A generic method was described to change surface biocompatibihty by introducing reactive functional groups onto surfaces of polymeric substrates and covalently binding them with biomolecules.A block copolymer with pro...A generic method was described to change surface biocompatibihty by introducing reactive functional groups onto surfaces of polymeric substrates and covalently binding them with biomolecules.A block copolymer with protected carboxylic acid functionality,poly（styrene-b-tert-butyl acrylate）（PS-PtBA）,was spin coated from solutions in toluene on a bioinert polystyrene（PS） substrate to form a bilayer structure：a surface layer of the poly（tert-butyl acrylate）（PtBA） blocks that order at the air-polymer interface and a bottom layer of the PS blocks that entangle with the PS substrate.The thickness of the PtBA layer and the area density of tert-butyl ester groups of PtBA increased linearly with the concentration of the spin coating solution until a 2 nm saturated monolayer coverage of PtBA was achieved at the concentration of 0.4%W/W.The protected carboxylic acid groups were generated by exposing the tert-butyl ester groups of PtBA to trifluoroacetic acid （TFA） for bioconjugation with FMRF peptides via amide bonds.The yield of the bioconjugation reaction for the saturated surface was calculated to be 37.1%based on X-ray photoelectron spectroscopy（XPS） measurements.The success of each functionalization step was demonstrated and characterized by XPS and contact angle measurements.This polymer functionalization/modification concept can be virtually applied to any polymeric substrate by choosing appropriate functional block copolymers and biomolecules to attain novel biocompatibility.展开更多
Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane(MPPM)with lactose-based polyols.The affinity is based on specific complexation between bo...Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane(MPPM)with lactose-based polyols.The affinity is based on specific complexation between boric acid and saccharide polyols.A photoinduced grafting-chemical reaction sequence was used to prepare these affinity membranes.Poly(2-aminoethyl methacrylate hydrochloride)[poly(AEMA)]was grafted on the surfaces of MPPM by UV-induced graft polymerization.Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with confocal laser scanning microscopy.It is concluded that lactose ligands can be covalently immobilized on the external surface and in the pores by the subsequent coupling of poly(AEMA)with lactobionic acid(LA).Physical and chemical properties of the affinity membranes were characterized by field emission scanning electron microscopy and Fourier Transform Infrared/Attenuated Total Refraction spectroscopy(FT-IR/ATR).3-Aminophenyl boric acid(3-APBA)was removed from aqueous solution by a single piece of lactose-functionalized MPPM in a dynamic filtration system.The results show that the 3-APBA removal reaches an optimal efficiency(39.5%)under the alkaline condition(pH9.1),which can be improved by increasing the immobilization density of LA.Regeneration of these affinity membranes can be easily realized through acid-base washing because the complexation of boric acid and saccharide polyol is reversible.展开更多
Among the several types of inorganic nanoparticles available,silica nanoparticles(SNP)have earned their relevance in biological applications namely,as bioimaging agents.In fact,uorescent SNP(FSNP)have been explored in...Among the several types of inorganic nanoparticles available,silica nanoparticles(SNP)have earned their relevance in biological applications namely,as bioimaging agents.In fact,uorescent SNP(FSNP)have been explored in this-eld as protective nanocarriers,overcoming some limitations presented by conventional organic dyes such as high photobleaching rates.A crucial aspect on the use of uorescent SNP relates to their surface properties,since it determines the extent of interaction between nanoparticles and biological systems,namely in terms of colloidal stability in water,cellular recognition and internalization,tracking,biodistribution and speci-city,among others.Therefore,it is imperative to understand the mechanisms underlying the interaction between biosystems and the SNP surfaces,making surface functionalization a relevant step in order to take full advantage of particle properties.The versatility of the surface chemistry on silica platforms,together with the intrinsic hydrophilicity and biocompatibility,make these systems suitable for bioimaging applications,such as those mentioned in this review.展开更多
Surface functionalization of sensor chip for probe immobilization is crucial for the biosensing applications of surface plasmon resonance(SPR)sensors.In this paper,we report a method circulating the dopamine aqueous s...Surface functionalization of sensor chip for probe immobilization is crucial for the biosensing applications of surface plasmon resonance(SPR)sensors.In this paper,we report a method circulating the dopamine aqueous solution to coat polydopamine film on sensing surface for surface functionalization of SPR chip.The polydopamine film with available thickness can be easily prepared by controlling the circulation time and the biorecognition elements can be immobilized on the polydopamine film for specific molecular interaction analysis.These opera-tions are all performed under flow condition in the fuidic system,and have the advantages of easy implementation,less time consuming,and low cost,because the reagents and devices used in the operations are routinely applied in most laboratories.In this study,the specific absorption between the protein A probe immobilized on the sensing surface and human immunoglobulin G in the buffer is monitored based on this surface functionalization strategy to demonstrated its feasibility for SPR biosensing applications.展开更多
Wetting condition of micro/nanostructured surface has received tremendous attention due to the potential applications in commercial,industrial,and military areas.Surfaces with extreme wetting properties,e.g.,superhydr...Wetting condition of micro/nanostructured surface has received tremendous attention due to the potential applications in commercial,industrial,and military areas.Surfaces with extreme wetting properties,e.g.,superhydrophobic or superhydrophilic,are extensively employed due to their superior anti-icing,drag reduction,enhanced boiling heat transfer,self-cleaning,and anti-bacterial properties depending on solid-liquid interfacial interactions.Laser-based techniques have gained popularity in recent years to create micro/nano-structured surface owing to their high flexibility,system precision,and ease for automation.These techniques create laser induced periodic surface structures(LIPSS)or hierarchical structures on substrate material.However,micro/nanostructures alone cannot attain the desired wettability.Subsequent modification of surface chemistry is essentially needed to achieve target extreme wettability.This review paper aims to provide a comprehensive review for both laser texturing techniques and the following chemistry modification methods.Recent research progress and fundamental mechanisms of surface structure generation via different types of lasers and various chemistry modification methods are discussed.The complex combination between the laser texturing and surface chemistry modification methods to decide the final wetting condition is presented.More importantly,surface functionalities of these surfaces with extreme wetting properties are discussed.Lastly,prospects for future research are proposed and discussed.展开更多
