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Despite the consensus on the origin of dialysis-related amyloidosis (DRA) being β 2 -microglobulin (β 2 m) aggregation, the debate on the underlying mechanism persists because of the continuous emergence of β 2 m variant- and pH-dependent contradictory results. By characterizing the native monomeric (initiation) and aggregated fibrillar (termination) states of β 2 m via a combination of two enhanced sampling approaches, we here propose a mechanism that explains the heterogeneous behavior of wild-type (WT) and pathogenic (V27M and D76N) β 2 m variants in physiological and disease-pertinent acidic pH environments. It appears that the higher retainment of monomeric native folds at neutral pH (native-like) distinguishes pathogenic β 2 m mutants from the WT (moderate loss). However, at acidic pH, all three variants behave similarly in producing a substantial amount of partially unfolded states (conformational switch, propensity), though with different extents (WT < V27M < D76N). Whereas at the fibrillar end, all β 2 m variants display a pH-dependent protofilament separation pathway and a higher protofilament binding affinity (stability) at acidic pH, where the relative order of binding affinity (WT < V27M < D76N) remains consistent with pH modulation. Combining these observations, we conclude that β 2 m variants possibly shift from native-like aggregation to conformational switch-initiated fibrillation as the pH is altered from neutral to acidic. The combined propensity-stability approach based on the initiation and termination points of β 2 m aggregation not only assists us in deciphering the mechanism but also emphasizes the protagonistic roles of both terminal points in the overall aggregation process.

The aberrant aggregation of TAR DNA-binding protein 43 kDa (TDP-43) in cells leads to the pathogenesis of multiple fatal neurodegenerative diseases. Decoding the proposed initial transition between its functional dimeric and aggregation-prone monomeric states can potentially design a viable therapeutic strategy, which is presently limited by the lack of structural detail of the full-length TDP-43. To achieve a complete understanding of such a delicate phase space, we employed a multiscale simulation approach that unearths numerous crucial features, broadly summarized in two categories: (1) state-independent features that involve inherent chain collapsibility, rugged polymorphic landscape dictated by the terminal domains, high β-sheet propensity, structural integrity preserved by backbone-based intrachain hydrogen bonds and electrostatic forces, the prominence of the C-terminal domain in the intrachain cross-domain interfaces, and equal participation of hydrophobic and hydrophilic (charged and polar) residues in cross-domain interfaces; and (2) dimerization-modulated characteristics that encompass slower collapsing dynamics, restricted polymorphic landscape, the dominance of side chains in interchain hydrogen bonds, the appearance of the N-terminal domain in the dimer interface, and the prominence of hydrophilic (specifically polar) residues in interchain homo- and cross-domain interfaces. In our work, the ill-known C-terminal domain appears as the most crucial structure-dictating domain, which preferably populates a compact conformation with a high β-sheet propensity in its isolated state stabilized by intrabackbone hydrogen bonds, and these signatures are comparatively faded in its integrated form. Validation of our simulated observables by a complementary spectroscopic approach on multiple counts ensures the robustness of the computationally predicted features of the TDP-43 aggregation landscape.

Aggregation of TDP-43 is linked to the pathogenesis of many neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS). Notably, electrostatic point mutations such as D169G and P112H, located within the highly conserved functional tandem RNA recognition motif (RRM) domains of the TDP-43 protein (TDP-43 tRRM ), have been identified in diseased patients as well. In this study, we address how the electrostatic mutations alter both the native state stability and aggregation propensity of TDP-43 tRRM . The mutants D169G and P112H show increased chemical stability compared to the TDP-43 tRRM at physiological pH. However, at low pH, both the mutants undergo a conformational change to form amyloid-like fibrils, though with variable rates─the P112H mutant being substantially faster than the other two sequences (TDP-43 tRRM and D169G mutant) showing comparable rates. Moreover, among the three sequences, only the P112H mutant undergoes a strong ionic strength-dependent aggregability trend. These observations signify the substantial contribution of the excess charge of the P112H mutant to its unique aggregation process. Complementary simulated observables with atomistic resolution assign the experimentally observed sequence-, pH-, and ionic strength-dependent aggregability pattern to the degree of thermal lability of the mutation site-containing RRM1 domain and its extent of dynamical anticorrelation with the RRM2 domain whose combination eventually dictate the extent of generation of aggregation-prone partially unfolded conformational ensembles. Our choice of a specific charge-modulated pathogenic mutation-based experiment-simulation-combination approach unravels the otherwise hidden residue-wise contribution to the individual steps of this extremely complicated multistep aggregation process.

The transition to a bioeconomy is attracting the use of wood powders for developing bio-based chemicals, fuels, and products to replace fossil-based products. Wood powder-based products depend on the properties and quality of wood powders. Despite many studies on their morphological and physical properties, studies on micromorphology and extractive micro-distribution are scarce. Here we investigated the effect of milling type and wood quality in terms of moisture content on microstructural changes and native extractive distribution in wood powders. The findings showed that non-dried and dried multi-blade shaft mill (MBSM) powders had smooth surfaces and less undamaged cellulosic fibre walls, and extractives were located in the cell lumen. Non-dried and dried hammer mill powders had a rough surface and fibres with structural deformations in their cell walls (e.g. dislocations). Extractives were redistributed on the particle surface as well as dispersed in the cell lumen for both types of hammer mill powders. In a word, the powders obtained from MBSM technology are more native in structure. The findings of the study can have implications for downstream processes., (© 2024. The Author(s).)

Several antiviral therapeutic approaches have been targeted toward the RNA-dependent RNA polymerase (RdRp) complex that is involved in viral genome replication. In SARS-CoV-2, although the RdRp is a multiprotein complex, the focus has been on the ligand binding catalytic core (nonstructural protein nsp12), and not the multiprotein functional dynamics. In this study, we focus on the conformational ensembles of the RdRp complex and their modulation by the presence of RNA, performing comprehensive microsecond-scale atomistic simulations of the apo- and RNA-bound complex. We delineate the differential impact of RNA on the constituent proteins, such as conformational polymorphisms, dominant segment-specific fluctuations, and the switch in dynamical crosstalk within the complex. We distinguish dynamical signatures of nsp7, nsp8, and nsp12 in the apo-state that are reduced in the presence of the RNA and appear to "prime" the complex for activity. Importantly, we identify a unique structural malleability of the nsp8 protein with high conformational heterogeneity in the apo state, especially at three sites (Y71 for nsp8A, and D52 and A66 for nsp8B). Our work highlights the functional implications of the polymorphism of nsp8 structures and reveals possibilities for the development of allosteric inhibitors.

