Morphological investigation of polylactide/microfibrillated cellulose composites

Optical microscopy and transmission electron microscopy have been used to investigate the morphology of polylactide (PLA)/microfibrillated cellulose (MFC) composites prepared by: compression molding of wet-comingled MFC and PLA latex or powder, twin-screw extrusion of the wet-comingled compounds, and solvent mixing of PLA with MFC or acetylated MFC. Compression molding of wet-comingled MFC and PLA latex or powder compounds resulted in a cellular MFC network, whereas solvent-cast films showed a more uniform dispersion of MFC fibers. Somewhat lower aggregate diameters observed in the acetylated MFC were assumed to be due to decreased MFC hydrophilicity and improved chemical affinity with the PLA matrix. The MFC networks in the commingled compounds were severely disrupted after twin-screw extrusion. This confirmed the limited deformability of the networks inferred from the extensive syneresis during the initial compression molding step, and accounted for substantial losses in stiffness reinforcement by the MFC after extrusion.     

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates. II. Evaluation of leachate treatment efficiency of different steps in a constructed pilot plant

Different methods for treatment of leachate from a municipal solid waste (MSW) landfill were tested in a pilot plant. Raw leachate was pre-treated with aeration and sedimentation, followed by several parallel individual steps such as bioremediation, chemical oxidation, ozonation, and geo-bed filters. The efficiency of different treatment steps was evaluated according to one previously developed protocol, which includes measurements of several parameters such as conductivity, pH, nutrients, chloride, metals, organic compounds, and acute toxicity before and after a treatment step. The treatment steps which showed the highest efficiency towards organic pollutants in leachate were ozone treatment and chemical oxidation. The use of an adsorption filter, a geo-bed with a mixture of peat and bottom ash with ca 10% remaining carbon, also had good effects. A combination of pre-treatment and a geo-bed filter with peat and carbon ash gave the best overall treatment results when water-quality parameters such as total organic carbon and ammonia-nitrogen were also considered.     

Adamantyl Side Chains as Anti-Aggregating Moieties in Dyes for Dye-Sensitized Solar Cells

Designing and evaluating novel dye concepts is crucial for the development of the field of dye-sensitized solar cells (DSSCs). In our recent report, the novel concept of tethering the anti-aggregation additive chenodeoxycholic acid (CDCA) to dyes for DSSC was introduced. Based on the performance improvements seen for this modification, the aim of this study is to see if a simplified anti-aggregation unit could achieve similar results. The following study reports the synthesis and photovoltaic characterization of two novel dyes decorated with the steric ethyladamantyl moiety on the π-spacer, and on the triarylamine donor. This modification is demonstrated to be successful in increasing the photovoltages in devices employing copper-based electrolytes compared to the non-modified reference dye. The best photovoltaic performance is achieved by a device prepared with the adamantyl decorated donor dye and CDCA, this device achieves a power conversion efficiency of 6.1 % (Short-circuit current=8.3 mA cm⁻², Open-circuit voltage=1054 mV, Fill factor=0.69). The improved photovoltaic performance seen for the adamantyl decorated donor demonstrate the potential of ethyladamantyl side chains as a tool to ensure surface protection of TiO₂.     

Long-Term,Single-Molecule Imaging of Proteins in Live Cells with Photoregulated Fluxional Fluorophores

Single-molecule localization microscopy (SMLM) can reveal nanometric details of biological samples, but its high phototoxicity hampers long-term imaging in live specimens. A significant part of this phototoxicity stems from repeated irradiations that are necessary for controlled switching of fluorophores to maintain the sparse labeling of the sample. Lower phototoxicity can be obtained using fluorophores that blink spontaneously, but controlling the density of single-molecule emitters is challenging. We recently developed photoregulated fluxional fluorophores (PFFs) that combine the benefits of spontaneously blinking dyes with photocontrol of emitter density. These dyes, however, were limited to imaging acidic organelles in live cells. Herein, we report a systematic study of PFFs that culminates in probes that are functional at physiological pH and operate at longer wavelengths than their predecessors. Moreover, these probes are compatible with HaloTag labeling, thus enabling timelapse, single-molecule imaging of specific protein targets for exceptionally long times.     

Investigating the Disordered and Membrane-Active Peptide A-Cage-C Using Conformational Ensembles

The driving forces and conformational pathways leading to amphitropic protein-membrane binding and in some cases also to protein misfolding and aggregation is the subject of intensive research. In this study, a chimeric polypeptide, A-Cage-C, derived from α-Lactalbumin is investigated with the aim of elucidating conformational changes promoting interaction with bilayers. From previous studies, it is known that A-Cage-C causes membrane leakages associated with the sporadic formation of amorphous aggregates on solid-supported bilayers. Here we express and purify double-labelled A-Cage-C and prepare partially deuterated bicelles as a membrane mimicking system. We investigate A-Cage-C in the presence and absence of these bicelles at non-binding (pH 7.0) and binding (pH 4.5) conditions. Using in silico analyses, NMR, conformational clustering, and Molecular Dynamics, we provide tentative insights into the conformations of bound and unbound A-Cage-C. The conformation of each state is dynamic and samples a large amount of overlapping conformational space. We identify one of the clusters as likely representing the binding conformation and conclude tentatively that the unfolding around the central W23 segment and its reorientation may be necessary for full intercalation at binding conditions (pH 4.5). We also see evidence for an overall elongation of A-Cage-C in the presence of model bilayers.     