BACKGROUND Dry eye disease(DED)is a multifactorial ocular surface disorder with rising prevalence.It is closely related to systemic health and psychological factors,such as sleep and mood disorders,which significantly...BACKGROUND Dry eye disease(DED)is a multifactorial ocular surface disorder with rising prevalence.It is closely related to systemic health and psychological factors,such as sleep and mood disorders,which significantly impact the quality of life of patients.AIM To explore the correlations between ocular surface function,sleep quality,and anxiety/depression in patients with DED.METHODS This was a cross-sectional investigative study that included 358 patients with DED between January 2022 and January 2025.Ocular surface was assessed using the ocular surface disease index(OSDI),tear film break-up time,fluorescein staining score,and Schirmer I test.The Pittsburgh Sleep Quality Index(PSQI),Self-Rating Anxiety Scale(SAS),and Self-Rating Depression Scale(SDS)were used to evaluate sleep quality and anxiety/depression levels.Correlation and linear regression analyses were used to explore the relationships.RESULTS The mean PSQI score of the patients was 9.94±2.18;the mean SAS score was 47.30±4.90,and the mean SDS score was 50.08±5.52.These suggested a prevalence of sleep and psychological abnormalities.There was a significant correlation between the indicators of ocular surface function(OSDI,tear film break-up time,fluorescein staining,and Schirmer I test)and PSQI,SAS,and SDS scores(P<0.05).Moreover,multiple regression revealed that age≥50 years(β=1.55,P=0.029),PSQI scores(β=0.58,P<0.001),SAS scores(β=0.17,P=0.017),and SDS scores(β=0.15,P=0.019)were independent predictors of the OSDI scores.CONCLUSION Ocular surface function in patients with DED is closely related to sleep quality and anxiety/depression,emphasizing the need for holistic clinical management.展开更多
Indium-based materials(e.g.,In_(2)O_(3))are a class of promising non-noble metal-based catalysts for electroreduction of carbon dioxide(CO_(2)).However,competitive hydrogen reduction reaction(HER)on indium-based catal...Indium-based materials(e.g.,In_(2)O_(3))are a class of promising non-noble metal-based catalysts for electroreduction of carbon dioxide(CO_(2)).However,competitive hydrogen reduction reaction(HER)on indium-based catalysts hampers CO_(2) reduction reaction(CO_(2)RR)process.We herein tune the interfacial microenvironment of In_(2)O_(3) through chemical graft of alkyl phosphoric acid molecules using a facile solution-processed strategy for the first time,which is distinguished from other researches that tailor intrinsic activity of In_(2)O_(3) themselves.The surface functionalization of alkyl phosphoric acids over In_(2)O_(3) is demonstrated to remarkably boost CO_(2) conversion.For example,octadecylphosphonic acid modified In_(2)O_(3) exhibits Faraday efficiency for H_(2) H_(2) H_(2)(FE)of as low as 6.6%and FEHCOOH of 86.5%at-0.67 V vs.RHE,which are far superior to parent In_(2)O_(3) counterparts(FE of 24.0%and FEHCOOH of 63.1%).Moreover,the enhancing effect of alkyl phosphoric acid functionalization is found to be closely related to the length of alkyl chains.By virtue of comprehensive experimental characterizations and molecular dynamics simulations,it is revealed that the modification of alkyl phosphoric acids significantly alters the interface microenvironment of the electrocatalyst,which changes the electrocatalyst surface from hydrophilic and aerophobic to hydrophobic and aerophilic.In this case,the water molecules are pushed away and more CO_(2) molecules are trapped,increasing local CO_(2) concentration at In_(2)O_(3) active sites,thus leading to the significantly enhanced CO_(2)RR and suppressed HER.This work highlights the importance of regulating the interfacial microenvironment of inorganic catalysts by molecular surface functionalization as a means for promoting the electrochemical performance in electrosynthesis and beyond.展开更多
Surface functionalization is a widely adopted technique for surface modification which allows researchers to customize surfaces to integrate with their research. Surface functionalization has been used recently to ada...Surface functionalization is a widely adopted technique for surface modification which allows researchers to customize surfaces to integrate with their research. Surface functionalization has been used recently to adapt surfaces to integrate with biological materials specifically to isolate cells or mimic biological tissues through cell patterning. Cell isolation and cell patterning both can be integrated with extant techniques or surfaces to customize the research to whatever needs to be tested. Substrates such as metals, biologically mimicking surfaces, environmental responsive surfaces, and even three-dimensional surfaces such as hydrogels have all been adapted to allow for functionalization for both patterning and isolation. In this review we have described both the advantages and disadvantages of these techniques and the related chemistries to better understand these tools and how best to apply them in the hope that we can further expand upon the research in the field.展开更多
Osteoarthritis is associated with the significantly increased friction of the joint,which results in progressive and irreversible damage to the articular cartilage.A synergistic therapy integrating lubrication enhance...Osteoarthritis is associated with the significantly increased friction of the joint,which results in progressive and irreversible damage to the articular cartilage.A synergistic therapy integrating lubrication enhancement and drug delivery is recently proposed for the treatment of early-stage osteoarthritis.In the present study,bioinspired by the self-adhesion performance of mussels and super-lubrication property of articular cartilages,a biomimetic self-adhesive dopamine methacrylamide-poly(2-methacryloyloxyethyl phosphorylcholine)(DMA-MPC)copolymer was designed and synthesized via free radical polymerization.The copolymer was successfully modified onto the surface of biodegradable mesoporous silica nanoparticles(bMSNs)by the dip-coating method to prepare the dual-functional nanoparticles(bMSNs@DMA-MPC),which were evaluated using a series of surface characterizations including the transmission electron microscope(TEM),Fourier transform infrared(FTIR)spectrum,thermogravimetric analysis(TGA),X-ray photoelectron spectroscopy(XPS),etc.The tribological test and in vitro drug release test demonstrated that the developed nanoparticles were endowed with improved lubrication performance and achieved the sustained release of an anti-inflammatory drug,i.e.,diclofenac sodium(DS).In addition,the in vitro biodegradation test showed that the nanoparticles were almost completely biodegraded within 10 d.Furthermore,the dual-functional nanoparticles were biocompatible and effectively reduced the expression levels of two inflammation factors such as interleukin-1β(IL-1β)and interleukin-6(IL-6).In summary,the surface functionalized nanoparticles with improved lubrication and local drug release can be applied as a potential intra-articularly injected biolubricant for synergistic treatment of early-stage osteoarthritis.展开更多