Lignin's antibacterial properties have become increasingly relevant due to the rise of microbial infectious diseases and antibiotic resistance. Lignin is capable of interacting electrostatically with bacteria and contains polyphenols that cause damage to their cell walls. These features make lignin a desirable material to exhibit antibacterial behavior. Therefore, lignin in antibacterial applications offers a novel approach to address the growing need for sustainable and effective antibacterial materials. Recent research has explored the incorporation of lignin in various biomedical applications, such as wound dressings, implants, and drug delivery systems, highlighting their potential as a sustainable alternative to synthetic antibacterial agents. Furthermore, the development of lignin-based nanomaterials with enhanced antimicrobial activity is an active area of research that holds great promise for the future. In this review, we have provided a summary of how lignin can be incorporated into different forms, such as composite and non-composite synthesis of antibacterial agents and their performances. The challenges and future considerations are also discussed in this review article., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

During stemwood harvesting, substantial volumes of logging residues are produced as a side stream. Nevertheless, industrially feasible processing methods supporting their use for other than energy generation purposes are scarce. Thus, the present study focuses on biorefinery processing, employing response surface methodology to optimize the pressurized extraction of industrially assorted needle-rich spruce logging residues with four solvents. Eighteen experimental points, including eight center point replicates, were used to optimize the extraction temperature (40-135 °C) and time (10-70 min). The extraction optimization for water, water with Na 2 CO 3 + NaHSO 3 addition, and aqueous ethanol was performed using yield, total dissolved solids (TDS), antioxidant activity (FRAP, ORAC), antibacterial properties ( E. coli , S. aureus ), total phenolic content (TPC), condensed tannin content, and degree of polymerization. For limonene, evaluated responses were yield, TDS, antioxidant activity (CUPRAC, DPPH), and TPC. Desirability surfaces were created using the responses showing a coefficient of determination ( R 2 ) > 0.7, statistical significance ( p ≤ 0.05), precision > 4, and statistically insignificant lack-of-fit ( p > 0.1). The optimal extraction conditions were 125 °C and 68 min for aqueous ethanol, 120 °C and 10 min for water, 111 °C and 49 min for water with Na 2 CO 3 + NaHSO 3 addition, and 134 °C and 41 min for limonene. The outcomes contribute insights to industrial logging residue utilization for value-added purposes., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The deleterious impact of Helicobacter pylori ( H. pylori ) on human health is contingent upon its ability to create and sustain colony structure, which in turn is dictated by the effective performance of flagella - a multi-protein rotary nanodevice. Hence, to design an effective therapeutic strategy against H. pylori , we here conducted a systematic search for an effective druggable site by focusing on the structure-dynamics-energetics-stability landscape of the junction points of three 1 : 1 protein complexes (FliF C -FliG N , FliG M -FliM M , and FliY C -FliN C ) that contribute mainly to the rotary motion of the flagella via the transformation of information along the junctions over a wide range of pH values operative in the stomach (from neutral to acidic). We applied a gamut of physiologically relevant perturbations in the form of thermal scanning and mechanical force to sample the entire quasi - and non-equilibrium conformational spaces available for the protein complexes under neutral and acidic pH conditions. Our perturbation-induced magnification of conformational distortion approach identified pH-independent protein sequence-specific evolution of precise thermally labile segments, which dictate the specific thermal unfolding mechanism of each complex and this complex-specific pH-independent structural disruption notion remains consistent under mechanical stress as well. Complementing the above observations with the relative rank-ordering of estimated equilibrium binding free energies between two protein sequences of a specific complex quantifies the extent of structure-stability modulation due to pH alteration, rationalizes the exceptional stability of H. pylori under acidic pH conditions, and identifies the pH-independent complex-sequence-segment-residue diagram for targeted drug design.

Inhomogeneity in single molecule electron transfer at the surface of lipid in a single vesicle has been explored by single molecule spectroscopic technique. In our study we took Di-methyl aniline (DMA), as the electron donor (D) and three different organic dyes as acceptor. These dyes are C153, C480 and C152 and they reside in different regions in the vesicle depending upon their preference of residence. For each probe, we found fluctuations in the single-molecule fluorescence decay, which are attributed to the variation in the reactivity of interfacial electron transfer. We found a non-exponential auto-correlation fluctuation of the intensity of the probe, which is ascribed to the kinetic disorder in the rate of electron transfer. We have also shown the power law distribution of the dark state (off time), which obeys the levy's statistics. We found a shift in lifetime distribution for the probe (C153) from 3.9 ns to 3.5 ns. This observed quenching is due to the dynamic electron transfer. We observed the kinetic disorderness in the electron transfer reaction for each dye. This source of fluctuation in electron transfer rate may be ascribed to the inherent fluctuation, occurring on the time scale of ~ 1.1 ms (for C153) of the vesicle, containing lipids., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

The emergence of a novel cross-α fibrillar structure, unlike the commonly observed sequence-independent cross-β one, of a 22-residue bacterial virulent amphipathic α-helical peptide of the phenol soluble modulin (PSM) family, PSMα3, with many deleterious effects on human life, has infused uncertainty to the paradigm of the intrinsically polymorphic, multivariate, multiphasic, and cross-sequence-cross-disease entangled protein aggregation landscape and hence on the identity of the therapeutic target. We, here, deconvolute the factors contributing to the genesis and hence the transition of lower to higher order aggregates of PSMα3 in its natural state and three noncanonical designed variants using conventional and enhanced sampling approach-based atomistic simulations. PSMα3 shows structural polymorphism with nominal α-helicity, substantial β-propensity, and dominant random-coil features, irrespective of the extent of aggregation. Moreover, the individual features of the overall amphipathicity operate alternatively depending on the extent and organization of aggregation; the dominance gradually moves from charged to hydrophobic residues with the progressive generation of higher order aggregates (dimer to oligomer to fibril) and with increasing orderedness of the self-assembled construct (oligomer vs dimer/fibril). Similarly, the contribution of interchain salt bridges decreases with increasing order of aggregation (dimer to oligomer to fibril). However, the intrachain salt bridges consistently display their role in all phases of aggregation. Such phase-independent features also include equivalent roles of electrostatic and van der Waals forces on intrachain interactions, sole contribution of van der Waals forces on interchain cross-talk, and negligible peptide-water relationship. Finally, we propose a conjugate peptide-based aggregation suppressor having a single-point proline mutation.

Whether single-molecule trajectories, observed experimentally or in molecular simulations, can be described using simple models such as biased diffusion is a subject of considerable debate. Memory effects and anomalous diffusion have been reported in a number of studies, but directly inferring such effects from trajectories, especially given limited temporal and/or spatial resolution, has been a challenge. Recently, we proposed that this can be achieved with information-theoretical analysis of trajectories, which is based on the general observation that non-Markov effects make trajectories more predictable and, thus, more "compressible" by lossless compression algorithms. Toy models where discrete molecular states evolve in time were shown to be amenable to such analysis, but its application to continuous trajectories presents a challenge: the trajectories need to be digitized first, and digitization itself introduces non-Markov effects that depend on the specifics of how trajectories are sampled. Here we develop a milestoning-based method for information-theoretical analysis of continuous trajectories and show its utility in application to Markov and non-Markov models and to trajectories obtained from molecular simulations., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

This research was done to evaluate the feasibility of using Albizia procera for manufacturing glulam beams. The physical and mechanical properties of the A. procera glulam beam were evaluated, and these properties were compared to those of the solid A. procera solid timber. The A. procera glulam beam's physical and mechanical properties were all superior to solid A. procera timber. In comparison to A. procera solid timber, A. procera glulam's density, water absorption (WA), linear expansion (LE), and thickness swelling (TS) all improved by 11.1, 48.4, 44.6, and 37.0%, respectively. Again, compared to A. procera solid timber, the modulus of rupture (MOR) and modulus of elasticity (MOE) of the A. procera glulam beam increased by 27.6 and 29.2%, respectively. Additionally, the ASTM specifications were met by the A. procera glulam beam. As a result, based on the properties, it is possible to make A. procera glulam beams as structural timber products., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (© 2023 The Authors.)

