The contributions of model studies for fundamental understanding of polymer mechanochemistry

The exciting field of polymer mechanochemistry has made great empirical progress in discovering reactions in which a stretching force accelerates scission of strained bonds using single molecule force spectroscopy and ultra-sonication experiments. Understanding why these reactions happen, i.e., the fundamental physical processes that govern coupling of macroscopic motion to chemical reactions, as well as discovering other patterns of mechanochemical reactivity require complementary techniques, which permit a much more detailed characterization of reaction mechanisms and the distribution of force in reacting molecules than are achievable in SMFS or ultrasonication. A molecular force probe allows the specific pattern of molecular strain that is responsible for localized reactions in stretched polymers to be reproduced accurately in non-polymeric substrates using molecular design rather than atomistically intractable collective motions of millions of atoms comprising macroscopic motion. In this review, we highlight the necessary features of a useful molecular force probe and describe their realization in stiff stilbene macrocycles. We describe how studying these macrocycles using classical tools of physical organic chemistry has allowed detailed characterizations of mechanochemical reactivity, explain some of the most unexpected insights enabled by these probes and speculate how they may guide the next stage of mechanochemistry.

Substrate Treatment Evaluation and Their Impact on Printing Results for Wearable Electronics

This paper presents a comparative study on the treatment techniques for flexible polymeric substrates and their impact on the printing results. Substrate treatments are central to optimization of the printing processes and a strict set of requirements are needed to achieve uniform and acceptable printing results. Therefore, this research is highlighting the most significant treatment methods used for fine-tuning the surface properties of different polymeric substrates. Besides the two commonly used treatment techniques of oxygen plasma and ultraviolet ozone, a new method of using surface cleaning liquid is applied for rapid treatment of polymeric substrates. Comparative study is carried out on the basis of cleaning steps required for substrate preparation, processing, robustness as well as on the final printed results on the substrates. All the three treatment techniques with similar processing protocol are applied on a single type of polyimide (PI) substrate. To further validate the applicability and manufacture of practical devices, the liquid cleaning method is also applied on Polyethylene terephthalate substrates for making proof-of-concept wearable temperature sensor. From the study it is concluded that the liquid surface cleaning method is advantageous in terms of easy processing, robustness and producing uniform printing results on diverse polymeric substrates.

Preparation of Composite Materials from Self-Assembled Chitin Nanofibers

Although chitin is a representative abundant polysaccharide, it is mostly unutilized as a material source because of its poor solubility and processability. Certain specific properties, such as biodegradability, biocompatibility, and renewability, make nanofibrillation an efficient approach for providing chitin-based functional nanomaterials. The composition of nanochitins with other polymeric components has been efficiently conducted at the nanoscale to fabricate nanostructured composite materials. Disentanglement of chitin microfibrils in natural sources upon the top-down approach and regeneration from the chitin solutions/gels with appropriate media, such as hexafluoro-2-propanol, LiCl/N, N-dimethylacetamide, and ionic liquids, have, according to the self-assembling bottom-up process, been representatively conducted to fabricate nanochitins. Compared with the former approach, the latter one has emerged only in the last one-and-a-half decade. This short review article presents the preparation of composite materials from the self-assembled chitin nanofibers combined with other polymeric substrates through regenerative processes based on the bottom-up approach.

The Carbon Source Controls the Secretion and Yield of Polysaccharide-Hydrolyzing Enzymes of Basidiomycetes

In the present study, the polysaccharide-hydrolyzing secretomes of Irpex lacteus (Fr.) Fr. (1828) BCC104, Pycnoporus coccineus (Fr.) Bondartsev and Singer (1941) BCC310, and Schizophyllum commune Fr. (1815) BCC632 were analyzed in submerged fermentation conditions to elucidate the effect of chemically and structurally different carbon sources on the expression of cellulases and xylanase. Among polymeric substrates, crystalline cellulose appeared to be the best carbon source providing the highest endoglucanase, total cellulase, and xylanase activities. Mandarin pomace as a growth substrate for S. commune allowed to achieve comparatively high volumetric activities of all target enzymes while wheat straw induced a significant secretion of cellulase and xylanase activities of I. lacteus and P. coccineus. An additive effect on the secretion of cellulases and xylanases by the tested fungi was observed when crystalline cellulose was combined with mandarin pomace. In I. lacteus the cellulase and xylanase production is inducible in the presence of cellulose-rich substrates but is suppressed in the presence of an excess of easily metabolizable carbon source. These enzymes are expressed in a coordinated manner under all conditions studied. It was shown that the substitution of glucose in the inoculum medium with Avicel provides accelerated enzyme production by I. lacteus and higher cellulase and xylanase activities of the fungus. These results add new knowledge to the physiology of basidiomycetes to improve cellulase production.

