A sustainable process to 100%bio-based nylons integrated chemical and biological conversion of lignocellulose

Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.

Critical Solvation Structures Arrested Active Molecules for Reversible Zn Electrochemistry

Aqueous Zn-ion batteries(AZIBs)have attracted increasing attention in next-generation energy storage systems due to their high safety and economic.Unfortunately,the side reactions,dendrites and hydrogen evolution effects at the zinc anode interface in aqueous electrolytes seriously hinder the application of aqueous zinc-ion batteries.Here,we report a critical solvation strategy to achieve reversible zinc electrochemistry by introducing a small polar molecule acetonitrile to form a“catcher”to arrest active molecules(bound water molecules).The stable solvation structure of[Zn(H_(2)O)_(6)]^(2+)is capable of maintaining and completely inhibiting free water molecules.When[Zn(H_(2)O)_(6)]^(2+)is partially desolvated in the Helmholtz outer layer,the separated active molecules will be arrested by the“catcher”formed by the strong hydrogen bond N-H bond,ensuring the stable desolvation of Zn^(2+).The Zn||Zn symmetric battery can stably cycle for 2250 h at 1 mAh cm^(-2),Zn||V_(6)O_(13) full battery achieved a capacity retention rate of 99.2%after 10,000 cycles at 10 A g^(-1).This paper proposes a novel critical solvation strategy that paves the route for the construction of high-performance AZIBs.

Bio-based rejuvenators in asphalt pavements:A comprehensive review and analytical study

The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.This paper offers a comprehensive review and analysis of bio-based rejuvenators as a promising avenue for enhancing the longevity and sustainability of asphalt.Through a multifaceted exploration,it delves into various aspects of this innovative approach.Providing a thorough overview of bio-based rejuvenators,the study highlights their renewable and environmentally friendly characteristics.It conducts an in-depth examination of a wide spectrum of bio-derived materials,including vegetable oils,waste-derived bio-products,and biopolymers,through a comprehensive survey.The paper evaluates how bio-based rejuvenators enhance aged asphalt binders and mixes,effectively mitigating the adverse impacts of aging.Furthermore,it investigates how these rejuvenators address environmental concerns by identifying compatibility issues,assessing long-term performance,and evaluating economic feasibility.Finally,the paper outlines potential advancements and research pathways aimed at optimizing the utilization of bio-based rejuvenators in asphalt concrete,thereby contributing to the sustainable evolution of road infrastructure.

Aqueous-phase reforming of hydroxyacetone solution to bio-based H_(2)over supported Pt catalysts

Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.

H-and J-aggregation of conjugated small molecules in organic solar cells

As H-and J-aggregation receive more and more attention in the research of organic solar cells(OSCs),especially in small molecular systems,deep understanding of aggregation behavior is needed to guide the design of conjugated small molecular structure and the fabrication process of OSC device.For this end,this review is written.Here,the review firstly introduced the basic information about H-and J-aggregation of conjugated small molecules in OSCs.Then,the characteristics of H-and J-aggregation and the methods to identify them were summarized.Next,it reviewed the research progress of H-and J-aggregation of conjugated small molecules in OSCs,including the factors influencing H-and J-aggregation in thin film and the effects of H-and J-aggregation on OPV performance.

Optimal and robust control of population transfer in asymmetric quantum-dot molecules

We present an optimal and robust quantum control method for efficient population transfer in asymmetric double quantum-dot molecules.We derive a long-duration control scheme that allows for highly efficient population transfer by accurately controlling the amplitude of a narrow-bandwidth pulse.To overcome fluctuations in control field parameters,we employ a frequency-domain quantum optimal control theory method to optimize the spectral phase of a single pulse with broad bandwidth while preserving the spectral amplitude.It is shown that this spectral-phase-only optimization approach can successfully identify robust and optimal control fields,leading to efficient population transfer to the target state while concurrently suppressing population transfer to undesired states.The method demonstrates resilience to fluctuations in control field parameters,making it a promising approach for reliable and efficient population transfer in practical applications.

Graphene effectively activating "dead" water molecules between manganese dioxide layers in potassium-ion battery

Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.

Role of self-assembled molecules’anchoring groups for surface defect passivation and dipole modulation in inverted perovskite solar cells

Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication,low hysteresis effects,and high stability.Despite these advantages,their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite-electrode interface,particularly at the buried interface between the perovskite and transparent conductive oxide(TCO).Recent efforts in the perovskite community have focused on designing novel self-assembled molecules(SAMs)to improve the quality of the buried interface.However,a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces.This understanding is crucial,particularly in terms of identifying chemically active anchoring groups.In this study,we used the star SAM([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite-TCO interface.Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages.These groups fulfill three key criteria:they provide the greatest potential for defect passivation,exhibit stable adsorption with defects,and exert significant regulatory effects on interface dipoles.Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties,which effectively neutralize local charges near defects.Among various defect types,iodine vacancies are the easiest to passivate,whereas iodine-substituted lead defects are the most challenging to passivate.Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs,contributing to the ongoing development of more efficient inverted perovskite solar cells.