The mechanism of protein aggregation can be broadly viewed as a shift from the native-state stabilizing intramolecular to the aggregated-phase sustaining intermolecular interactions. Understanding the role of electrostatic forces on the extent of modulation of this switch has recently evolved as a topic of monumental significance as protein aggregation has lately been connected to charge modifications of an aging proteome. To decipher the distinctive role of electrostatic forces on the extremely complicated phase separation landscape, we opted for a combined in vitro-in silico approach to ascertain the structure-dynamics-stability-aggregability relationship of the functional tandem RRM domains of the ALS-related protein TDP-43 (TDP-43 tRRM ), under a bivariate solution condition in terms of pH and salt concentration. Under acidic pH conditions, the native TDP-43 tRRM protein creates an aggregation-prone entropically favorable partially unfolded conformational landscape due to enthalpic destabilization caused by the protonation of the buried ionizable residues and consequent overwhelming fluctuations of selective segments of the sequence leading to anti-correlated movements of the two domains of the protein. The evolved fluffy ensemble with a comparatively exposed backbone then easily interacts with incoming protein molecules in the presence of salt via typical amyloid-aggregate-like intermolecular backbone hydrogen bonds with a considerable contribution originating from the dispersion forces. Subsequent exposure to excess salt at low pH conditions expedites the aggregation process via an electrostatic screening mechanism where salt shows preferential binding to the positively charged side chain. The applied target observable-specific approach complementarity unveils the hidden information landscape of an otherwise complex process with unquestionable conviction.

The present state of understanding the mechanism of Spinocerebellar Ataxia-1, a fatal neurodegenerative disease linked to the protein Ataxin-1 (ATXN1), is baffled by a set of self-contradictory, and hence, inconclusive observations. This fallacy poses a bottleneck to the effective designing of curable drugs as the field is currently missing the specific druggable site. To understand the fundamentals of pathogenesis, we tried to decipher the intricacies of the extremely complicated landscape by targeting the relevant species that supposedly dictate the structure-function paradigm. The atomic-level description and characterization of the dynamism of the systems reveal the existence of structural polymorphism in all the leading stakeholders of the overall system. The very existence of conformational heterogeneity in every species creates numerous possible combinations of favorable interactions because of the variability in segmental cross-talks and hence claims its role in the choice of routes between functional activity and dysfunctional disease-causing aggregation. Despite this emergent configurational diversity, there is a common mode of operative intermolecular forces that dictates the extent of stability of all the multimeric complexes due to the localized population of a specific type of residue. The present research proposes a dynamic switch mechanism between aggregability and functional activity, based on the logical interpretation of the estimated variables, which is practically dictated by the effective concentration of the interacting species involved in the cell., (© 2022 Wiley Periodicals LLC.)

Multiple daily injections via subcutaneous route are the primary modes of insulin delivery for patients with Diabetes Mellitus. While this process is invasive, painful and may cause patients to develop lipohypertrophy at injection site, the perception of fear surrounding this process causes patients to delay in initiation and remain persistent with insulin therapy over time. Moreover, poor glycemic control may often lead to acute complications, such as severe hypoglycemia and nocturnal hypoglycemia, especially in older patients with diabetes. To address the imperative need for a patient-convenient non-invasive insulin therapy, an insulin-loaded arginine-coated self-emulsifying nanoglobule system (INS-LANano) was developed for nasal delivery of insulin with a biodegradable cationic surfactant-Lauroyl Ethyl Arginate (LAE). Incorporation of LAE resulted in formation of positively charged nanoglobules with L-arginine oriented on the surface. LANano enabled binding of insulin molecules on the surface of nanoglobules via an electrostatic interaction between negatively charged α-helix and LAE molecules at physiological pH. INS-LANano showed a hydrodynamic diameter of 23.38 nm with a surface charge of +0.118 mV. The binding efficiency of insulin on LANano globules was confirmed by zeta potential, circular dichroism (CD) spectroscopy and centrifugal ultrafiltration studies. The attachment of insulin with permeation-enhancing nanoglobules demonstrated significantly higher in vitro permeability of insulin of 15.2% compared to insulin solution across human airway epithelial cell (Calu-3) monolayer. Upon intranasal administration of INS-LANano to diabetic rats at 2 IU/kg insulin dose, a rapid absorption of insulin with significantly higher Cmax of 14.3 mU/L and relative bioavailability (BA) of 23.3% was observed. Therefore, the INS-LANano formulation significant translational potential for intranasal delivery of insulin.

The acid-base behavior of amino acids plays critical roles in several biochemical processes. Depending on the interactions with the protein environment, the p K a values of these amino acids shift from their respective solution values. As the side chains interact with the polypeptide backbone, a pH-induced change in the protonation state of aspartic and glutamic acids might significantly influence the structure and stability of a protein. In this work, we have combined two-dimensional infrared spectroscopy and molecular dynamics simulations to elucidate the pH-induced structural changes in an antimicrobial enzyme, lysozyme, over a wide range of pH. Simultaneous measurements of the carbonyl signals arising from the backbone and the acidic side chains provide detailed information about the pH dependence of the local and global structural features. An excellent agreement between the experimental and the computational results allowed us to obtain a residue-specific molecular understanding. Although lysozyme retains the helical structure for the entire pH range, one distinct loop region (residues 65-75) undergoes local structural deformation at low pH. Interestingly, combining our experiments and simulations, we have identified the aspartic acid residues in lysozyme, which are influenced the most/least by pH modulation.

The growing demand for energy and environmental issues are the main concern for the sustainable development of modern society. Replacing toxic and expensive materials with inexpensive and biodegradable biomaterials is the main challenge for researchers. Nanocomposites are of the utmost consideration for their application in energy storage devices because of their specific electrochemical properties. Cellulose-based bionanocomposites have added a new dimension to this field since these are developed from available renewable biomaterials. Studies on developing electrodes, separators, collectors, and electrolytes for the batteries have been conducted based on these composites rigorously. Electrodes and separators made of these composites for the supercapacitors have also been investigated. Researchers have used a wide range of micro- and nano-structural cellulose along with nanostructured inorganic materials to produce cellulose-based bionanocomposites for energy devices, i.e., supercapacitors and batteries. The presence of cellulosic materials enhances the loading capacity of active materials and uniform porous structure in the electrode matrix. Thus, it has shown improved electrochemical properties. Therefore, these can help to develop biodegradable, lightweight, malleable, and strong energy storage devices. In this review article, the manufacturing process, properties, applications, and possible opportunities of cellulose-based bionanocomposites in energy storage devices have been emphasized. Its challenges and opportunities have also been discussed., Competing Interests: The authors declare no conflict of interest., (© 2023 The Authors.)