Graphene-like borophene was theoretically proposed and recently synthesized on Al(111)surface,however,how to conquer its structural instability is still an open question.By means of density functional theory computati...Graphene-like borophene was theoretically proposed and recently synthesized on Al(111)surface,however,how to conquer its structural instability is still an open question.By means of density functional theory computations,we theoretically predicted that honeycomb borophene can be well stabilized by double-sided surface passivation with monovalent functional groups(X=F,Cl,Br,I,OH,and NH2)due to the electron redistributions.The system undergoes the transition from metallic to semiconducting upon functionalization,while the energy gap depends on the choice of functional groups.Under external strain,the gap values can be manipulated over a broad range.Our further calculations indicated that the functionalized borophene possesses moderate and anisotropic carrier mobility,which is comparable to or even higher than some 2D materials such as MoS2 and phosphorene.Our work provides a feasible strategy to effectively stabilize the graphene-like borophene and tune the electronic properties with great potentials for electronic applications.展开更多
Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomer...Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.展开更多
Hydrogel scaffolds have numerous potential applications in the tissue engineering field.However,tough hydrogel scaffolds implanted in vivo are seldom reported because it is difficult to balance biocompatibility and hi...Hydrogel scaffolds have numerous potential applications in the tissue engineering field.However,tough hydrogel scaffolds implanted in vivo are seldom reported because it is difficult to balance biocompatibility and high mechanical properties.Inspired by Chinese ramen,we propose a universal fabricating method(printing-P,training-T,cross-linking-C,PTC&PCT)for tough hydrogel scaffolds to fill this gap.First,3D printing fabricates a hydrogel scaffold with desired structures(P).Then,the scaffold could have extraordinarily high mechanical properties and functional surface structure by cycle mechanical training with salting-out assistance(T).Finally,the training results are fixed by photo-cross-linking processing(C).The tough gelatin hydrogel scaffolds exhibit excellent tensile strength of 6.66 MPa(622-fold untreated)and have excellent biocompatibility.Furthermore,this scaffold possesses functional surface structures from nanometer to micron to millimeter,which can efficiently induce directional cell growth.Interestingly,this strategy can produce bionic human tissue with mechanical properties of 10 kPa-10 MPa by changing the type of salt,and many hydrogels,such as gelatin and silk,could be improved with PTC or PCT strategies.Animal experiments show that this scaffold can effectively promote the new generation of muscle fibers,blood vessels,and nerves within 4 weeks,prompting the rapid regeneration of large-volume muscle loss injuries.展开更多
Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operati...Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.展开更多
Magnetically responsive microstructured functional surface(MRMFS),capable of dynamically and reversibly switching the surface topography under magnetic actuation,provides a wireless,noninvasive,and instantaneous way t...Magnetically responsive microstructured functional surface(MRMFS),capable of dynamically and reversibly switching the surface topography under magnetic actuation,provides a wireless,noninvasive,and instantaneous way to accurately control the microscale engineered surface.In the last decade,many studies have been conducted to design and optimize MRMFSs for diverse applications,and significant progress has been accomplished.This review comprehensively presents recent advancements and the potential prospects in MRMFSs.We first classify MRMFSs into one-dimensional linear array MRMFSs,two-dimensional planar array MRMFSs,and dynamic self-assembly MRMFSs based on their morphology.Subsequently,an overview of three deformation mechanisms,including magnetically actuated bending deformation,magnetically driven rotational deformation,and magnetically induced self-assembly deformation,are provided.Four main fabrication strategies employed to create MRMFSs are summarized,including replica molding,magnetization-induced self-assembly,laser cutting,and ferrofluid-infused method.Furthermore,the applications of MRMFS in droplet manipulation,solid transport,information encryption,light manipulation,triboelectric nanogenerators,and soft robotics are presented.Finally,the challenges that limit the practical applications of MRMFSs are discussed,and the future development of MRMFSs is proposed.展开更多
This study proposes an alternative calculation mode for stresses on the slip surface(SS).The calculation of the normal stress(NS)on the SS involves examining its composition and expanding its unknown using the Taylor ...This study proposes an alternative calculation mode for stresses on the slip surface(SS).The calculation of the normal stress(NS)on the SS involves examining its composition and expanding its unknown using the Taylor series.This expansion enables the reasonable construction of a function describing the NS on the SS.Additionally,by directly incorporating the nonlinear Generalized Hoke-Brown(GHB)strength criterion and utilizing the slope factor of safety(FOS)definition,a function of the shear stress on the SS is derived.This function considers the mutual feedback mechanism between the NS and strength parameters of the SS.The stress constraints conditions are then introduced at both ends of the SS based on the spatial stress relation of one point.Determining the slope FOS and stress solution for the SS involves considering the mechanical equilibrium conditions and the stress constraint conditions satisfied by the sliding body.The proposed approach successfully simulates the tension-shear stress zone near the slope top and provides an intuitive description of the concentration effect of compression-shear stress of the SS near the slope toe.Furthermore,compared to other methods,the present method demonstrates superior processing capabilities for the embedded nonlinear GHB strength criterion.展开更多