Large-scale interplant exchange of macromolecules between soybean and dodder under nutrient stresses

Parasitic plants and their hosts communicate through haustorial connections.Nutrient deficiency is a common stress for plants,yet little is known about whether and how host plants and parasites communicate during adaptation to such nutrient stresses.In this study,we used transcriptomics and proteomics to analyze how soybean(Glycine max)and its parasitizing dodder(Cuscuta australis)respond to nitrate and phosphate deficiency(-N and-P).After-N and-P treatment,the soybean and dodder plants exhibited substantial changes of transcriptome and proteome,although soybean plants showed very few transcriptional responses to-P and dodder did not show any transcriptional changes to either-N or-P.Importantly,large-scale interplant transport of mRNAs and proteins was detected.Although the mobile mRNAs only comprised at most 0.2%of the transcriptomes,the foreign mobile proteins could reach 6.8%of the total proteins,suggesting that proteins may be the major forms of interplant communications.Furthermore,the interplant mobility of macromolecules was specifically affected by the nutrient regimes and the transport of these macromolecules was very likely independently regulated.This study provides new insight into the communication between host plants and parasites under stress conditions.

Modulating perovskite crystallization and band alignment using coplanar molecules for high-performance indoor photovoltaics

The proper bandgap and exceptional photostability enable CsPbI_(3) as a potential candidate for indoor photovoltaics(IPVs),but indoor power conversion efficiency(PCE) is impeded by serious nonradiative recombination stemming from challenges in incomplete DMAPbI_(3) conversion and lattice structure distortion.Here,the coplanar symmetric structu re of hexyl sulfide(HS) is employed to functionalize the CsPbI_(3) layer for fabricating highly efficient IPVs.The hydrogen bond between HS and DMAI promotes the conversion of DMAPbI_(3) to CsPbI_(3),while the copianar symmetric structure enhances crystalline order.Simultaneously,surface sulfidation during HS-induced growth results in the in situ formation of PbS,spontaneously creating a CsPbI_(3) N-P homojunction to enhance band alignment and carrier mobility.As a result,the CsPbI_(3)&HS devices achieve an impressive indoor PCE of 39.90%(P_(in):334.6 μW cm^(-2),P_(out):133.5 μW cm^(-2)) under LED@2968 K,1062 lux,and maintain over 90% initial PCE for 800 h at ^(3)0% air ambient humidity.

Emerging molecules,tools,technology,and future of surgical knife in gastroenterology

The 21^(st) century has started with several innovations in the medical sciences,with wide applications in health care management.This development has taken in the field of medicines(newer drugs/molecules),various tools and technology which has completely changed the patient management including abdominal surgery.Surgery for abdominal diseases has moved from maximally invasive to minimally invasive(laparoscopic and robotic)surgery.Some of the newer medicines have its impact on need for surgical intervention.This article focuses on the development of these emerging molecules,tools,and technology and their impact on present surgical form and its future effects on the surgical intervention in gastroenterological diseases.

Elastic Bio-based Polyurethane Nanofibrous Membrane with Robust Waterproof and Breathable Properties

Elastic bio-based waterproof and breathable membranes(EBWBMs) allow the passage of water vapor effectively and resist the penetration of liquid water,making it ideal for use under extreme conditions.In this study,we used a facile strategy to design the bio-based polyurethane(PU) nanofibrous membranes with the nanoscale porous structure to provide the membranes with high waterproof and breathable performances.The optimization of nanofibrous membrane formation was accomplished by controlling the relative ambient humidity to modulate the cooperating effects of charge dissipation and non-solvent-induced phase separation.The obtained EBWBMs showed multiple functional properties,with a hydrostatic pressure of 86.41 kPa and a water vapor transmission(WVT) rate of 10.1 kg·m^(-2)·d^(-1).After 1 000 cycles of stretching at 40% strain,the EBWBMs retained over 59% of the original maximum stress and exhibited an ideal elasticity recovery ratio of 85%.Besides,even after 80% deformation,the EBWBMs still maintained a hydrostatic pressure of 30.65 kPa and a WVT rate of 13.6 kg·m^(-2)·d^(-1),suggesting that bio-based PU nanofibrous membranes could be used for protection under extreme conditions.