One of the most abundant, prevailing, and life-threatening human diseases that are currently baffling the scientific community is type 2 diabetes (T2D). The self-association of human amylin has been implicated in the pathogenesis of T2D, though with an inconclusive understanding of the mechanism. Hence, we focused on the characterization of the conformational ensembles of all the species that are believed to define the structural polymorphism of the aggregation process - the functional monomeric, the initially self-associated oligomeric, and the structured protofibril - by employing near-equilibrium, non-equilibrium, and equilibrium atomistic simulations on the sporadic, two familial variants (S20G and G33R), and their proline-substituted forms (S20P and G33P). The dynamic near-equilibrium assays hint toward - the abundance of helical conformation in the monomeric state, the retainment of the helicity in the initial self-associated oligomeric phase pointing toward the existence of the helix-helix association mechanism, the difference in preference of specific segments to have definite secondary structural features, the phase-dependent variability in the dominance of specific segments and mutation sites, and the simultaneous presence of generic and unique features among various sequences. Furthermore, the non-equilibrium pulling assays exemplify a generic sequential unzipping mechanism of the protofibrils, however, the sequence-dependent uniqueness comes from the difference in location and magnitude of the control of a specific terminus. Importantly, the equilibrium thermodynamic assays efficiently rank order the potential of aggregability among sequences and consequently suggests the probability of designing effective aggregation suppressors against sporadic and familial amylin variants incorporating proline as the mutation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Mechanical and corrosion properties of welded duplex stainless steel (DSS) structures are of paramount consideration in many engineering applications. The current research investigates the mechanical properties and corrosion integrity of duplex stainless-steel weldment in a simulated 3.5% NaCl environment using specially developed novel electrodes without the addition of alloying elements to the flux samples. Two different types of fluxes having basicity indexes of 2.40 and 0.40 were used to coat E1 and E2 electrodes respectively for DSS plate welding. The thermal stability of the formulated flux was evaluated using thermogravimetric analysis. The chemical composition, using optical emission spectroscopy, and the mechanical and corrosion properties of the welded joints were evaluated as per different ASTM standards. X-ray diffraction was used to find out the phases present in the DSS welded joints while a scanning electron equipped with EDS was used for microstructural examination of the weldments. The ultimate tensile strength of welded joints made using the E1 electrode was in the range of 715-732 MPa and that of the E2 electrode was found to be 606-687 MPa. The hardness was increased with increased welding current from 90 to 110 A. The welded joint with E1 electrode coated with basic flux has better mechanical properties. The steel structure in 3.5% NaCl environment possesses substantial resistance to corrosion attack. This validates the performance of the welded joints made by the newly developed electrode. The results are discussed on the basis of the depletion of alloying elements such as Cr and Mo observed from the weldments with the coated electrodes E1 and E2 as well as precipitation of the Cr 2 N in the welded joints made by E1 and E2 electrodes., (© 2022. The Author(s).)

Melocanna baccifera is the most common bamboo species which grows naturally and gregariously covering large tracts of land in the forests of Chittagong Hill Tracts of Bangladesh. However, there is limited information about the chemical characterization of its culms for its utilization and processing. This paper aimed to determine the effect of age and height position on the chemical properties of M. baccifera . The highest value of holocellulose content was 74.66% for the top portion of 3-year-old bamboo, while the bottom part of 3-year-old bamboo showed the highest value of lignin (27.83%) and extractive (5.24%) content. For caustic soda (1% NaOH) solubility, the bottom portion of 1-year-old bamboo had shown the maximum value (25.67%), and it was the lowest (19.10%) for the top portion of 3-year-old bamboo. Ageing had a significant ( p < 0.05) effect on all chemical properties, while the height position had a significant effect on the holocellulose and lignin content and water solubility. The chemical properties of M. baccifera can enable its proper utilization in the downstream process., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Anthocephalus chinensis (Lam.) A. Rich ex Walp is widely used as raw materials in particleboard and match industries in Bangladesh. The current study aimed to identify the drying characteristics of A. Chinensis wood for succeeding industrial usages. A compartment kiln dryer (heat and vent dryer) was used in this study. The drying characteristics and drying quality of A. Chinensis wood were measured. The boards reached 6-10% moisture content in 13 days from their green condition. The total proportions of the check, twist, and collapse in boards were 22.5, 32.5, and 7.3%, respectively. The volumetric shrinkage was 21.67%. Based on this study, further study may help to develop a complete drying schedule of A. Chinensis wood with fewer drying defects for application at industrial level., Competing Interests: The authors declare no conflict of interest., (© 2022 The Author(s).)

Alzheimer's disease is undoubtedly the most well-studied neurodegenerative disease. Consequently, the amyloid-β (Aβ) protein ranks at the top in terms of getting attention from the scientific community for structural property-based characterization. Even after decades of extensive research, there is existing volatility in terms of understanding and hence the effective tackling procedures against the disease that arises due to the lack of knowledge of both specific target- and site-specific drugs. Here, we develop a multidimensional approach based on the characterization of the common static-dynamic-thermodynamic trait of the monomeric protein, which efficiently identifies a small target sequence that contains an inherent tendency to misfold and consequently aggregate. The robustness of the identification of the target sequence comes with an abundance of a priori knowledge about the length and sequence of the target and hence guides toward effective designing of the target-specific drug with a very low probability of bottleneck and failure. Based on the target sequence information, we further identified a specific mutant that showed the maximum potential to act as a destabilizer of the monomeric protein as well as enormous success as an aggregation suppressor. We eventually tested the drug efficacy by estimating the extent of modulation of binding affinity existing within the fibrillar form of the Aβ protein due to a single-point mutation and hence provided a proof of concept of the entire protocol.

One of the prevailing life-threatening incurable neurodegenerative diseases that are presently endangering human society as a whole, and hence, baffling the entire spectrum of the scientific and pharmaceutical world, is Alzheimer's disease (AD). AD is a manifestation of self-assembly of both wild-type (sporadic) and mutated (familial) forms of the amyloid-β peptide, a proteolytic product of the amyloid precursor protein, where the self-assembly results in the genesis of pathogenic fibrillar aggregates. Currently prevailing diagnostic and hence therapeutic challenges originate from the unavailability of a specific predictor for clinical observables. The continuous emergence of novel pathogenic mutants with unpredictable phenotypes adds immensely to the nonspecific nature of the problem. The current research reports a simple physical parameter, the binding affinity of a protofilament to its protofibril, which predicts the clinical observables of familial AD with astounding accuracy and more importantly, without any adjustable parameters.