The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) tri...The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.展开更多
Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(A...Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(Au/CNT-O and Au/CNT-N)catalyst for base-free oxidation of monosaccharide into sugar acid.Au/CNT-O and Au/CNT-N surfaces successfully introduced oxygen-and nitrogen-containing functional groups,respectively.The highest yields of gluconic acid and xylonic acid were 93.3%and 94.3%,respectively,using Au/CNT-N at 90℃ for 240 min,which is higher than that of using Au/CNT-O.The rate constants for monosaccharide decomposition and sugar acid formation in Au/CNT-N system were higher,while the corresponding activation energy was lower than in Au/CNT-O system.DFT calculation revealed that the mechanism of glucose oxidation to gluconic acid involves the adsorption and activation of O_(2),adsorption of glucose,dissociation of the formyl C-H bond and formation of O-H bond,and formation and desorption of gluconic acid.The activation energy barrier for the glucose oxidation over Au/CNT-N is lower than that of Au/CNT-O.The nitrogen-containing functional groups are more beneficial for accelerating monosaccharide oxidation and enhancing sugar acid selectivity than oxygen-containing functional groups.This work presents a useful guidance for designing and developing highly active catalysts for producing high-value-added chemicals from biomass.展开更多
We present a novel approach for tailoring the laser induced surface topography upon femtosecond(fs)pulsed laser irradiation.The method employs spatially controlled double fs laser pulses to actively regulate the hydro...We present a novel approach for tailoring the laser induced surface topography upon femtosecond(fs)pulsed laser irradiation.The method employs spatially controlled double fs laser pulses to actively regulate the hydrodynamic microfluidic motion of the melted layer that gives rise to the structures formation.The pulse train used,in particular,consists of a previously unexplored spatiotemporal intensity combination including one pulse with Gaussian and another with periodically modulated intensity distribution created by Direct Laser Interference Patterning(DLIP).The interpulse delay is appropriately chosen to reveal the contribution of the microfluidic melt flow,while it is found that the sequence of the Gaussian and DLIP pulses remarkably influences the surface profile attained.Results also demonstrate that both the spatial intensity of the double pulse and the effective number of pulses per irradiation spot can further be modulated to control the formation of complex surface morphologies.The underlying physical processes behind the complex patterns’generation were interpreted in terms of a multiscale model combining electron excitation with melt hydrodynamics.We believe that this work can constitute a significant step forward towards producing laser induced surface structures on demand by tailoring the melt microfluidic phenomena.展开更多
Melt extrusion-based additive manufacturing(ME-AM)is a promising technique to fabricate porous scaffolds for tissue engi-neering applications.However,most synthetic semicrystalline polymers do not possess the intrinsi...Melt extrusion-based additive manufacturing(ME-AM)is a promising technique to fabricate porous scaffolds for tissue engi-neering applications.However,most synthetic semicrystalline polymers do not possess the intrinsic biological activity required to control cell fate.Grafting of biomolecules on polymeric surfaces of AM scaffolds enhances the bioactivity of a construct;however,there are limited strategies available to control the surface density.Here,we report a strategy to tune the surface density of bioactive groups by blending a low molecular weight poly(ε-caprolactone)5k(PCL5k)containing orthogonally reactive azide groups with an unfunctionalized high molecular weight PCL75k at different ratios.Stable porous three-dimensional(3D)scaf-folds were then fabricated using a high weight percentage(75 wt.%)of the low molecular weight PCL 5k.As a proof-of-concept test,we prepared films of three different mass ratios of low and high molecular weight polymers with a thermopress and reacted with an alkynated fluorescent model compound on the surface,yielding a density of 201-561 pmol/cm^(2).Subsequently,a bone morphogenetic protein 2(BMP-2)-derived peptide was grafted onto the films comprising different blend compositions,and the effect of peptide surface density on the osteogenic differentiation of human mesenchymal stromal cells(hMSCs)was assessed.After two weeks of culturing in a basic medium,cells expressed higher levels of BMP receptor II(BMPRII)on films with the conjugated peptide.In addition,we found that alkaline phosphatase activity was only significantly enhanced on films contain-ing the highest peptide density(i.e.,561 pmol/cm^(2)),indicating the importance of the surface density.Taken together,these results emphasize that the density of surface peptides on cell differentiation must be considered at the cell-material interface.Moreover,we have presented a viable strategy for ME-AM community that desires to tune the bulk and surface functionality via blending of(modified)polymers.Furthermore,the use of alkyne-azide“click”chemistry enables spatial control over bioconjugation of many tissue-specific moieties,making this approach a versatile strategy for tissue engineering applications.展开更多
文摘A generic method was described to change surface biocompatibihty by introducing reactive functional groups onto surfaces of polymeric substrates and covalently binding them with biomolecules.A block copolymer with protected carboxylic acid functionality,poly（styrene-b-tert-butyl acrylate）（PS-PtBA）,was spin coated from solutions in toluene on a bioinert polystyrene（PS） substrate to form a bilayer structure：a surface layer of the poly（tert-butyl acrylate）（PtBA） blocks that order at the air-polymer interface and a bottom layer of the PS blocks that entangle with the PS substrate.The thickness of the PtBA layer and the area density of tert-butyl ester groups of PtBA increased linearly with the concentration of the spin coating solution until a 2 nm saturated monolayer coverage of PtBA was achieved at the concentration of 0.4%W/W.The protected carboxylic acid groups were generated by exposing the tert-butyl ester groups of PtBA to trifluoroacetic acid （TFA） for bioconjugation with FMRF peptides via amide bonds.The yield of the bioconjugation reaction for the saturated surface was calculated to be 37.1%based on X-ray photoelectron spectroscopy（XPS） measurements.The success of each functionalization step was demonstrated and characterized by XPS and contact angle measurements.This polymer functionalization/modification concept can be virtually applied to any polymeric substrate by choosing appropriate functional block copolymers and biomolecules to attain novel biocompatibility.