Classification of Graeco‐Latin Cubes

A q‐ary code of length n, size M, and minimum distance d is called an code. An code with is said to be maximum distance separable (MDS). Here one‐error‐correcting () MDS codes are classified for small alphabets. In particular, it is shown that there are unique (5, 5³, 3)₅ and (5, 7³, 3)₇ codes and equivalence classes of (5, 8³, 3)₈ codes. The codes are equivalent to certain pairs of mutually orthogonal Latin cubes of order q, called Graeco‐Latin cubes.     

Determination of conditional stability constants for some divalent transition metal ion‐EDTA complexes by electrospray ionization mass spectrometry

Conditional stability constants of coordination complexes comprising divalent transition metals, Cu²⁺, Ni²⁺, Zn²⁺, Co²⁺, and ethylenediaminetetraacetic acid (EDTA) were determined utilizing electrospray ionization mass spectrometry. The deviation of signal response of a reference complex was monitored at addition of a second metal ion. The conditional stability constant for the competing metal was then determined through solution equilibria equations. The method showed to be applicable to a system where Co²⁺ and Zn²⁺ competed for EDTA at pH 5. When Cu²⁺ and Ni²⁺ competed for EDTA, the equilibrium changed over time. This change was shown to be affected in rate and size by the type of organic solvent added. In this work, 30% of either methanol or acetonitrile was used. It was found that if calibration curves are prepared for both metal complexes in solution and the measurements are repeated with sufficient time space, any change in equilibrium of sample solutions will be discovered. Copyright © 2014 John Wiley & Sons, Ltd.     

Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics

A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe₂, CF₃, CO₂Me, CN, NO₂, ?C?C‐(p‐C₆H₄?NHex₂), ?C?C?(p‐C₆H₄?CO₂Oct)) at [RhX(PMe₃)₄] ( 1 ) (X=?C?C?SiMe₃ ( a ), ?C?C‐(p‐C₆H₄?NMe₂) ( b ), ?C?C?C?C?(p‐C₆H₄?NPh₂) ( c ) or ?C?C?{p‐C₆H₄‐C?C?(p‐C₆H₄‐N(C₆H₁₃)₂)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S₁ state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (Φ_ISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T₁ state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated.     

The effect of Fenton chemistry on the properties of microfibrillated cellulose

A fully bleached birch kraft pulp was treated with acidic hydrogen peroxide in the presence of ferrous ions (Fenton’s reagent) and thereafter treated mechanically in a colloid mill to produce a product containing microfibrillated cellulose (MFC). The produced MFC products were chemically and morphologically characterized and compared with MFC products produced without pretreatment as well as with enzymatic hydrolysis. Fenton treatment resulted in an increase in total charge and number of carbonyl groups while the intrinsic viscosity decreased. The Fenton treated pulps were easier to process mechanically i.e. they reached a higher specific surface area at a given mechanical treatment time and the MFC produced had a stable water-fibre suspension for at least 8 weeks compared to enzymatic pretreated pulps and pulps not subjected to any pretreatment.     

New insights into the mechanisms behind the strengthening of lignocellulosic fibrous networks with polyamines

Polyelectrolytes have been used extensively in the papermaking industry for various purposes. Although recent studies have shown that polyamines can be efficient dry-strength additives, the mechanism governing the strength enhancement of paper materials following the adsorption of polyamines onto pulp fibres is still not well understood. In this study, the effect of the adsorption of polyallylamine hydrochloride (PAH) onto the surface of unbleached kraft pulp fibres was investigated on both the fibre and the network scale. Isolated fibre crosses were mechanically tested to evaluate the impact of the chemical additive on the interfibre joint strength on the microscopic scale and the effect was compared with that previously observed on the paper sheet scale. X-ray microtomography was used to understand structural changes in the fibrous network following the adsorption of a polyamine such as PAH. Using image analysis methods, it was possible to determine the number of interfibre contacts (or joints) per unit length of fibre as well as the average interfibre joint contact area. The results showed that the median interfibre joint strength increased by 18 % upon adsorption of PAH. This can be achieved both by a larger molecular contact area in the contact zones and by a stronger molecular adhesion. The addition of the polymer also increased the number of efficient interfibre contacts per sheet volume. This combination of effects is the reason why polyamines such as PAH can increase the dry tensile strength of paper materials.