Fibril Width Research Articles

An Optimized Fibril Network Morphology Enables High-Efficiency and Ambient-Stable Polymer Solar Cells.

Morphological stability is crucially important for the long‐term stability of polymer solar cells (PSCs). Many high‐efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene‐4,8‐dione (T1‐Cl) via a random copolymerization approach. It is found that all the copolymers can self‐assemble into a fibril nanostructure in films. By altering the T1‐Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT‐4F, O‐INIC3, EH‐INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high‐efficiency and ambient‐stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.

Facile preparation of nanochitins via acid assisted colloid milling in glycerol

A facile route was developed for the production of nanochitins. Acid-assisted glycerol swelling at 120 °C and low-intensity colloid milling were found to be sufficient for the successful nanofibrillation of purified chitin. The glycerol together with a small amount of sulfuric acid was employed to break the hydrogen bonds between the chitin fibrils, and then the excessively swelled chitin bundles were easily disassembled to the nanoscale through mechanical disintegrations. Despite their good dispersibility in glycerol, the prepared nanochitins were also well-dispersed in acidic and neutral aqueous solutions. Optimal reaction conditions such as the amount of sulfuric acid and processing time for colloid milling were determined to be 0.64% w/w sulfuric acid (based on the whole reaction system) and 2 h, respectively. Under the optimal conditions, nanochitins with a fibril width of less than 50 nm and length of several microns were obtained with high yield (approximately 85%).

Effect of Fibril Length on the Ice Recrystallization Inhibition Activity of Nanocelluloses

Ice recrystallization inhibition (IRI) activity has been recently discovered on nanocelluloses, which enables potential applications in several fields. This study focused on the effect of fibril length on the IRI activity of nanocelluloses. The 2, 2, 6, 6-tetramethylpiperidine-1-oxyl oxidized cellulose nanofibrils (TEMPO-CNFs) with similar surface charge densities (SCDs) and fibril widths, but with different fibril lengths were prepared by sonication treatment. The IRI activity of nanocelluloses was enhanced in TEMPO-CNFs receiving sonication less than 30 min because of the reduction of fibril aggregation. Further increase of sonication time to 60 and 120 min led to a decreased IRI activity due to the reduction of fibril lengths. Our results indicate longer nanocelluloses are more IRI active. The IRI activity was not correlated with the viscosity or gelling properties of nanocellulose dispersions. Research findings are useful in producing nanocelluloses with enhanced IRI activity and in understanding the underlying IRI mechanism.

Controlling the Microstructure of Conjugated Polymers in High‐Mobility Monolayer Transistors via the Dissolution Temperature

AbstractIt remains a challenge to precisely tailor the morphology of polymer monolayers to control charge transport. Herein, the effect of the dissolution temperature (Tdis) is investigated as a powerful strategy for morphology control. Low Tdis values cause extended polymer aggregation in solution and induce larger nanofibrils in a monolayer network with more pronounced π–π stacking. The field‐effect mobility of the corresponding monolayer transistors is significantly enhanced by a factor of four compared to devices obtained from high Tdis with a value approaching 1 cm2 V−1 s−1. Besides that, the solution kinetics reveal a higher growth rate of aggregates at low Tdis, and filtration experiments further confirm that the dependence of the fibril width in monolayers on Tdis is consistent with the aggregate size in solution. The generalizability of the Tdis effect on polymer aggregation is demonstrated using three other conjugated polymer systems. These results open new avenues for the precise control of polymer aggregation for high‐mobility monolayer transistors.

Controlling the Microstructure of Conjugated Polymers in High-Mobility Monolayer Transistors via the Dissolution Temperature.

It remains a challenge to precisely tailor the morphology of polymer monolayers to control charge transport. Herein, the effect of the dissolution temperature (T dis) is investigated as a powerful strategy for morphology control. Low T dis values cause extended polymer aggregation in solution and induce larger nanofibrils in a monolayer network with more pronounced π–π stacking. The field‐effect mobility of the corresponding monolayer transistors is significantly enhanced by a factor of four compared to devices obtained from high T dis with a value approaching 1 cm2 V−1 s−1. Besides that, the solution kinetics reveal a higher growth rate of aggregates at low T dis, and filtration experiments further confirm that the dependence of the fibril width in monolayers on T dis is consistent with the aggregate size in solution. The generalizability of the T dis effect on polymer aggregation is demonstrated using three other conjugated polymer systems. These results open new avenues for the precise control of polymer aggregation for high‐mobility monolayer transistors.