基金Supported by the National Natural Science Foundation of China(50933006)the National Basic Research Program of China(2009CB623401)
文摘Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane(MPPM)with lactose-based polyols.The affinity is based on specific complexation between boric acid and saccharide polyols.A photoinduced grafting-chemical reaction sequence was used to prepare these affinity membranes.Poly(2-aminoethyl methacrylate hydrochloride)[poly(AEMA)]was grafted on the surfaces of MPPM by UV-induced graft polymerization.Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with confocal laser scanning microscopy.It is concluded that lactose ligands can be covalently immobilized on the external surface and in the pores by the subsequent coupling of poly(AEMA)with lactobionic acid(LA).Physical and chemical properties of the affinity membranes were characterized by field emission scanning electron microscopy and Fourier Transform Infrared/Attenuated Total Refraction spectroscopy(FT-IR/ATR).3-Aminophenyl boric acid(3-APBA)was removed from aqueous solution by a single piece of lactose-functionalized MPPM in a dynamic filtration system.The results show that the 3-APBA removal reaches an optimal efficiency(39.5%)under the alkaline condition(pH9.1),which can be improved by increasing the immobilization density of LA.Regeneration of these affinity membranes can be easily realized through acid-base washing because the complexation of boric acid and saccharide polyol is reversible.
基金FCT for her Ph.D grant(SFRH/BD/88334/2012).Thanks are due to Aveiro University and to FCT/MEC for the-nancial support to QOPNA(FCT UID/QUI/00062/2013),CICECO-Aveiro Institute of Materials(FCT UID/CTM/50011/2013),CESAM(FCT UID/MAR/LA0017/2013)and CQE(FCT UID/QUI/0100/2013)research units,through national funds and where applicable co-nanced by the FEDER,within the PT2020 Partnership Agreement.
文摘Among the several types of inorganic nanoparticles available,silica nanoparticles(SNP)have earned their relevance in biological applications namely,as bioimaging agents.In fact,uorescent SNP(FSNP)have been explored in this-eld as protective nanocarriers,overcoming some limitations presented by conventional organic dyes such as high photobleaching rates.A crucial aspect on the use of uorescent SNP relates to their surface properties,since it determines the extent of interaction between nanoparticles and biological systems,namely in terms of colloidal stability in water,cellular recognition and internalization,tracking,biodistribution and speci-city,among others.Therefore,it is imperative to understand the mechanisms underlying the interaction between biosystems and the SNP surfaces,making surface functionalization a relevant step in order to take full advantage of particle properties.The versatility of the surface chemistry on silica platforms,together with the intrinsic hydrophilicity and biocompatibility,make these systems suitable for bioimaging applications,such as those mentioned in this review.
基金This research was made possible with the financial support from NSFC China(61275188,61378089,81470029,61361160416)the 863 project,China,the Technology Development Program of Shenzhen City,the Committee of Science and Technology Innovation of Shenzhen(JCYJ20140902110354241)Science and Technology Project of Guangdong Province(2015A010106002).
文摘Surface functionalization of sensor chip for probe immobilization is crucial for the biosensing applications of surface plasmon resonance(SPR)sensors.In this paper,we report a method circulating the dopamine aqueous solution to coat polydopamine film on sensing surface for surface functionalization of SPR chip.The polydopamine film with available thickness can be easily prepared by controlling the circulation time and the biorecognition elements can be immobilized on the polydopamine film for specific molecular interaction analysis.These opera-tions are all performed under flow condition in the fuidic system,and have the advantages of easy implementation,less time consuming,and low cost,because the reagents and devices used in the operations are routinely applied in most laboratories.In this study,the specific absorption between the protein A probe immobilized on the sensing surface and human immunoglobulin G in the buffer is monitored based on this surface functionalization strategy to demonstrated its feasibility for SPR biosensing applications.
基金Project(52105175)supported by the National Natural Science Foundation of ChinaProject(BK20210235)supported by the Natural Science Foundation of Jiangsu Province,ChinaProject(JSSCBS20210121)supported by the Jiangsu Provincial Innovative and Entrepreneurial Doctor Program,China。
文摘Wetting condition of micro/nanostructured surface has received tremendous attention due to the potential applications in commercial,industrial,and military areas.Surfaces with extreme wetting properties,e.g.,superhydrophobic or superhydrophilic,are extensively employed due to their superior anti-icing,drag reduction,enhanced boiling heat transfer,self-cleaning,and anti-bacterial properties depending on solid-liquid interfacial interactions.Laser-based techniques have gained popularity in recent years to create micro/nano-structured surface owing to their high flexibility,system precision,and ease for automation.These techniques create laser induced periodic surface structures(LIPSS)or hierarchical structures on substrate material.However,micro/nanostructures alone cannot attain the desired wettability.Subsequent modification of surface chemistry is essentially needed to achieve target extreme wettability.This review paper aims to provide a comprehensive review for both laser texturing techniques and the following chemistry modification methods.Recent research progress and fundamental mechanisms of surface structure generation via different types of lasers and various chemistry modification methods are discussed.The complex combination between the laser texturing and surface chemistry modification methods to decide the final wetting condition is presented.More importantly,surface functionalities of these surfaces with extreme wetting properties are discussed.Lastly,prospects for future research are proposed and discussed.
文摘BACKGROUND Dry eye disease(DED)is a multifactorial ocular surface disorder with rising prevalence.It is closely related to systemic health and psychological factors,such as sleep and mood disorders,which significantly impact the quality of life of patients.AIM To explore the correlations between ocular surface function,sleep quality,and anxiety/depression in patients with DED.METHODS This was a cross-sectional investigative study that included 358 patients with DED between January 2022 and January 2025.Ocular surface was assessed using the ocular surface disease index(OSDI),tear film break-up time,fluorescein staining score,and Schirmer I test.The Pittsburgh Sleep Quality Index(PSQI),Self-Rating Anxiety Scale(SAS),and Self-Rating Depression Scale(SDS)were used to evaluate sleep quality and anxiety/depression levels.Correlation and linear regression analyses were used to explore the relationships.RESULTS The mean PSQI score of the patients was 9.94±2.18;the mean SAS score was 47.30±4.90,and the mean SDS score was 50.08±5.52.These suggested a prevalence of sleep and psychological abnormalities.There was a significant correlation between the indicators of ocular surface function(OSDI,tear film break-up time,fluorescein staining,and Schirmer I test)and PSQI,SAS,and SDS scores(P<0.05).Moreover,multiple regression revealed that age≥50 years(β=1.55,P=0.029),PSQI scores(β=0.58,P<0.001),SAS scores(β=0.17,P=0.017),and SDS scores(β=0.15,P=0.019)were independent predictors of the OSDI scores.CONCLUSION Ocular surface function in patients with DED is closely related to sleep quality and anxiety/depression,emphasizing the need for holistic clinical management.