First-principles study on the co-adsorption of water and oxygen molecules on chalcopyrite(112)-M surface

Chalcopyrite is a common copper-bearing mineral with antiferromagnetic properties.However,this property has rarely been considered in previous studies for detailed adsorption behaviors of molecules on chalcopyrite.Based on density functional theory(DFT),new adsorption pathways by H_(2)O and O_(2)on the chalcopyrite metal terminated(112)surface((112)-M)is found in this work.First,through simulating the adsorption of an isolated water molecule and monolayer water molecules,it is confirmed that H_(2)O molecules tend to adsorb on the surface Fe atoms more than on the surface Cu atoms.Then,we studied various adsorption behaviors of the O_(2)molecule.It is found that the adsorption on the hollow FeAFe site is the most stable case;however,O_(2)is undissociated.Two adsorption cases will happen when H_(2)OAO_(2)adsorb simultaneously on the surface.For the S site,the H_(2)O molecule thoroughly dissociated and formed SAO species,and the other case is H_(2)O undissociated adsorbing at the Cu site.For the former case,it is interesting that H_(2)O is dissociated before O_(2).

Therapies for Tau-associated neurodegenerative disorders:targeting molecules,synapses,and cells

Advances in experimental and computational technologies continue to grow rapidly to provide novel avenues for the treatment of neurodegenerative disorders. Despite this, there remain only a handful of drugs that have shown success in late-stage clinical trials for Tau-associated neurodegenerative disorders. The most commonly prescribed treatments are symptomatic treatments such as cholinesterase inhibitors and N-methyl-D-aspartate receptor blockers that were approved for use in Alzheimer's disease. As diagnostic screening can detect disorders at earlier time points, the field needs pre-symptomatic treatments that can prevent, or significantly delay the progression of these disorders(Koychev et al., 2019). These approaches may be different from late-stage treatments that may help to ameliorate symptoms and slow progression once symptoms have become more advanced should early diagnostic screening fail. This mini-review will highlight five key avenues of academic and industrial research for identifying therapeutic strategies to treat Tau-associated neurodegenerative disorders. These avenues include investigating(1) the broad class of chemicals termed “small molecules”;(2) adaptive immunity through both passive and active antibody treatments;(3) innate immunity with an emphasis on microglial modulation;(4) synaptic compartments with the view that Tau-associated neurodegenerative disorders are synaptopathies. Although this mini-review will focus on Alzheimer's disease due to its prevalence, it will also argue the need to target other tauopathies, as through understanding Alzheimer's disease as a Tau-associated neurodegenerative disorder, we may be able to generalize treatment options. For this reason, added detail linking back specifically to Tau protein as a direct therapeutic target will be added to each topic.

Fully Bio-Based Composites of Poly(Lactic Acid)Reinforced with Cellulose-Graft-Poly-(ε-Caprolactone)Copolymers

Due to the increasing demand for modified polylactide(PLA)meeting“double green”criteria,the research on sustainable plasticizers for PLA has attracted broad attentions.This study reported an open-ring polymerization method to fabricate cellulose(MCC)-g-PCL(poly(ε-caprolactone))copolymers with a fully sustainable and biodegradable component.MCC-g-PCL copolymers were synthesized,characterized,and used as green plasticizers for the PLA toughening.The results indicated that the MCC-g-PCL derivatives play an important role in the compatibility,crystallization,and toughening of the PLA/MCC-g-PCL composites.The mechanical properties of the fully bio-based PLA/MCC-g-PCL composites were optimized by adding 15 wt%MCC-g-PCL,that is,the elongation at break was 22.6%(~376%higher than that of neat PLA),the tensile strength was 47.3 MPa(comparable to that of neat PLA),and the impact strength was 26 J/m(~130%higher than that of neat PLA).DSC results indicated that MCC-g-PCL reduced the Tg of the PLA blend.When the addition amount was 15 wt%,the Tg of the blend was 58.4°C.Compared with MCC,MCC-g-PCL polyester plasticizer has better thermal stability,T5%(°C)can still be maintained above 300°C.The rheological results showed that MCC-g-PCL acted as a plasticizer,the introduction of PCL flexible chain increased the mobility of PLA molecular chain,and decreased the complex viscosity,storage modulus and loss modulus of PLA blends.The MCC-g-PCL derivatives,as a new green plastic additive,have shown an interesting prospect to prepare fully bio-based composites.

Synthesis,Characterization and Water Absorption Analysis of Highly Hygroscopic Bio-based Co-polyamides 56/66

This study aims to develop highly hygroscopic bio-based co-polyamides(CPs)by melt co-polycondensation of polyamide(PA)56 salt and PA66 salt with varying molar fractions.The functional groups and the chemical structure of the prepared samples were determined by Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(^(1)H-NMR)spectroscopy.The relative viscosity was determined with an Ubbelohde viscometer.The melting behavior and the thermal stability of CPs were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Furthermore,the water absorption behavior of CP hot-pressed film was studied.The results reveal that the melting point,the crystallization temperature and the crystallinity of CPs firstly decrease and then increase with the molar fraction of PA66 in CPs.The copolymerization of PA56 with PA66 leads to an obvious increase in water absorption.The CPs with PA66 molar fraction of 50%possess a high saturated water absorption rate of 17.6%,compared to 11.6%for pure PA56 and 7.8%for pure PA66.