Coupling Nanofibril Lateral Size and Residual Lignin to Tailor the Properties of Lignocellulose Films

AbstractLignocellulosic nanofibrils (LCNF) are produced from a single source of unbleached, oxidized wood fibers by serial disintegration, high‐pressure microfluidization, and homogenization. Sequential centrifugation enables fractionation by fibril width (≈5, ≈9, and ≈18 nm). LCNF residual lignin of high molecular mass reports together with the finest fraction (LCNF‐fine), whereas the more strongly cellulose‐bound lignin, of relatively lower molecular mass, associates with the coarsest fraction (LCNF‐coarse). Hot pressing softens the amorphous lignin, which fills the interstices between fibrils and acts as an in‐built interfacial cross‐linker. Thus, going from the LCNF‐fine to the LCNF‐course films, it is possible to obtain a range of values for the structural consolidation (density from 0.9 to 1.2 g cm−3 and porosity from 19% to 40%), surface roughness (RMS from ≈6 to 13 nm), and strength (elastic modulus from 8 to ≈12 GPa). The concentration of free hydroxyl groups controls effectively the direct surface interactions with liquids. The apparent surface energy dispersive component tracks with the total surface free energy and appears to be strongly influenced by the higher porosity as the fibril lateral size increases. The results demonstrate the possibility to tailor nanofibril cross‐linking and associated optical and thermo‐mechanical performance of LCNF films.

Rheology of microfibrillated cellulose (MFC) suspensions: influence of the degree of fibrillation and residual fibre content on flow and viscoelastic properties

The influence of the degree of fibrillation (DoF), i.e. the fibril width distribution, on the rheological properties of microfibrilated cellulose (MFC) suspensions was investigated. To extend the understanding of the dominating effect of either fibril diameter alone or diameter size distribution, flow curves (viscosity against shear rate) and viscoelastic measurements were performed on single, double and ternary component mixtures of medium and highly fibrillated MFCs and pulp fibres across a range of solids content. The data were quantified using classical and recently introduced descriptors, and presented in comprehensive 3D/ternary contour plots to identify qualitative trends. It was found that several rheological properties followed the trends that are generally described in the literature, i.e. that an increasing DoF increases the MFC suspension network strength. It was, however, also found that coarse pulp fibres can have additional effects that cannot be explained by the increased fibril widths alone. It is hypothesised that the increased stiffness (directly caused by the larger fibril width) as well as the reduced mobility of the pulp fibres are additional contributors. The data are discussed in relation to recent findings in the field of rheology and related morphological models of MFC suspension flow behaviour.

The Impact of Device Polarity on the Performance of Polymer–Fullerene Solar Cells

AbstractDiketopyrrolopyrrole (DPP)‐conjugated polymers are a versatile class of semiconductors for application in organic solar cells because of their tunable optoelectronic properties. A record power conversion efficiency (PCE) of 9.4% was recently achieved for DPP polymers, but further improvements are required to reach true efficiency limits. Using five DPP polymers with different chemical structures and molecular weights, the device performance of polymer:fullerene solar cells is systematically optimized by considering device polarity, morphology, and light absorption. The polymer solubility is found to have a significant effect on the optimal device polarity. Soluble polymers show a 10–25% increase in PCE in inverted device configurations, while the device performance is independent of device polarity for less soluble DPP derivatives. The difference seems related to the polymer to fullerene weight ratio at the ZnO interface in inverted devices, which is higher for more soluble DPP polymers. Optimization of the nature of the cosolvent to narrow the fibril width of polymers in the blends toward the exciton diffusion length enhances charge generation. Additionally, the use of a retroreflective foil increases absorption of light. Combined, the effects afford a PCE of 9.6%, among the highest for DPP‐based polymer solar cells.