基金support from the National Natural Science Foundation of China(Nos.52002015,22275010,22105016,U1707603,21625101 and 21521005)the Fundamental Research Funds for the Central Universities(No.buctrc202006)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(No.FC202203).
文摘Indium-based materials(e.g.,In_(2)O_(3))are a class of promising non-noble metal-based catalysts for electroreduction of carbon dioxide(CO_(2)).However,competitive hydrogen reduction reaction(HER)on indium-based catalysts hampers CO_(2) reduction reaction(CO_(2)RR)process.We herein tune the interfacial microenvironment of In_(2)O_(3) through chemical graft of alkyl phosphoric acid molecules using a facile solution-processed strategy for the first time,which is distinguished from other researches that tailor intrinsic activity of In_(2)O_(3) themselves.The surface functionalization of alkyl phosphoric acids over In_(2)O_(3) is demonstrated to remarkably boost CO_(2) conversion.For example,octadecylphosphonic acid modified In_(2)O_(3) exhibits Faraday efficiency for H_(2) H_(2) H_(2)(FE)of as low as 6.6%and FEHCOOH of 86.5%at-0.67 V vs.RHE,which are far superior to parent In_(2)O_(3) counterparts(FE of 24.0%and FEHCOOH of 63.1%).Moreover,the enhancing effect of alkyl phosphoric acid functionalization is found to be closely related to the length of alkyl chains.By virtue of comprehensive experimental characterizations and molecular dynamics simulations,it is revealed that the modification of alkyl phosphoric acids significantly alters the interface microenvironment of the electrocatalyst,which changes the electrocatalyst surface from hydrophilic and aerophobic to hydrophobic and aerophilic.In this case,the water molecules are pushed away and more CO_(2) molecules are trapped,increasing local CO_(2) concentration at In_(2)O_(3) active sites,thus leading to the significantly enhanced CO_(2)RR and suppressed HER.This work highlights the importance of regulating the interfacial microenvironment of inorganic catalysts by molecular surface functionalization as a means for promoting the electrochemical performance in electrosynthesis and beyond.
基金We would like to thank the National Science Foundation CBET （No. 1512598）, the NSF CAREER Award CBET （No. 1653925） and the American Heart Association （No. 16SDG26940002） for funding support. Finally, we would also like to thank Stacie Chen and Spencer Mamer for stimulating conversation and advice about the paper.
文摘Surface functionalization is a widely adopted technique for surface modification which allows researchers to customize surfaces to integrate with their research. Surface functionalization has been used recently to adapt surfaces to integrate with biological materials specifically to isolate cells or mimic biological tissues through cell patterning. Cell isolation and cell patterning both can be integrated with extant techniques or surfaces to customize the research to whatever needs to be tested. Substrates such as metals, biologically mimicking surfaces, environmental responsive surfaces, and even three-dimensional surfaces such as hydrogels have all been adapted to allow for functionalization for both patterning and isolation. In this review we have described both the advantages and disadvantages of these techniques and the related chemistries to better understand these tools and how best to apply them in the hope that we can further expand upon the research in the field.
基金financially supported by the National Natural Science Foundation of China(52022043 and 21868011)Tsinghua University-Peking Union Medical College Hospital Initiative Scientific Research Program(20191080593)+2 种基金Precision Medicine Foundation,Tsinghua University,China(10001020107)the National Key R&D Program of China(2017YFC1103800)Research Fund of State Key Laboratory of Tribology,Tsinghua University,China(SKLT2022C18).
文摘Osteoarthritis is associated with the significantly increased friction of the joint,which results in progressive and irreversible damage to the articular cartilage.A synergistic therapy integrating lubrication enhancement and drug delivery is recently proposed for the treatment of early-stage osteoarthritis.In the present study,bioinspired by the self-adhesion performance of mussels and super-lubrication property of articular cartilages,a biomimetic self-adhesive dopamine methacrylamide-poly(2-methacryloyloxyethyl phosphorylcholine)(DMA-MPC)copolymer was designed and synthesized via free radical polymerization.The copolymer was successfully modified onto the surface of biodegradable mesoporous silica nanoparticles(bMSNs)by the dip-coating method to prepare the dual-functional nanoparticles(bMSNs@DMA-MPC),which were evaluated using a series of surface characterizations including the transmission electron microscope(TEM),Fourier transform infrared(FTIR)spectrum,thermogravimetric analysis(TGA),X-ray photoelectron spectroscopy(XPS),etc.The tribological test and in vitro drug release test demonstrated that the developed nanoparticles were endowed with improved lubrication performance and achieved the sustained release of an anti-inflammatory drug,i.e.,diclofenac sodium(DS).In addition,the in vitro biodegradation test showed that the nanoparticles were almost completely biodegraded within 10 d.Furthermore,the dual-functional nanoparticles were biocompatible and effectively reduced the expression levels of two inflammation factors such as interleukin-1β(IL-1β)and interleukin-6(IL-6).In summary,the surface functionalized nanoparticles with improved lubrication and local drug release can be applied as a potential intra-articularly injected biolubricant for synergistic treatment of early-stage osteoarthritis.
基金L.K.gratefully acknowledges financial support from the ARC Discovery Project(DP190101607)Z.C.acknowledges the National Science Foundation-Center for the Advancement of Wearable Technologies(CAWT)(Grant 1849243).