Water hyacinth (WH) is considered as the worst aquatic weed in the world because of its rapid growth and fast spread into new areas of fresh water bodies. We investigated the potentiality of using WH as a raw material for production of handmade paper and compost in Bangladesh. Potash pulping was done using potassium hydroxide (KOH) at different alkali concentrations (8-12%) with a liquor to solid ratio of 7:1 at 145 °C for 2 h. The pulp was bleached using hydrogen peroxide (H 2 O 2 ), and pulp properties (brightness, tear index and tensile index) of bleached and unbleached pulps were analyzed following the respective TAPPI standards. The produced black liquor was mixed with WH along with kitchen bio-wastes to produce compost. The properties of the compost were tested following the published protocols, i.e., wet digestion, Kjeldahl, vanadomolybdophosphoric acid, and Flame Spectrophotometry methods. Brightness, tensile index and tear index of bleached hand sheets were found to be 37.2%, 49.2 N m/g and 6.79 m.Nm 2 /g, respectively suggesting significant contribution of bleaching on WH paper quality. Addition of black liquor significantly increased the nitrogen and potassium content of bio-waste compost. Thus, WH can be used as a raw material for making handmade paper while the process by-product can be supplemented to improve the nutritional quality of compost. Such cottage-industry fabrication of WH green products could be developed to control the infestation of WH in water bodies, and this technology may provide for new possible sustainable livelihood option., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In this study, bio-adhesives from natural rubber latex (NRL) were combined with starch and formic acid to fabricate jute stick-based particleboards (JSPs). Different blends of NRL, starch, and formic acid, i.e. , 6 : 1 : 1, 2 : 1 : 1, and 2 : 3 : 3, were used to produce particleboards using a pressing temperature of 180 °C and applied pressure of 5 MPa using a 5 min pressing time. The particleboards were tested for physical, mechanical, and thermal properties according to ANSI standards. Based on initial screening, the best formula (NRL/starch/formic acid of 2 : 3 : 3) was used to optimize the temperature and pressing time for the highest board performance. The highest density, tensile strength, modulus of elasticity, and modulus of rupture were 830 g cm -3 , 10.51, 2380, and 20.05 N mm -2 , respectively. Thermo-gravimetric analysis indicated that thermal decomposition of samples primarily occurred in a temperature range of 265 to 399 °C, indicating good thermal performance. The measured physical and mechanical properties of the produced JSPs fulfilled the production standards. However, fulfilling the water absorption and thickness swelling criteria was a challenge. The results indicate that NRL is a promising alternative binder when blended with starch and formic acid., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. It is here mentionable that several authors from the article author list have applied for a provisional patent (Application Number: P/BD/2018/000291) related to the research work and the final patent application is now in processing., (This journal is © The Royal Society of Chemistry.)

Healthcare waste comprises the waste generated by healthcare facilities, medical laboratories and biomedical research facilities. Improper treatment of this waste poses serious risks of disease transmission to waste pickers, waste workers, health workers, patients, and the community in general through exposure to infectious agents. Poor management of the waste emits harmful and deleterious contaminants into society. However, contamination of highly contagious agents such as the COVID-19 virus has created enormous instability in healthcare waste handling and subsequent recycling because of the volume of the waste generated and its contagious nature. Several countries have adopted safety measures to combat this contamination and manage healthcare waste; however, these measures are insufficient and vary depending on the context of the country. In addition, the WHO has set out guidelines for management of healthcare waste. These guidelines are helping to manage the highly contagious healthcare waste resulting from the current pandemic. Proper healthcare waste management may add value by reducing the spread of the COVID-19 virus and increasing the recyclability of materials instead of sending them to landfill. Disinfecting and sorting out healthcare waste facilitates sustainable management and allows their utilization for valuable purposes. This review discusses the different healthcare solid waste management strategies practiced in different countries, the challenges faced during this management, and the possible solutions for overcoming these challenges. It also provides useful insights into healthcare solid waste management scenarios during the COVID-19 pandemic and a possible way forward., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

How do trees support their upright massive bodies? The support comes from the incredibly strong and stiff, and highly crystalline nanoscale fibrils of extended cellulose chains, called cellulose nanofibers. Cellulose nanofibers and their crystalline parts-cellulose nanocrystals, collectively nanocelluloses, are therefore the recent hot materials to incorporate in man-made sustainable, environmentally sound, and mechanically strong materials. Nanocelluloses are generally obtained through a top-down process, during or after which the original surface chemistry and interface interactions can be dramatically changed. Therefore, surface and interface engineering are extremely important when nanocellulosic materials with a bottom-up process are fabricated. Herein, the main focus is on promising chemical modification and nonmodification approaches, aiming to prospect this hot topic from novel aspects, including nanocellulose-, chemistry-, and process-oriented surface and interface engineering for advanced nanocellulosic materials. The reinforcement of nanocelluloses in some functional materials, such as structural materials, films, filaments, aerogels, and foams, is discussed, relating to tailored surface and/or interface engineering. Although some of the nanocellulosic products have already reached the industrial arena, it is hoped that more and more nanocellulose-based products will become available in everyday life in the next few years., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Municipal solid waste (MSW) represents an inevitable by-product of human activity and a major crisis for communities across the globe. In recent times, the recycling of MSW has drawn attention as the process can add value through resources from the recovered waste materials and facilitates the process of circular economy. However, during the unprecedented coronavirus (COVID-19) outbreak, the risk of infection with the highly contagious virus has proven detrimental to the continuation of MSW as a valuable resource. The volume of waste, especially household waste, is higher; face masks, PPE (personal protective equipment), and hazardous materials such as batteries and empty chlorine bottles are examples of extra waste that have arisen during the pandemic. Various countries have set up initiatives for MSW management, including safety measurements for employees in the MSW management sector. The use of disinfectant prior to sorting waste, as well as storing waste for 9 days, may help to inactivate the COVID-19 virus, ensuring an appropriate safety level for MSW management. This work aimed at studying different MSW management strategies, specific challenges, and possible solutions for better understanding for those involved in waste management, in addition to providing a possible management strategy during and post-COVID-19 pandemic.

This study investigates the efficacy of chemically modified bone adhesive as a formaldehyde-free binder for wood-based industries. Two different types of adhesive are formulated after chemical modification of bone powder using sulfuric acid (0.5 m) and polyvinyl acetate (PVA). Gel time, solid content, Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), viscosity, and single lap joint test for shear strength are analyzed in order to assess the adhesive properties. To analyze the efficacy of the formulated adhesive, particleboards are fabricated using boiled and unboiled sugarcane bagasse. The physical and mechanical properties of the fabricated panels are measured following ASTM standards. It is found that adhesive Type C (T-C) has the shortest gel time of 4.2 min for the highest shear strength, i.e., 5.31 MPa. The particleboard (BTC-2) fabricated using T-C adhesive shows a highest density of 0.73 g cm -3 , a modulus of elasticity (MOE) of 1975 N mm -2 , and a modulus of rupture (MOR) of 11.80 N mm -2 . The dimensional stability of the fabricated particleboards does not follow the standard requirements; however, further study might be helpful for using the chemically modified bone adhesive as a biobased adhesive., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Global Challenges published by Wiley‐VCH GmbH.)