Recent Progress of Surface Passivation Molecules for Perovskite Solar Cell Applications

Due to the solution processable nature,the prepared perovskite films are polycrystalline with considerable number of defects.These defects,especially defects at interface accelerate the carrier recombination and reduce the carrier collection.Besides,the surface defects also affect the long-term stability of the perovskite solar cells(PVSCs).To solve this problem,surface passivation molecules are introduced at selective interface(the interface between perovskite and carrier selective layer).This review summarizes recent progress of small molecules used in PVSCs.Firstly,different types of defect states in perovskite films are introduced and their effects on device performance are discussed.Subsequently,surface passivation molecules are divided into four categories,and the interaction between the functional groups of the surface passivation molecules and selective defect states in perovskite films are highlighted.Finally,we look into the prospects and challenges in design noble small molecules for PVSCs applications.

MOLECULES AND NEW INTERACTIONAL STRUCTURES FOR A(2+1)-DIMENSIONAL GENERALIZED KONOPELCHENKO-DUBROVSKY-KAUP-KUPERSHMIDT EQUATION

Soliton molecules(SMs)of the(2+1)-dimensional generalized KonopelchenkoDubrovsky-Kaup-Kupershmidt(gKDKK)equation are found by utilizing a velocity resonance ansatz to N-soliton solutions,which can transform to asymmetric solitons upon assigning appropriate values to some parameters.Furthermore,a double-peaked lump solution can be constructed with breather degeneration approach.By applying a mixed technique of a resonance ansatz and conjugate complexes of partial parameters to multisoliton solutions,various kinds of interactional structures are constructed;There include the soliton molecule(SM),the breather molecule(BM)and the soliton-breather molecule(SBM).Graphical investigation and theoretical analysis show that the interactions composed of SM,BM and SBM are inelastic.

Eco-friendly physical blowing agent mass loss of bio-based polyurethane rigid foam materials

Through systematical experiment design, the physical blowing agent(PBA) mass loss of bio-based polyurethane rigid foam(PURF)in the foaming process was measured and calculated in this study, and different eco-friendly PBA mass losses were measured quantitatively for the first time. The core of the proposed method is to add water to replace the difference, and this method has a high fault tolerance rate for different foaming forms of foams. The method was proved to be stable and reliable through the standard deviations σ1and σ2for R1(ratio of the PBA mass loss to the material total mass except the PBA) and R2(ratio of the PBA mass loss to the PBA mass in the material total mass) in parallel experiments. It can be used to measure and calculate the actual PBA mass loss in the foaming process of both bio-based and petroleumbased PURF. The results show that the PBA mass loss in PURF with different PBA systems is controlled by its initial mass content of PBA in PU materials ω. The main way for PBA to dissipate into the air is evaporation/escape along the upper surface of foam. This study further reveals the mechanism of PBA mass loss: the evaporation/escape of PBA along the upper surface of foam is a typical diffusion behavior. Its spread power comes from the difference between the chemical potential of PBA in the interface layer and that in the outside air. For a certain PURF system, R1has approximately linear relationship with the initial mass content of PBA in PU materials ω, which can be expressed by the functional relationship R1= kω, where k is a variable related to PBA’s own attributes.

CO_(2)-Responsive Smart Foams Stabilized by an Extremely Rigid Bio-Based Surfactant

Environment friendly and intelligent surfactants have attracted great attention in recent years.A bio-based CO_(2)responsive surfactant rosin acid dimaleimide choline(R-BMI-C)with an extremely rigid skeleton was prepared using rosin and choline as raw materials by Diels-Alder addition reaction and acid-base neutralization reactions.Its structure was confirmed by IR and^(1)H NMR spectra.The foams’properties of R-BMI-C could be adjusted by bubbling CO_(2)/N_(2)to change the structure of the surfactant.At pH 10.4,R-BMI-C forms an unstable foam with a half-life of 1.5 h.When the pH was reduced to 7.4 by bubbling CO_(2),R-BMI-C forms an extremely stable foam with a half-life of 336 h.The surfactant R-BMI-C changed from bola type to conventional type when bubbling CO_(2).And the internal aggregation structure of R-BMI-C aqueous solution changed from spherical micelles to laminar micelles according to the cryogenic-transmission electron microscope.We know that the lamellar structure tends to adsorb at the air/water interface or is trapped in the foam film,which slows down the foam coarsening and agglomeration process,resulting in a significant increase in foam stability.R-BMI-C could be used in oil extraction,fire-fighting and chemical decontamination due to its excellent foaming,stabilization and defoaming properties.