文摘Graphene-like borophene was theoretically proposed and recently synthesized on Al(111)surface,however,how to conquer its structural instability is still an open question.By means of density functional theory computations,we theoretically predicted that honeycomb borophene can be well stabilized by double-sided surface passivation with monovalent functional groups(X=F,Cl,Br,I,OH,and NH2)due to the electron redistributions.The system undergoes the transition from metallic to semiconducting upon functionalization,while the energy gap depends on the choice of functional groups.Under external strain,the gap values can be manipulated over a broad range.Our further calculations indicated that the functionalized borophene possesses moderate and anisotropic carrier mobility,which is comparable to or even higher than some 2D materials such as MoS2 and phosphorene.Our work provides a feasible strategy to effectively stabilize the graphene-like borophene and tune the electronic properties with great potentials for electronic applications.
基金financially supported by the National Natural Science Foundation of China(62464010)Spring City Plan-Special Program for Young Talents(K202005007)+3 种基金Yunnan Talents Support Plan for Yong Talents(XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(202101BA070001-138)Key Laboratory of Artificial Microstructures in Yunnan Higher EducationFrontier Research Team of Kunming University 2023。
文摘Zinc-ion batteries(ZIBs)are inexpensive and safe,but side reactions on the Zn anode and Zn dendrite growth hinder their practical applications.In this study,1,3,5-triformylphloroglycerol(Tp)and various diamine monomers(p-phenylenediamine(Pa),benzidine(BD),and 4,4"-diamino-p-terphenyl(DATP))were used to synthesize a series of two-dimensional covalent-organic frameworks(COFs).The resulting COFs were named TpPa,TpBD,and TpDATP,respectively,and they showed uniform zincophilic sites,different pore sizes,and high Young's moduli on the Zn anode.Among them,TpPa and TpBD showed lower surface work functions and higher ion transfer numbers,which were conducive to uniform galvanizing/stripping zinc and inhibited dendrite growth.Theoretical calculations showed that TpPa and TpBD had wider negative potential region and greater adsorption capacity for Zn2+than TpDATP,providing more electron donor sites to coordinate with Zn^(2+).Symmetric cells protected by TpPa and TpBD stably cycled for more than 2300 h,whereas TpDATP@Zn and the bare zinc symmetric cells failed after around 150 and200 h.The full cells containing TpPa and TpBD modification layers also showed excellent cycling capacity at 1 A/g.This study provides comprehensive insights into the construction of highly reversible Zn anodes via COF modification layers for advanced rechargeable ZIBs.
基金supported by the Innovative Research Group Project of the National Natural Science Foundation of China(T2121004)Key Programme(52235007)National Outstanding Youth Foundation of China(52325504).
文摘Hydrogel scaffolds have numerous potential applications in the tissue engineering field.However,tough hydrogel scaffolds implanted in vivo are seldom reported because it is difficult to balance biocompatibility and high mechanical properties.Inspired by Chinese ramen,we propose a universal fabricating method(printing-P,training-T,cross-linking-C,PTC&PCT)for tough hydrogel scaffolds to fill this gap.First,3D printing fabricates a hydrogel scaffold with desired structures(P).Then,the scaffold could have extraordinarily high mechanical properties and functional surface structure by cycle mechanical training with salting-out assistance(T).Finally,the training results are fixed by photo-cross-linking processing(C).The tough gelatin hydrogel scaffolds exhibit excellent tensile strength of 6.66 MPa(622-fold untreated)and have excellent biocompatibility.Furthermore,this scaffold possesses functional surface structures from nanometer to micron to millimeter,which can efficiently induce directional cell growth.Interestingly,this strategy can produce bionic human tissue with mechanical properties of 10 kPa-10 MPa by changing the type of salt,and many hydrogels,such as gelatin and silk,could be improved with PTC or PCT strategies.Animal experiments show that this scaffold can effectively promote the new generation of muscle fibers,blood vessels,and nerves within 4 weeks,prompting the rapid regeneration of large-volume muscle loss injuries.
文摘Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.
基金financially supported by the Shenzhen Science and Technology Project(Project Nos.JCYJ20220818102201003,JCYJ20220818100001002)the Shenzhen Sustainable Development Special Project(Project No.KCXFZ20230731094500001)+1 种基金the National Natural Science Foundation of China(Project Nos.51975597,52175446)the Natural Science Foundation of Guangdong Province(Project No.2022B1515020011)。
文摘Magnetically responsive microstructured functional surface(MRMFS),capable of dynamically and reversibly switching the surface topography under magnetic actuation,provides a wireless,noninvasive,and instantaneous way to accurately control the microscale engineered surface.In the last decade,many studies have been conducted to design and optimize MRMFSs for diverse applications,and significant progress has been accomplished.This review comprehensively presents recent advancements and the potential prospects in MRMFSs.We first classify MRMFSs into one-dimensional linear array MRMFSs,two-dimensional planar array MRMFSs,and dynamic self-assembly MRMFSs based on their morphology.Subsequently,an overview of three deformation mechanisms,including magnetically actuated bending deformation,magnetically driven rotational deformation,and magnetically induced self-assembly deformation,are provided.Four main fabrication strategies employed to create MRMFSs are summarized,including replica molding,magnetization-induced self-assembly,laser cutting,and ferrofluid-infused method.Furthermore,the applications of MRMFS in droplet manipulation,solid transport,information encryption,light manipulation,triboelectric nanogenerators,and soft robotics are presented.Finally,the challenges that limit the practical applications of MRMFSs are discussed,and the future development of MRMFSs is proposed.