In this study, defatted rice bran (RB) is used to prepare an environmentally friendly adhesive through chemical modifications. The RB is mixed with distilled water with ratios of 1:5 and 1:4 to prepare Type A and Type B adhesives, respectively having pH of 6, 8 and 10. Type A adhesive is prepared by treating RB with 1% potassium permanganate and 4% poly(vinyl alcohol), whereas Type B is formulated by adding 17.3% formaldehyde and 5.7% urea to RB. Viscosity, gel time, solid content, shear strength, Fourier transform infrared (FTIR) spectroscopy is carried out, and glass transition temperature ( T g ), and activation energy ( E a ) are determined to evaluate the performance of the adhesives. E a data reveal that adhesives prepared at mild alkaline (pH 8) form long-chain polymers. Gel time is higher in the fabricated adhesives than that of the commercial urea formaldehyde (UF). FTIR data suggest that functional groups of the raw RB are chemically modified, which enhances the bondability of the adhesives. Shear strength data indicates that bonding strength increases with increasing pH. Similar results are also observed for physical and mechanical properties of fabricated particleboards with the adhesives. The results demonstrate that RB-based adhesives can be used as a potential alternative to currently used UF-based resin., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Global Challenges published by Wiley‐VCH GmbH.)

Melanoma or malignant melanoma is a type of skin cancer that develops when melanocyte cells, damaged by excessive exposure to harmful UV radiations, start to grow out of control. Though less common than some other kinds of skin cancers, it is more dangerous because it rapidly metastasizes if not diagnosed and treated at an early stage. The distinction between benign and melanocytic lesions could at times be perplexing, but the manifestations of the disease could fairly be distinguished by a skilled study of its histopathological and clinical features. In recent years, deep convolutional neural networks (DCNNs) have succeeded in achieving more encouraging results yet faster and computationally effective systems for detection of the fatal disease are the need of the hour. This paper presents a deep learning-based 'You Only Look Once (YOLO)' algorithm, which is based on the application of DCNNs to detect melanoma from dermoscopic and digital images and offer faster and more precise output as compared to conventional CNNs. In terms with the location of the identified object in the cell, this network predicts the bounding box of the detected object and the class confidence score. The highlight of the paper, however, lies in its infusion of certain resourceful concepts like two phase segmentation done by a combination of the graph theory using minimal spanning tree concept and L-type fuzzy number based approximations and mathematical extraction of the actual affected area of the lesion region during feature extraction process. Experimented on a total of 20250 images from three publicly accessible datasets-PH2, International Symposium on Biomedical Imaging (ISBI) 2017 and The International Skin Imaging Collaboration (ISIC) 2019, encouraging results have been obtained. It achieved a Jac score of 79.84% on ISIC 2019 dataset and 86.99% and 88.64% on ISBI 2017 and PH2 datasets, respectively. Upon comparison of the pre-defined parameters with recent works in this area yielded comparatively superior output in most cases.

We study intrachain dynamics of intrinsically disordered proteins, as manifested by the time scales of loop formation, using atomistic simulations, experiment-parametrized coarse-grained models, and one-dimensional theories assuming Markov or non-Markov dynamics along the reaction coordinate. Despite the generally non-Markov character of monomer dynamics in polymers, we find that the simplest model of one-dimensional diffusion along the reaction coordinate (equated to the distance between the loop-forming monomers) well captures the mean first passage times to loop closure measured in coarse-grained and atomistic simulations, which, in turn, agree with the experimental values. This justifies use of the one-dimensional diffusion model in interpretation of experimental data. At the same time, the transition path times for loop closure in longer polypeptide chains show significant non-Markov effects; at intermediate times, these effects are better captured by the generalized Langevin equation model. At long times, however, atomistic simulations predict long tails in the distributions of transition path times, which are at odds with both the one-dimensional diffusion model and the generalized Langevin equation model.

To perform specific functional activities, the majority of proteins should fold into their distinct three-dimensional conformations. However, the biologically active conformation of a protein is generally found to be marginally stable than the other conformations that the chain can adopt. How a protein finds its native conformation from its post-synthesis unfolded structure in a complex conformational landscape is the unsolved question that still drives the protein folding community. Here, we report the folding mechanism of a globular protein, ubiquitin, from its chemically denatured state using all-atom molecular dynamics simulations. From the kinetic analysis of the simulated trajectories we show that the folding process can be described by the hydrophobic collapse mechanism, initiated by the "dewetting transition", and subsequently assisted by the origination of an N-terminal folding nucleus, and finally supported by a native salt-bridge interaction between K11 and E34. We show that ubiquitin folds via an intermediate. Finally, we confirm the presence of "biological water" and explain its role to the folding process., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Transfer acts as a crucial bridge between the chemical vapor deposition (CVD) synthesis of large-scale graphene and its applications, but the quality evolution of a graphene film during transfer remains unclear. Here we use scanning Raman spectroscopy to monitor as-grown graphene during each step of wet transfer including floating on etchant solution, loaded onto a target substrate, and with additional annealing. Results show that the etchant solution results in strong compressive strain and p-type doping to floating graphene, but both are significantly reduced after the sample is loaded and rinsed especially for the doping. An annealing treatment increases the compressive strain in graphene but hardly its doping level. Moreover, when a poly(methyl methacrylate) (PMMA) layer is used to assist the transfer, it does not only increase the p-type doping of floating graphene but also lowers the crystalline quality of annealed graphene. Therefore, to obtain graphene with better quality, besides the attempts of improving CVD synthesis for its larger domain sizes, universal and easy-to-use polymer-free transfer techniques must be developed as well., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Many proteins are disordered under physiological conditions. How efficiently they can search for their cellular targets and how fast they can fold upon target binding is determined by their intrinsic dynamics, which have thus attracted much recent attention. Experiments and molecular simulations show that the inherent reconfiguration timescale for unfolded proteins has a solvent friction component and an internal friction component, and the microscopic origin of the latter, along with its proper mathematical description, has been a topic of considerable debate. Internal friction varies across different proteins of comparable length and increases with decreasing denaturant concentration, showing that it depends on how compact the protein is. Here we report on a systematic atomistic simulation study of how confinement, which induces a more compact unfolded state, affects dynamics and friction in disordered peptides. We find that the average reconfiguration timescales increase exponentially as the peptide's spatial dimensions are reduced; at the same time, confinement broadens the spectrum of relaxation timescales exhibited by the peptide. There are two important implications of this broadening: First, it limits applicability of the common Rouse and Zimm models with internal friction, as those models attempt to capture internal friction effects by introducing a single internal friction timescale. Second, the long-tailed distribution of relaxation times leads to anomalous diffusion effects in the dynamics of intramolecular distances. Analysis and interpretation of experimental signals from various measurements that probe intramolecular protein dynamics (such as single-molecule fluorescence correlation spectroscopy and single-molecule force spectroscopy) rely on the assumption of diffusive dynamics along the distances being probed; hence, our results suggest the need for more general models allowing for anomalous diffusion effects.

