Recently published in Joule,Feng Liu and colleagues from Shanghai Jiaotong University reported a record-breaking 20.8%power conversion efficiency in organic solar cells(OSCs)with an interpenetrating fibril network act...Recently published in Joule,Feng Liu and colleagues from Shanghai Jiaotong University reported a record-breaking 20.8%power conversion efficiency in organic solar cells(OSCs)with an interpenetrating fibril network active layer morphology,featuring a bulk p-in structure and proper vertical segregation achieved through additive-assisted layer-by-layer deposition.This optimized hierarchical gradient fibrillar morphology and optical management synergistically facilitates exciton diffusion,reduces recombination losses,and enhances light capture capability.This approach not only offers a solution to achieving high-efficiency devices but also demonstrates the potential for commercial applications of OSCs.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
Objective Previous studies indicated a close correlation between manual acupuncture(MA)analgesia and the mobilization of extracellular adenosine triphosphate(ATP)at the acupoints.This study attempted to investigate wh...Objective Previous studies indicated a close correlation between manual acupuncture(MA)analgesia and the mobilization of extracellular adenosine triphosphate(ATP)at the acupoints.This study attempted to investigate whether this relationship is altered with the manipulation patterns of MA.Additionally,we further testified whether these two events parallelly varied with different frequencies of electroacupuncture(EA).Methods Male SD rats were randomly divided into four groups:blank group,model group,MA group,and EA group.MA group was further divided into four sub-groups:standard MA,sham MA,lifting-thrusting MA,and shallow MA.Similarly,EA group was categorized based on current frequency into 2 Hz,2–100 Hz,100 Hz,and ARL67156+100 Hz sub-groups.For the behavioral tests,each group comprised 4–8 rats;for extracellular ATP assessment,each group consisted of 3–6 rats.Complete Freund’s adjuvant(CFA)was injected into the left ankle joint cavity to create an acute adjuvant arthritis(AA)model.A 20-minute session of either MA at left Zusanli(ST36)or EA at bilateral ST36 was administered on AA rats.Thermal hyperalgesia of the hind paw was determined.Extracellular ATP in the interstitial space at ST36(inters.ATP)was extracted using microdialysis and quantified via a luciferase-luciferin assay.Results Modeling induced tenderness at ST36(P<0.001)and higher ATP mobilization(P<0.05)in response to MA.Both standard MA(P<0.001)and lifting-thrusting manipulation(P<0.001)exhibited a remarkable analgesic effect,which was not observed with sham MA,deep insertion plus retention.Verum MA(P<0.001)rather than sham intervention,significantly elevated inters.ATP levels.Notably,shallow MA,penetrating the skin layer and needling with twirling-rotating,demonstrated analgesia and increasing inters.ATP level(P<0.05).Regarding EA,treatments at frequencies of 2 Hz(P<0.01),2–100 Hz(P<0.05),and 100 Hz(P<0.05)significantly alleviated pain.Only the 2–100 Hz(P<0.05)and 100 Hz(P<0.01)interventions,particularly in the latter,potentiated ATP mobilization.Preventing ATP hydrolysis dampened the analgesic effects of the standard MA and 100 Hz EA.Conclusion There is a general correlation between ATP mobilization at the acupoint and the analgesic effect of MA and EA.However,the underlying mechanisms related to shallow MA and 2 Hz EA remain to be elucidated.展开更多
Objective The analgesic effect of acupuncture has been widely accepted.Nevertheless,the mechanism behind its analgesic effect remains elusive,thus impeding the progress of research geared toward enhancing the analgesi...Objective The analgesic effect of acupuncture has been widely accepted.Nevertheless,the mechanism behind its analgesic effect remains elusive,thus impeding the progress of research geared toward enhancing the analgesic effect of acupuncture.This paper investigated the role of acupuncture needle surface textures on acupuncture’s analgesic effect by creating four experimental acupuncture needles with different patterns of surface augmentation.Methods Four types of acupuncture needles with different surface textures(the lined needle,circle needle,sandpaper needle,and threaded needle)were designed.Additionally,the force/torque measurement system used a robot arm and mechanical sensor to measure the force on the needle during insertion and manipulation.To perform acupuncture analgesia experiments,four experimental acupuncture needles and a normal needle were inserted into