Effects of steam explosion on the characteristics of windmill palm fiber and its application to fiberboard

Windmill palm fiber (WPF) obtained from the leaf sheath was treated by steam explosion under the pressure of 2.0 MPa for 120 s to modify and improve the properties of the panels manufactured with it. For comparison, an alkali treatment and acid treatment have also been used to treat WPF. Fiber analysis, scanning electron microscopy (SEM) observation, Fourier transform infrared spectroscopy (FTIR) and chemical composition analysis showed that after the steam explosion treatment: (1) the length, width and fine elements of the windmill palm fibrils were more influenced by the steam explosion treatment than by the other two treatments. (2) A great number of spinulose spherical silica bodies and waxy layers were observed on the surfaces of all the fibers except for the steam explosion treated windmill palm fiber (SEWPF) surfaces, and (3) the cellulose fraction correspondingly increased with the decrease of the hemicelluloses and lignin contents. Finally, the SEWPFs were used to produce fiberboards, and the modulus of rupture (MOR), internal bond (IB), water absorption (WA) and thickness swell (TS) of the fiberboards were measured. The results showed that the WA and TS of the fiberboards made of SEWPF decreased 22 and 32%, respectively, in relation to those made of WPF, whereas the IB increased 46%. It is suggested that steam explosion can be a feasible approach to modify WPF and expand its uses.

Non-destructive determination of collagen fibril width in extruded collagen fibres by piezoresponse force microscopy

Extruded collagen fibres are a promising platform for tissue engineering applications. Ensuring that the functional properties of the engineered tissues possess similar structural properties as native tissues is important for biomedical applications. Advanced imaging tools including scanning electron microscopy (SEM) and atomic force microscopy (AFM) have revealed the structural features of collagen fibrils within such fibres; however, these techniques often require modification steps that can alter the sample in the process. Here, lateral piezoresponse force microscopy (LPFM), which is sensitive to the polar orientation of piezoelectric collagen fibrils, is demonstrated as a promising tool to assess the width of individual fibrils and moreover map their organisation and polar orientation without altering the sample. Within the fibres studied, the collagen fibrils showed a highly anisotropic arrangement with preferred alignment along the length of the fibre. Fibril widths of 74 ± 18 nm and 73 ± 19 nm in untreated and bleached fibres, respectively, were measured from LPFM amplitude images. These values agreed with values from SEM (70 ± 10 nm) and AFM (71 ± 19 nm) measurements that could only be obtained from bleached fibres.

Revalorization of selected municipal solid wastes as new precursors of “green” nanocellulose via a novel one-pot isolation system: A source perspective

In the present work, four types of newly chosen municipal solid wastes (Panax ginseng, spent tea residue, waste cotton cloth, and old corrugated cardboard) were studied as the promising sources for nanocellulose, which has efficiently re-engineered the structure of waste products into highly valuable nanocellulose materials. The nanocellulose was produced directly via a facile one-pot oxidative hydrolysis process by using H2O2/Cr(NO3)3 solution as the bleaching agent and hydrolysis medium under acidic condition. The isolated nanocellulose products were well-characterized in terms of chemical composition, product yield, morphological structure and thermal properties. The study has found that the crystallinity index of the obtained nanocellulose products were significantly higher (62.2–83.6%) than that of its starting material due to the successive elimination of lignin, hemicellulose and amorphous regions of cellulose, which were in good agreement with the FTIR analysis. The evidence of the successful production of nanocellulose was given by TEM observation which has revealed the fibril widths were ranging from 15.6 to 46.2nm, with high cellulose content (>90%), depending on the cellulosic origin. The physicochemical properties of processed samples have confirmed that the isolation of high purity nanocellulose materials from different daily spent products is possible. The comparative study can help to provide a deep insight on the possibility of revalorizing the municipal solid wastes into nanocellulose via the simple and versatile one-pot isolation system, which has high potential to be used in commercial applications for sustainable development.

A zinc oxide-modified hydroxyapatite-based cement facilitated new crystalline-stoichiometric and amorphous apatite precipitation on dentine.