Recent single-molecule experiments probed transition paths of biomolecular folding and, in particular, measured the time biomolecules spend while crossing their free energy barriers. A surprising finding from these studies is that the transition barriers crossed by transition paths, as inferred from experimentally observed transition path times, are often lower than the independently determined free energy barriers. Here we explore memory effects leading to anomalous diffusion as a possible origin of this discrepancy. Our analysis of several molecular dynamics trajectories shows that the dynamics of common reaction coordinates used to describe protein folding is subdiffusive, at least at sufficiently short times. We capture this effect using a one-dimensional fractional Brownian motion (FBM) model, in which the system undergoes a subdiffusive process in the presence of a potential of mean force, and show that this model yields much broader distributions of transition path times with stretched exponential long-time tails. Without any adjustable parameters, these distributions agree well with the transition path times computed directly from protein trajectories. We further discuss how the FBM model can be tested experimentally.

In a dye sensitized photoelectrosynthesis cell (DSPEC), the relative orientation of the catalyst and chromophore plays an important role in determining the device efficiency. Here we introduce a new, robust atomic layer deposition (ALD) procedure for the preparation of molecular chromophore-catalyst assemblies on wide bandgap semiconductors. In this procedure, solution deposited, phosphonate derivatized metal complexes on metal oxide surfaces are treated with reactive metal reagents in the gas phase by ALD to form an outer metal ion bridging group, which can bind a second phosphonate containing species from solution to establish a R 1 -PO 2 -O-M-O-PO 2 -R 2 type surface assembly. With the ALD procedure, assemblies bridged by Al(III), Sn(IV), Ti(IV), or Zr(IV) metal oxide units have been prepared. To evaluate the performance of this new type of surface assembly, intra-assembly electron transfer was investigated by transient absorption spectroscopy, and light-driven water splitting experiments under steady-state illumination were conducted. A SnO 2 bridged assembly on SnO 2 /TiO 2 core/shell electrodes undergoes light-driven water oxidation with an incident photon to current efficiency (IPCE) of 17.1% at 440 nm. Light-driven water reduction with a ruthenium trisbipyridine chromophore and molecular Ni(II) catalyst on NiO films was also used to produce H 2 . Compared to conventional solution-based procedures, the ALD approach offers significant advantages in scope and flexibility for the preparation of stable surface structures.

Electrocatalysts are critically important for a secure energy future, as they facilitate the conversion between electrical and chemical energy. Molecular catalysts offer precise control of structure that enables understanding of structure-reactivity relationships, which can be difficult to achieve with heterogeneous catalysts. Molecular electrocatalysts can be immobilized on surfaces by covalent bonds or through non-covalent interactions. Advantages of surface immobilization include the need for less catalyst, avoidance of bimolecular decomposition pathways, and easier determination of catalyst lifetime. This Minireview highlights surface immobilization of molecular electrocatalysts for reduction of O 2 , oxidation of H 2 O, production of H 2 , and reduction of CO 2 ., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A long time ago, Kuhn predicted that long polymers should approach a limit where their global motion is controlled by solvent friction alone, with ruggedness of their energy landscapes having no consequences for their dynamics. In contrast, internal friction effects are important for polymers of modest length. Internal friction in proteins, in particular, affects how fast they fold or find their binding targets and, as such, has attracted much recent attention. Here we explore the molecular origins of internal friction in unfolded proteins using atomistic simulations, coarse-grained models and analytic theory. We show that the characteristic internal friction timescale is directly proportional to the timescale of hindered dihedral rotations within the polypeptide chain, with a proportionality coefficient b that is independent of the chain length. Such chain length independence of b provides experimentally testable evidence that internal friction arises from concerted, crankshaft-like dihedral rearrangements. In accord with phenomenological models of internal friction, we find the global reconfiguration timescale of a polypeptide to be the sum of solvent friction and internal friction timescales. At the same time, the time evolution of inter-monomer distances within polypeptides deviates both from the predictions of those models and from a simple, one-dimensional diffusion model.

In this study, films of gallium oxide (Ga2O3) were prepared through remote plasma atomic layer deposition (RP-ALD) using triethylgallium and oxygen plasma. The chemical composition and optical properties of the Ga2O3 thin films were investigated; the saturation growth displayed a linear dependence with respect to the number of ALD cycles. These uniform ALD films exhibited excellent uniformity and smooth Ga2O3-GaN interfaces. An ALD Ga2O3 film was then used as the gate dielectric and surface passivation layer in a metal-oxide-semiconductor high-electron-mobility transistor (MOS-HEMT), which exhibited device performance superior to that of a corresponding conventional Schottky gate HEMT. Under similar bias conditions, the gate leakage currents of the MOS-HEMT were two orders of magnitude lower than those of the conventional HEMT, with the power-added efficiency enhanced by up to 9 %. The subthreshold swing and effective interfacial state density of the MOS-HEMT were 78 mV decade(-1) and 3.62 × 10(11) eV(-1) cm(-2), respectively. The direct-current and radio-frequency performances of the MOS-HEMT device were greater than those of the conventional HEMT. In addition, the flicker noise of the MOS-HEMT was lower than that of the conventional HEMT.

Protein aggregation and amyloid formation are implicated in many diseases as well as in other biological phenomena. Recent studies have suggested that amyloid formation of tumor suppressor p53 can lead to loss of its physiological function, resulting in accelerated cancer progression. Design of cancer therapeutics, therefore, requires understanding of the mechanism of p53 aggregation. Here, we have employed atomistic simulations to characterize the aggregation process of the aggregation-prone (as suggested by experimental studies) p53 fragment (LTIITLE, 252-258) and to assess the efficiency of its I254R mutant as an aggregation suppressor. We show that the wild-type sequence attains stable β-sheet rich structure in the parallely arranged dimeric form, which dissociates in a sequential manner under mechanical force. The wild-type sequence further displays high aggregation propensity self-assembling into structures with parallel peptide arrangement. The I254R mutation destabilizes the dimer, changes the mechanical dissociation of the dimer to cooperative unfolding, reduces the aggregation propensity of the sequence, and alters the relative orientation of the peptides in the aggregate. Addition of the wild-type sequence, however, partially restores the aggregation propensity of the I254R mutant.