Preproteins couple the intrinsic dynamics of SecA to its ATPase cycle to translocate via a catch and release mechanism

Protein machines undergo conformational motions to interact with and manipulate polymeric substrates. The Sec translocase promiscuously recognizes, becomes activated and secretes >500 non-folded preprotein clients across bacterial cytoplasmic membranes. Here, we reveal that the intrinsic dynamics of the translocase ATPase, SecA, and of preproteins combine to achieve translocation. SecA possesses an intrinsically dynamic preprotein clamp attached to an equally dynamic ATPase motor. Alternating motor conformations are finely controlled by the γ-phosphate of ATP, while ADP causes motor stalling, independently of clamp motions. Functional preproteins physically bridge these independent dynamics. Their signal peptide promotes clamp closing; their mature domain overcomes the rate limiting ADP release. While repeated ATP cycles shift the motor between unique states, multiple conformationally frustrated prongs in the clamp repeatedly catch and release trapped preprotein segments until translocation completion. This universal mechanism allows any preprotein to promiscuously recognize the translocase, usurp its intrinsic dynamics and become secreted.

The Carbon Source Controls the Secretion and Yield of Polysaccharide-Hydrolyzing Enzymes of Basidiomycetes

In the present study, the polysaccharide-hydrolyzing secretomes of Irpex lacteus BCC104, Pycnoporus coccineus BCC310, and Schizophyllum commune BCC632 were analyzed in submerged fermentation conditions to elucidate the effect of chemically and structurally different carbon sources on the expression of cellulases and xylanase. Among polymeric substrates, crystalline cellulose appeared to be the best carbon source providing the highest endoglucanase, total cellulase, and xylanase activities. Mandarin pomace as a growth substrate for S. commune allowed to achieve comparatively high volumetric activities of all target enzymes while wheat straw induced a significant secretion of cellulase and xylanase activities of I. lacteus and P. coccineus. A synergistic effect on the secretion of cellulases and xylanases by the tested fungi was observed when crystalline cellulose was combined with mandarin pomace. In I. lacteus the cellulase and xylanase production is inducible in the presence of cellulose-rich substrates but is suppressed in the presence of an excess of easily metabolizable carbon source. These enzymes are expressed in a coordinated manner under all conditions studied. It was shown that the substitution of glucose in the inoculum medium with Avicel provides accelerated enzyme production by I. lacteus and higher cellulase and xylanase activities of the fungus. These results add new knowledge to the physiology of basidiomycetes to improve cellulase production.

Insights into Biodegradable Polymer-Supported Titanium Dioxide Photocatalysts for Environmental Remediation

During the past two decades, immobilization of titanium dioxide (TiO2), a well-known photocatalyst, on several polymeric substrates has extensively gained ground since it limits the need of post-treatment separation stages. Taking into account the numerous substrates tested for supporting TiO2 photocatalysts, the use of biodegradable polymer seems a hopeful option owing to its considerable merits, including the flexible nature, low price, chemical inertness, mechanical stability and wide feasibility. The present review places its emphasis on recently published research articles (2011–2021) and exhibits the most innovative studies facilitating the eco-friendly biodegradable polymers to fabricate polymer-based photocatalysts, while the preparation details, photocatalytic performance and reuse of the TiO2/polymer photocatalysts is also debated. The biodegradable polymers examined herein comprise of chitosan (CS), cellulose, alginate, starch, poly(lactid acid) (PLA), polycaprolactone (PCL) and poly(lactide-co-glycolide) (PLGA), while an emphasis on the synthetical pathway (dip-coating, electrospinning, etc.) of the photocatalysts is provided.

Invisible and Flexible Printed Sensors Based on ITO Nanoparticle Ink for Security Applications

Here, we propose a method to create a transparent security system based on printed conductive indium tin oxide (ITO)—the most widely used transparent conducting oxide material integrated into the devices with high transparency. Commonly used solution-processed ITO annealing methods are utilizing temperatures which are limiting the use of flexible polymeric substrates. Our method combines inkjet printing on flexible temperature-stable colorless polyimide (CPI) substrate with fast flash lamp annealing (FLA). In this study, millisecond pulses of visible light from a xenon lamp induce rapid heating of the ITO films up to 650°C through the light-absorbing additional layer of a colored organic dye onto printed ITO, whereas the CPI bulk never exceeds the melting point. Fabricated flexible ITO patterns on CPI film processed with the flash lamp annealing through the dye layer exhibit a transmittance of up to 85% at the wavelength of 550 nm and sheet resistance of 520 Ω/sq for a 70 nm layer thickness. With the proposed technology of our demonstrator realization—transparent glass/window or any other object such as a curved door lock can be used for integrating a touch-enabled transparent security access system, which would be completely invisible.