To evaluate the remineralization ability of two endodontic sealer cements. Mid-coronal dentine surfaces were subjected to: (i) 37% phosphoric acid (PA) or (ii) 0.5mol L-1 ethylenediaminetetraacetic acid (EDTA) conditioning prior to the application of two experimental hydroxyapatite-based cements, containing sodium hydroxide (calcypatite) or zinc oxide oxiapatite respectively. Samples were stored in simulated body fluid for 24h or 21days. Remineralization of the dentine surfaces were studied by Raman spectroscopy (mapping with K-means cluster and hierarchical cluster analysis) was undertaken. Nanoroughness and collagen fibril width measurements were performed with an atomic force microscopy. ANOVA and Student-Newman-Keuls test were performed (α=0.05). Phosphoric acid+oxiapatite promoted both the highest dentine mineralization (P<0.05) and crystallographic maturity at the dentine surface. Noncrystalline amorphous-like apatites were also formed. Dentine treated with PA+calcypatite attained the roughest surface (P<0.05) with minimal fibril width (P<0.05). Cross-linking of collagen only became greater in the group PA+oxiapatite after 21days. The maximum relative mineral concentration and structure of collagen linked to the amide I and ratio amide III/AGEs was obtained after using PA+calcypatite at 21-days time-point (P<0.05). EDTA produced a lower stoichiometric hydroxyapatite (P<0.05) with decreased maturity, at the expense of carbonate band widening, although it favoured the nucleation of carbonated calcium phosphate. Dentine surfaces treated with PA+oxiapatite attained the highest dentine remineralization with both crystalline-stoichiometric and amorphous apatites, at 21days. EDTA conditioning facilitated amorphous-bulk mineral precipitation. The amorphization was more intense after using oxiapatite and provided an ion-rich environment favouring insitu dentine remineralization.

PH-sensitivity and Conformation Change of the N-terminal Methacrylated Peptide VK20

ABSTRACTN-terminal methacrylation of peptide MAX1, which is capable of conformational changes by variation of the pH, results in a peptide, named VK20. Increasing the reactivity of this terminal group enables further coupling reactions or chemical modifications of the peptide. However, this end group functionalization may influence the ability of conformational changes of VK20, as well as its properties. In this paper, the influence of pH on the transition between random coil and ß-sheet conformation of VK20, including the transition kinetics, were investigated. At pH values of 9 and higher, the kinetics of ß-sheet formation increased for VK20, compared to MAX1. The self-assembly into ß-sheets recognized by the formation of a physically crosslinked gel was furthermore indicated by a significant increase of G’. An increase in pH (from 9 to 9.5) led to a faster gelation of the peptide VK20. Simultaneously, G’ was increased from 460 ± 70 Pa (at pH 9) to 1520 ± 180 Pa (at pH 9.5). At the nanoscale, the gel showed a highly interconnected fibrillary network structure with uniform fibril widths of approximately 3.4 ± 0.5 nm (N=30). The recovery of the peptide conformation back to random coil resulted in the dissolution of the gel, whereby the kinetics of the recovery depended on the pH. Conclusively, the ability of MAX1 to undergo conformational changes was not affected by N-terminal methacrylation whereas the kinetics of pH-sensitive ß-sheet formations has been increased.

Facile cellulose nanofibrils amidation using a ‘one-pot’ approach

We report a ‘one-pot’ synthetic approach for TEMPO (2,2,6,6-tetramethyl-piperidin-1-oxyl) oxidized cellulose nanofibrils (TOCN) surface amidation by coupling up to 70% of superficial carboxylic units in TOCN with long alkyl chain primary amines (dodecylamine and octadecylamine) using TBTU [O-(1H-benzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium tetrafluoroborate] uronium salt as coupling agent. Raw TOCNs were produced from commercial microcrystalline cellulose and have an elongated highly tangled morphology with nanometric diameters and lengths up to several micrometers with a crystallinity of 62%. TOCN´s degree of oxidation was 1.25 mmol –COOH groups/g cellulose. The TOCN-amidated products named TOCN-AMDC12 and TOCN-AMDC18 depending upon to the primary amine used for the synthesis (dodecylamine –C12– for the former and octadecylamine –C18– for the latter), were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy with attenuated total reflectance and X-ray diffraction. After amidation the hydrated gel-like TOCNs become a cream-colored gel insoluble in water and soluble in toluene. IR data indicates formation of an amide bond after the reaction, and FESEM images suggest a slight increase in fibril width as a result of the long-chain amide derivatives grafted onto the TOCN’s surface. Thermal stability and hydrophobicity of the products were determined using thermogravimetrical analysis and contact angle (CA) measurements. The TOCN-amidated products showed improved thermal properties with maximum decomposition temperatures of 347 and 358 °C, for TOCN-AMDC12 and TOCN-AMDC18 respectively, when compared to the raw TOCN (Td 340 °C); and high hydrophobicity with CA of 61° and 67°, respectively. Finally, the proposed method for TOCN amidation has advantages over current amidation approaches in that it is performed in aqueous media, does not require heating and occurs rapidly (2 h).

Review on the Aerogel-Type Oil Sorbents Derived from Nanocellulose

Because of the severe risk of oil pollution and increasing concerns about the sustainability of sorbent materials, there are considerable interests across the world to develop cost-effective, reusable, and environmentally friendly oil sorbents derived from renewable resources. Nanocellulose is a new family of promising cellulosic materials with a cellulose fibril width in the order of nanometer range (i.e., 2–100 nm). As a class of newly developed cellulose aerogels, nanocellulose-derived ones combine intriguing interconnected three-dimensional porous characteristics of aerogel-type materials such as high porosity, large surface area, and low density with fascinating advantages related to naturally occurring nanocellulose: impressive mechanical properties, abundant sources, natural renewability, excellent biodegradability, and ease to surface modification. Therefore, nanocellulose-based aerogels are very ideal “green” oil sorbents after either appropriate hydrophobic modifications or carbonization. This p...

Surfactant-free emulsions stabilized by tempo-oxidized bacterial cellulose

In order to seek a safe, biodegradable, and sustainable solid stabilizer for food, topical and pharmaceutical emulsions, individualized cellulose nanofibers were prepared by oxidizing bacterial cellulose (BC) in a Tempo-mediated system; their ability to stabilize oil/water interface was investigated. Significant amounts of C6 carboxylate groups were selectively formed on each cellulose microfibril surface, so that the hydrophilicity was strengthened, leading to lower contact angles. Meanwhile, both the length and width of fibrils were decreased significantly, by partial cleavage of numerous numbers of inter- and intra-fibrillar hydrogen bonds. Tempo-oxidized BC (TOBC) was more effective than BC in stabilizing oil-water interface, attributing to the much smaller size. Fibril dosage and oxidation degree exerted a great influence on the stability and particle size distribution of emulsion samples. When the fibril dosage was 0.7wt.%, the sample was so stable that it did not experience creaming and coalescence over 8 months. The 2-TOBC coated droplets showed the greatest stability, although both the zeta potential and the electric repulsion were the largest for the 10-TOBC analogue, which was manipulated by the wettability of fibrils. In addition, the stability of samples was analyzed from the viewpoint of particle size distribution. Consequently, fibril size and wettability are two counterbalanced factors influencing the stability of TOBC-stabilized emulsions; a combination of suitable wettability and size imparts TOBC-stabilized emulsion high stability. As a kind of biomass-based particle stabilizer, TOBC showed great potential applications in food, topical and pharmaceutical formulations.

Viscoelastic Properties of Core-Shell-Structured, Hemicellulose-Rich Nanofibrillated Cellulose in Dispersion and Wet-Film States.

We report the viscoelastic properties of core-shell-structured, hemicellulose-rich nanofibrillated cellulose (NFC) in dispersion and wet-film states. The hemicellulose-rich NFC (hemicellulose neutral sugars 23%, carboxylate 0.2 mmol g(-1)), prepared from Japanese persimmons, had a core crystallite thickness of 2.3 nm and unit fibril thickness of 4.2 nm. A carboxylate-rich NFC (hemicellulose neutral sugars 7%, carboxylate 0.9 mmol g(-1)) with crystallite and fibril widths of 2.5 and 3.3 nm, respectively, was used as a reference. The solid-concentration dependencies of the storage moduli of gel-like water dispersions of the hemicellulose-rich NFC were weaker than those of carboxylate-rich NFC, and the dispersions were loosely flocculated even at high salt concentrations and low pH values. The viscoelastic properties of wet NFC films were similar to those of their dispersions; the hemicellulose-rich NFC films were significantly less sensitive to salt concentration and pH and were soft and swollen at high salt concentrations and low pH values.