The study was conducted to evaluate the quality of dissolving pulp of Musa sapientum L. (banana) plant stem and its potential for biorefinery. Introduction of pre-hydrolysis prior to any alkaline pulping process helps to reduce the content of hemicellulose and consequently produce acceptably high content of cellulose pulp. Water pre-hydrolysis was done at 150°C for 90min. The amount of lignin, xylan and glucan in the extracted pre-hydrolysis liquor (PHL) was 1.6, 4.9 and 1.6%, respectively. Pulping of pre-extracted chips was done following soda-AQ, alkaline sulfite and kraft process. The ratio of chip to liquor was 1:7 for both pre-hydrolysis and pulping. The kraft pulping process with 20% active alkali and 25% sulfidity at 150°C for 90min showed the best result. The lowest kappa number was 26.2 with a considerable pulp yield of 32.7%. The pulp was bleached by acidic NaClO2 and the consistency was 10% based on air-dried pulp. The lowest amount of 7% NaClO2 was used for the bleaching sequence of D0ED1ED2. After D0ED1ED2 bleaching, the pulp showed that α-cellulose, brightness and ash were 91.9, 77.9 and 1.6% respectively. The viscosity was 19.9cP. Hence, there is a possibility to use banana plant stem as a raw material for dissolving grade pulp and other bioproducts., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12 hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24 hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

Gram-negative bacteria like Yersinia, Pseudomonas, and Aeromonas need type III secretion system (T3SS) for their pathogenicity. V-antigen and its regulator are essential for functioning of T3SS. There is significant functional conservation amongst V-antigen and its regulator belonging to the Ysc family. In this study, we have structurally characterized the inter-genus complexes of V-antigen and its regulator. ConSurf analysis demonstrates that V-antigens belonging to the Ysc family show high structural identity predominantly confined to the two long helical regions. The regulator of V-antigen shows high conservation in its first intramolecular coiled-coil domain, responsible for interaction with V-antigen. ∆LcrG(1-70) localizes within the groove formed by long helices of LcrV, as observed in PcrV-∆PcrG(13-72) interaction. Inter-genus complexes of LcrV-PcrG and PcrV-LcrG exhibited elongated conformation and 1:1 heterodimeric state like the native complex of PcrV-PcrG and LcrV-LcrG. Both native and inter-genus complexes showed rigid tertiary structure, solvent-exposed hydrophobic patches, and cooperative melting behavior with high melting temperature. LcrV-PcrG and PcrV-LcrG showed nanomolar affinity of interaction, identical to PcrV-PcrG interaction, but stronger than LcrV-LcrG interaction. Calcium (a secretion blocker of T3SS) propels all the complexes towards a highly monodisperse form. Calcium and magnesium increase the helicity of the native and inter-genus complexes, and causes helix-helix stabilization. Stabilization of helices leads to a slight increase in the melting temperature by 1.5-2.0 °C. However, calcium does not alter the affinity of interaction of V-antigen and its regulator, emphasizing the effect of divalent of cations at the structural level without any regulatory implications. Therefore, the structural conservation of these inter-genus complexes could be the basis for their functional complementation.

The synthesis and characterization of cationic two-dimensional metallamacrocycles having a hexagonal shape and cavity are described. Both macrocycles utilize a pyrazine motif containing an organometallic acceptor tecton with platinum(II) centers along with different donor ligands. While one macrocycle is a relatively larger [6 + 6], the other is a relatively smaller [2 + 2] polygon. A unique feature of the smaller ensemble is that it is an irregular polygon in which all six edges are not of equal length. Molecular modeling of these macrocycles confirmed the presence of hexagonal cavities. The ability of these π-electron rich macrocycles to act as potential hosts for relatively electron deficient nitroaromatics (DNT = 2,4-dinitrotoluene and PA = picric acid) has been studied using isothermal titration calorimetry (ITC) as a tool. Molecular dynamics simulation studies were subsequently performed to gain critical insight into the binding interactions between the nitroaromatic guest molecules (PA/DNT) and the ionic macrocycles reported herein.

Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex.

The design, synthesis, and characterization of a new pyrazine-based ditopic platinum(II) organometallic complex are reported. The molecular structure of the organoplatinum pyrazine dipod was determined by single-crystal X-ray crystallography. The potential utility of this organometallic ditopic acceptor as a building block in the construction of neutral metallasupramolecular macrocycles containing the pyrazine motif was explored. Pyrazine motifs containing supramolecules were characterized by multinuclear NMR (including (1)H DOSY), mass spectrometry, and elemental analysis. The geometry of each supramolecular framework was optimized by employing the PM6 semiempirical molecular orbital method to predict its shape and size. The ability of the pyrazine-based organoplatinum complex to act as a host for nitroaromatic guest (2,4-dinitrotoluene and PA) molecules was explored by isothermal titration calorimetry (ITC). The binding stoichiometry and thermodynamic parameters of these host-guest complexation reactions were evaluated using ITC. Theoretical calculations were performed to obtain insight into the binding pattern between the organometallic host and nitroaromatic guests. The preferable binding propensity of the binding sites of complex 1 for both nitroaromatics (PA and 2,4-dinitrotoluene) determined by molecular simulation studies corroborates well with the experimental results as obtained by ITC experiments.

This paper aims to investigate the light output power (LOP) of InGaN-based light-emitting diodes (LEDs) grown on patterned sapphire substrates (PSSs) with different symmetry. The GaN epitaxial layers grown on the hexagonal lattice arrangement PSS (HLAPSS) have a lower compressive strain than the ones grown on the square lattice arrangement PSS (SLAPSS). The quantum-confined Stark effect (QCSE) is also affected by the residual compressive strain. Based on the experimentally measured data and the ray tracing simulation results, the InGaN-based LED with the HLAPSS has a higher LOP than the one with the SLAPSS due to the weaker QCSE within multiple-quantum wells (MQWs).

A hydrogen-evolving homogeneous Ni(P2N2)2 electrocatalyst with peripheral ester groups has been covalently attached to a 1,2,3-triazolyllithium-terminated planar glassy carbon electrode surface. Coupling proceeds with both the Ni(0) and the Ni(II) complexes. X-ray photoemission spectra show excellent agreement between the Ni(0) coupling product and its parent complex, and voltammetry of the surface-confined system shows that a single species predominates with a surface density of 1.3 × 10(-10) mol cm(-2), approaching the value estimated for a densely packed monolayer. With the Ni(II) system, both photoemission and voltammetric data show speciation to unidentified products on coupling, and the surface density is 6.7 × 10(-11) mol cm(-2). The surface-confined Ni(0) complex is an electroctalyst for hydrogen evolution, showing the onset of catalytic current at the same potential as the soluble parent complex. Decomposition of the surface-confined species is observed in acidic acetonitrile. This is interpreted to reflect the lability of the Ni(II)-phosphine interaction and the basicity of the free phosphine and bears on concurrent efforts to implement surface-confined Ni(P2N2)2 complexes in electrochemical or photoelectrochemical devices.

The reaction of a lithium acetylide-ethylenediamine complex with azide-terminated glassy carbon surfaces affords 1,2,3-triazolyllithium surface groups that are active toward covalent C-C coupling reactions, including salt metathesis with an aliphatic halide and nucleophilic addition at an aldehyde. Surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry of electrode samples shows narrow, symmetric peaks indicating uniform attachment. X-ray photoelectron and reflectance infrared spectroscopic data provide further support for the surface-attached products. Formation of the 1,2,3-triazolyllithium linkage requires neither a catalyst nor a strained alkyne. Coverages obtained by this route are similar to those obtained by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) of ethynylferrocene with surface azides. Preconditioning of the glassy carbon disk electrodes at ambient temperature under nitrogen affords coverages comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen.