for the derivation of the weight‐average molecular weight (M_w) and of the z‐average square radius of gyration (<R_g²>_z) from such plots is presented and discussed. Depending on the average size and shape distribution, the use of polynomial fittings allows the applicability of the Zimm method well beyond the standard condition q²<R_g²>_z<<1, q being the scattering wavevector. In addition, the derivation of the w/z‐average mass/length ratio M_L of the polymers from only partially linear Casassa plots, from which large errors in the derived M_L values can be made, is analyzed. By combining the Casassa method with the complementary Holtzer plots, it is usually possible to assess the reliability of the results and give an estimate of their accuracy. However, it was also found that apparently linear Casassa plots, allowing a good estimate of the M_L value, may arise in particular situations even when the Holtzer plot would indicate otherwise.