Real‐Time Photoluminescence Studies of Structure Evolution in Organic Solar Cells

A method to study the structural evolution of organic bulk heterojunctions via real‐time, in‐situ, steady‐state photoluminescence (PL) is presented. In‐situ PL, in combination with real‐time transmission and reflection measurements, allows us to quantitatively describe the progression of intimate mixing during blade coating of two OPV systems: the common model system poly(3‐hexylthiophene‐2,5‐diyl)/phenyl‐C61‐butyric‐acid‐methyl ester (P3HT/PCBM), and the higher power conversion efficiency system 7,7′‐(4,4bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b′]dithiophene‐2,6‐diyl)bis(6‐fluoro‐5‐(5′‐hexyl‐[2,2′‐bithiophen]‐5‐yl)benzo[c][1,2,5]thiadiazaole), p‐DTS(FBTTh2)2/[70]PCBM. Evaluating the time dependence of the PL intensity during drying using a 3D‐random‐walk diffusion model allows for the quantitative determination of the ratio of characteristic domain size to exciton diffusion length during solidification in the presence of the processing additives 1‐chloronaphtalene (CN), 1,8‐octanedithiol (ODT), and 1,8‐diiodooctane (DIO). In both cases, the obtained results are in good agreement with the typically observed fibril widths and grain sizes, for P3HT and p‐DTS(FBTTh2)2, respectively.

Phototriggered fibril-like environments arbitrate cell escapes and migration from endothelial monolayers

Cell detachment and migration from the endothelium occurs during vasculogenesis and also in pathological states. Here, we use a novel approach to trigger single cell release from an endothelial monolayer by in-situ opening of adhesive, fibril-like environment using light-responsive ligands and scanning lasers. Cell escapes from the monolayer were observed on the fibril-like adhesive tracks with 3–15 μm width. The frequency of endothelial cell escapes increased monotonically with the fibril width and with the density of the light-activated adhesive ligand. Interestingly, treatment with VEGF induced cohesiveness within the cell layer, preventing cell leaks. When migrating through the tracks, cells presented body lateral reduction and nuclear deformation imposed by the line width and dependent on myosin contractility. Cell migration mode changed from mesenchymal to amoeboid-like when the adhesive tracks narrowed (≤5 μm). Moreover, cell nucleus was shrunk showing packed DNA on lines narrower than the nuclear dimensions in a mechanisms intimately associated with the stress fibers. This platform allows the detailed study of escapes and migratory transitions of cohesive cells, which are relevant processes in development and during diseases such as organ fibrosis and carcinomas.

Control over fibril width via different solubility additives for diketopyrrolopyrrole-based photovoltaic devices

Control over polymeric bulk heterojunction (BHJ) morphology is one of the key factors in obtaining high-efficiency devices. The domain size influence on device performance is widely considered critical. In this paper, the fibril width of 3,6-bis-(thiophen-2-yl)-N,N′-bis(2-octyl-1-dodecyl)-1,4-dioxo-pyrrolo[3,4-c]pyrrole and thieno[3,2-b]thiophene (PDBT-TT):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) blend thin film was adjusted by different processing additives. By decreasing the solubility of PDBT-TT in different additives, the fibril width can be decreased from 65.7nm to 14.8nm. It is possible that the PDBT-TT seed-crystallite nuclei concentration is higher in the relatively low solubility solvents than that in the relatively high solubility solvents, thus leading to the formation of narrower fibrils. The PDBT-TT/PC71BM narrow fibrillar interpenetrating network structure was beneficial to exciton separation and charge transport processes. As a result, the solar cell with the narrowest fibril width has a higher short circuit current (Jsc) and fill factor (FF), thus achieving optimized device performance from less than 1% to 4.75%.