Mercerized cellulose biocomposites: a study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties

In this study the effect of the mercerization degree on the water retention value (WRV) and tensile properties of compression molded sulphite dissolving pulp was evaluated. The pulp was treated with 9, 10, or 11 % aqueous NaOH solution for 1 h before compression molding. To study the time dependence of mercerization the pulp was treated with 12 wt% aqueous NaOH for 1, 6 or 48 h. The cellulose I and II contents of the biocomposites were determined by solid state cross polarization/magic angle spinning carbon 13 nuclear magnetic resonance (CP/MAS ¹³C NMR) spectroscopy. By spectral fitting of the C6 and C1 region the cellulose I and II content, respectively, could be determined. Mercerization decreased the total crystallinity (sum of cellulose I and cellulose II content) and it was not possible to convert all cellulose I to cellulose II in the NaOH range investigated. Neither increased the conversion significantly with 12 wt% NaOH at longer treatment times. The slowdown of the cellulose I conversion was suggested as being the result from the formation of cellulose II as a consequence of coalescence of anti-parallel surfaces of neighboring fibrils (Blackwell et al. in Tappi 61:71–72, 1978; Revol and Goring in J Appl Polym Sci 26:1275–1282, 1981; Okano and Sarko in J Appl Polym Sci 30:325–332, 1985). Compression molding of the partially mercerized dissolving pulps yielded biocomposites with tensile properties that could be correlated to the decrease in cellulose I content in the pulps. Mercerization introduces cellulose II and disordered cellulose and lowered the total crystallinity reflected as higher water sensitivity (higher WRV values) and poorer stiffness of the mercerized biocomposites.     

High-resolution in vivo imaging of blood vessels without labeling

We demonstrate that both oxyhemoglobin and deoxyhemoglobin have sequential two-color, two-photon absorption properties that can serve as endogenous contrasts in microvasculature imaging. Using a sensitive modulation transfer technique, we are able to image hemoglobin in red blood cells with micrometer resolution, both in vitro and in vivo. We show that excellent contrast from hemoglobin without any labeling can be obtained in tissue.     

Topochemical acetylation of cellulose nanopaper structures for biocomposites: mechanisms for reduced water vapour sorption

Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m²/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS ¹³C-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.     

A Tandem In Situ Peptide Cyclization through Trifluoroacetic Acid Cleavage

We present a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions. Our approach involves simultaneous in situ deprotection, cyclization and trifluoroacetic acid (TFA) cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N‐terminus. The reaction proceeds via a highly active succinimide intermediate, which was isolated and characterized. The structure of a model cyclic peptide was solved by NMR spectroscopy. Theoretical calculations support the proposed mechanism of cyclization. Our new methodology is applicable for the formation of macrocycles in solid‐phase synthesis of peptides and organic molecules.     

Polysaccharide‐Based Oleogels Prepared with an Emulsion‐Templated Approach

The preparation and characterization of oleogels structured by using a combination of a surface‐active and a non‐surface‐active polysaccharide through an emulsion‐templated approach is reported. Specifically, the oleogels were prepared by first formulating a concentrated oil‐in‐water emulsion, stabilized with a combination of cellulose derivatives and xanthan gum, followed by the selective evaporation of the continuous water phase to drive the network formation, resulting in an oleogel with a unique microstructure and interesting rheological properties, including a high gel strength, G′>4000 Pa, shear sensitivity, good thixotropic recovery, and good thermostability.     

Supralinearity in nuclear research emulsions

Nuclear emulsions processed in discriminating developers, intended to suppress small latent image sites, exhibit supralinear sensitometric blackness-exposure curves, whose character varies according to developing time, concentration, and composition, yielding hittedness ranging from 1 to 8, singly and in combination. These emulsion-processing combinations display the phenomena called ion-kill (sensitization by the transit of a single charged particle) and gamma- kill (sensitization by the overlap of secondary electron paths, whether from x-rays or from the delta-rays of heavy ions) in radiobiology. Here emulsions are blackened by x-rays when these same plates reveal no electron tracks, or no alpha-particle tracks, or even no fission fragment tracks. The supralinearity of the emulsion response to x-rays, and the consequent suppression of low LET radiations suggest that these materials have the potential to mimic the response of biological systems to particulate radiations of different charge and speed.     

High water‐content thermoresponsive hydrogels via electrostatic macrocrosslinking of cellulose nanofibrils

Atom transfer radical polymerization (ATRP) has been utilized to synthesize tri‐ and star‐block copolymers of poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) and quaternized poly(2‐(dimethylamino)ethyl methacrylate) (qPDMAEMA). The block copolymers, all with a minimum of two cationically charged blocks, were sequentially used for electrostatic macrocrosslinking of a dilute dispersion of anionic TEMPO‐oxidized cellulose nanofibrils (CNF, 0.3 wt%), forming free‐standing hydrogels. The cationic block copolymers adsorbed irreversibly to the CNF, enabling the formation of ionically crosslinked hydrogels, with a storage modulus of up to 2.9 kPa. The ability of the block copolymers to adsorb to CNF was confirmed by quartz crystal microbalance with dissipation monitoring (QCM‐D) and infrared spectroscopy (FT‐IR), and the thermoresponsive properties of the hydrogels were investigated by rheological stress and frequency sweep, and gravimetric measurements. This method was shown to be promising for the facile production of thermoresponsive hydrogels based on CNF. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3415–3424     

Effects of feedback from collimating, focusing, and spot-array generating outcoupler gratings in surface-emitting semiconductor lasers

We experimentally demonstrate that a grating outcoupler used for complex beam shaping (spot-array generation) can produce unintentional optical feedback that severely disturbs the integrated in-plane laser that illuminates the coupler. Simulations show that these outcouplers, in contrast to conventional collimating or focusing outcouplers, tend to produce high levels of feedback in spite of the detuning used to suppress feedback. Further, this feedback is focused to high intensity in the laser gain medium. This focused light acts as a seed for the nonlinear self-focusing that causes wave-front distortion and filamentation, which degrades the beam quality.     

Single-frequency operation of a high-power, long-wavelength semiconductor disk laser

An optically pumped, high-power, single-frequency semiconductor disk laser is demonstrated. A thin (50 microm) diamond bonded to an InGaAsP gain chip provides the combined functions of heat removal and spectral filtering, thus eliminating the need for the additional intracavity etalons that are usually employed for single-frequency operation. In a short cavity (4 mm) configuration we obtained a maximum output power of 470 mW at 0 degrees C and 170 mW at 20 degrees C in a near-diffraction-limited beam (M2 < 1.2). The emission wave-length was 1549 nm and the linewidth was less than 200 MHz.