No abstract

Oxidation of cellulose with periodate under aqueous conditions yields dialdehyde cellulose, a promising functional cellulose derivative. The main obstacles for this oxidation have been its slow kinetics and the dilute reaction conditions, requiring considerable amounts of water and energy. In this study, these drawbacks are overcome by conducting the oxidation at high cellulosic pulp consistency with a cellulose/water weight ratio of 1:4. The oxidizer, cellulose, and water are efficiently mixed in a ball mill. Oxidation occurs mostly in the subsequent step, during the resting time (no further milling/mixing is required). The reaction and resource efficiency of the process are optimized by experimental design and a maximum aldehyde content of 8 mmol g−1 is obtained with a periodate/cellulose molar ratio of 1.25, a milling time of 2 min, and a resting time of 8 h. The developed method allows fine tuning of the oxidation level and is a key step towards the sustainable periodate oxidation of cellulose also on larger scale.

Cellulose derivatives have many potential applications in the field of biomaterials and composites, in addition to several ways of modification leading to them. Silanization in aqueous media is one of the most promising routes to create multipurpose and organic–inorganic hybrid materials. Silanization has been widely used for cellulosic and nano-structured celluloses, but was a problem so far if to be applied to the common cellulose derivative “dialdehyde cellulose” (DAC), i.e., highly periodate-oxidized celluloses. In this work, a straightforward silanization protocol for dialdehyde cellulose is proposed, which can be readily modified with (3-aminopropyl)triethoxysilane. After thermal treatment and freeze-drying, the resulting product showed condensation and cross-linking, which was studied with infrared spectroscopy and 13C and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. The cross-linking involves both links of the hydroxyl group of the oxidized cellulose with the silanol groups (Si-O-C) and imine-type bonds between the amino group and keto functions of the DAC (-HC=N-). The modification was achieved in aqueous medium under mild reaction conditions. Different treatments cause different levels of hydrolysis of the organosilane compound, which resulted in diverse condensed silica networks in the modified dialdehyde cellulose structure.

Localized strained silicon was observed with a suitable resolution in a real semiconductor device\ud by tip-enhanced Raman spectroscopy (TERS). The device was made via a standard industrial process\ud and its silicon trench isolation structures were used for the silicon strain analysis obtaining\ud results according to finite element method-based simulation data. We have achieved a reliable and\ud repeatable enhancement factor obtaining a trace of strained silicon along the structure with suitable\ud nanometer spatial resolution compatible with IC industry requirements. We demonstrate that the\ud complexity to analyze a real 3D structure, directly from the production lines and not ad hoc realized,\ud entails the challenges to individuate the optimal tip shape, tip contact angle, tip composition,\ud tip positioning system, laser power, and wavelength to achieve an appropriate plasmon resonance\ud inducing a relevant signal to noise ratio. This work gives the base to address the development in\ud TERS optimization for real industrial applications