基金Project(52278380)supported by the National Natural Science Foundation of ChinaProject(2023JJ30670)supported by the National Science Foundation of and Technology Major Project of Hunan Province,China。
文摘This study proposes an alternative calculation mode for stresses on the slip surface(SS).The calculation of the normal stress(NS)on the SS involves examining its composition and expanding its unknown using the Taylor series.This expansion enables the reasonable construction of a function describing the NS on the SS.Additionally,by directly incorporating the nonlinear Generalized Hoke-Brown(GHB)strength criterion and utilizing the slope factor of safety(FOS)definition,a function of the shear stress on the SS is derived.This function considers the mutual feedback mechanism between the NS and strength parameters of the SS.The stress constraints conditions are then introduced at both ends of the SS based on the spatial stress relation of one point.Determining the slope FOS and stress solution for the SS involves considering the mechanical equilibrium conditions and the stress constraint conditions satisfied by the sliding body.The proposed approach successfully simulates the tension-shear stress zone near the slope top and provides an intuitive description of the concentration effect of compression-shear stress of the SS near the slope toe.Furthermore,compared to other methods,the present method demonstrates superior processing capabilities for the embedded nonlinear GHB strength criterion.
基金Project(2012CB722803)supported by the Key Project of National Basic Research and Development Program of ChinaProject(U1202271)supported by the National Natural Science Foundation of ChinaProject(IRT1250)supported by the Program for Innovative Research Team in University of Ministry of Education of China
文摘The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.
基金supported by the National Youth Talent Support Program,National Natural Science Foundation of China(No.31971614)State Key Laboratory of Pulp and Paper Engineering(No.2022PY02)+3 种基金the National Program for Support of Topnotch Young Professionals(No.x2qsA4210090)Guangdong Basic and Applied Basic Research Foundation(Nos.2021A1515110205,2021A1515110622,2021A1515110245 and 2020A1515110705)Science and Technology Basic Resources Investigation Program of China(No.2019FY100900)the National Key Research and Development Program of China(No.2021YFC2101604).
文摘Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(Au/CNT-O and Au/CNT-N)catalyst for base-free oxidation of monosaccharide into sugar acid.Au/CNT-O and Au/CNT-N surfaces successfully introduced oxygen-and nitrogen-containing functional groups,respectively.The highest yields of gluconic acid and xylonic acid were 93.3%and 94.3%,respectively,using Au/CNT-N at 90℃ for 240 min,which is higher than that of using Au/CNT-O.The rate constants for monosaccharide decomposition and sugar acid formation in Au/CNT-N system were higher,while the corresponding activation energy was lower than in Au/CNT-O system.DFT calculation revealed that the mechanism of glucose oxidation to gluconic acid involves the adsorption and activation of O_(2),adsorption of glucose,dissociation of the formyl C-H bond and formation of O-H bond,and formation and desorption of gluconic acid.The activation energy barrier for the glucose oxidation over Au/CNT-N is lower than that of Au/CNT-O.The nitrogen-containing functional groups are more beneficial for accelerating monosaccharide oxidation and enhancing sugar acid selectivity than oxygen-containing functional groups.This work presents a useful guidance for designing and developing highly active catalysts for producing high-value-added chemicals from biomass.
基金support by the European Union’s Horizon 2020 research and innovation program through the project BioCombs4Nanofibres(Grant Agreement No.862016)。
文摘We present a novel approach for tailoring the laser induced surface topography upon femtosecond(fs)pulsed laser irradiation.The method employs spatially controlled double fs laser pulses to actively regulate the hydrodynamic microfluidic motion of the melted layer that gives rise to the structures formation.The pulse train used,in particular,consists of a previously unexplored spatiotemporal intensity combination including one pulse with Gaussian and another with periodically modulated intensity distribution created by Direct Laser Interference Patterning(DLIP).The interpulse delay is appropriately chosen to reveal the contribution of the microfluidic melt flow,while it is found that the sequence of the Gaussian and DLIP pulses remarkably influences the surface profile attained.Results also demonstrate that both the spatial intensity of the double pulse and the effective number of pulses per irradiation spot can further be modulated to control the formation of complex surface morphologies.The underlying physical processes behind the complex patterns’generation were interpreted in terms of a multiscale model combining electron excitation with melt hydrodynamics.We believe that this work can constitute a significant step forward towards producing laser induced surface structures on demand by tailoring the melt microfluidic phenomena.
基金the European Research Council starting grant “Cell Hybridge” for financial support under the Horizon2020 framework program (Grant#637308)the Province of Limburg for support and funding
文摘Melt extrusion-based additive manufacturing(ME-AM)is a promising technique to fabricate porous scaffolds for tissue engi-neering applications.However,most synthetic semicrystalline polymers do not possess the intrinsic biological activity required to control cell fate.Grafting of biomolecules on polymeric surfaces of AM scaffolds enhances the bioactivity of a construct;however,there are limited strategies available to control the surface density.Here,we report a strategy to tune the surface density of bioactive groups by blending a low molecular weight poly(ε-caprolactone)5k(PCL5k)containing orthogonally reactive azide groups with an unfunctionalized high molecular weight PCL75k at different ratios.Stable porous three-dimensional(3D)scaf-folds were then fabricated using a high weight percentage(75 wt.%)of the low molecular weight PCL 5k.As a proof-of-concept test,we prepared films of three different mass ratios of low and high molecular weight polymers with a thermopress and reacted with an alkynated fluorescent model compound on the surface,yielding a density of 201-561 pmol/cm^(2).Subsequently,a bone morphogenetic protein 2(BMP-2)-derived peptide was grafted onto the films comprising different blend compositions,and the effect of peptide surface density on the osteogenic differentiation of human mesenchymal stromal cells(hMSCs)was assessed.After two weeks of culturing in a basic medium,cells expressed higher levels of BMP receptor II(BMPRII)on films with the conjugated peptide.In addition,we found that alkaline phosphatase activity was only significantly enhanced on films contain-ing the highest peptide density(i.e.,561 pmol/cm^(2)),indicating the importance of the surface density.Taken together,these results emphasize that the density of surface peptides on cell differentiation must be considered at the cell-material interface.Moreover,we have presented a viable strategy for ME-AM community that desires to tune the bulk and surface functionality via blending of(modified)polymers.Furthermore,the use of alkyne-azide“click”chemistry enables spatial control over bioconjugation of many tissue-specific moieties,making this approach a versatile strategy for tissue engineering applications.