the Zusanli(ST36)acupoint of rats with inflammatory pain.By comparing the force and torque and the analgesic efficacy of the different acupuncture needles,these experiments tested the role of acupuncture needle body texture on acupuncture analgesia.Results The analgesic effects of different acupuncture needle body textures varied.Specifically,the force required to penetrate the skin with the lined needle was not greater than that for the normal needle;however,the needle with inscribed circles and the sandpaper-roughened needle both required greater force for insertion.Additionally,the torque of the lined needle reached 2×10^(-4)N·m under twisting manipulation,which was four times greater the torque of a normal needle(5×10^(-5)N·m).Furthermore,the lined needle improved pain threshold and mast cell degranulation rate compared to the normal needle.Conclusion Optimizing the texture of acupuncture needles can enhance acupuncture analgesia.The texture of our experimental acupuncture needles had a significant impact on the force needed to penetrate the skin and the torque needed to manipulate the needle;it was also linked to variable analgesic effects.This study provides a theoretical basis for enhancing the analgesic efficacy of acupuncture through the modification of needles and promoting the development of acupuncture therapy.展开更多
Eu^(2+)doped fluorosilicate glass-ceramics containing BaF_(2) nanocrystals have high potential as spectral conversion materials for organic solar cells.However,it is difficult to realize the efficient design of BaF_(2...Eu^(2+)doped fluorosilicate glass-ceramics containing BaF_(2) nanocrystals have high potential as spectral conversion materials for organic solar cells.However,it is difficult to realize the efficient design of BaF_(2):Eu^(2+)doped fluorosilicate glass and to vividly observe the glass microstructure in experiment through traditional trial-and-error glass preparation method.BaF_(2):Eu^(2+)doped fluorosilicate glassceramics with high transparency,and high photoluminescence(PL)performance were predicted,designed and prepared via molecular dynamics(MD)simulation method.By MD simulation prediction,self-organized nanocrystallization was realized to inhibit the abnormal growth of nanocrystals due to[AlO_(4)]tetrahedra formed in the fluoride-oxide interface.The introduction of NaF reduces the effective phonon energy of the glass because Na+will prompt Al^(3+)to migrate from the fluoride phase to the silicate phase and interface.The local environment of Eu^(2+)is optimized by predicting the doping concentration of EuF_(3) and 2 mol%EuF3 is the best concentration in this work.Glass-ceramics sample GC2Eu as spectral conversion layer was successfully applied on organic solar cells to obtain more available visible phonons with a high photoelectric conversion efficiency(PCE).This work confirms the guidance of molecular dynamics simulation methods for fluorosilicate glasses design.展开更多
The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its ...The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.展开更多
Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a...Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a grand challenge to realize self-sustained motion in soft robots subject to unchanging environment,without complex geometry or a control module.In this work,we report soft robots based on an anisotropic cylindrical hydrogel showing self-regulated,continuous rolling motions under constant light irradiation.The robots are animated by mirror-symmetry-breaking induced by photothermal strain gradient.The self-sustained motion is attributed to the fast and reversible deformation of the gel and the autonomous refresh of the irradiated region during the rolling motion.The hydrogel robots can reach a rolling speed of 1.27 mm·s^(-1)on a horizonal surface and even climb a ramp of 18°at a speed of 0.57 mm·s^(-1)in an aqueous environment.Furthermore,the hydrogel robots can overcome an obstacle,with rolling direction controllable through irradiation angle of the light and local irradiation on selective regions.This work suggests a facile strategy to develop hydrogel robots and may provide unforeseen inspirations for the design of self-regulated soft robots by using other intelligent materials.展开更多
Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change ma...Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change materials.Here,we report a tiramisu-like composite(GMP),where the typical“crust-and-cheese”hierarchical structure is replicated by an innovative two-step bidirectional freezing assembly(BFA)and compressive densification.Hierarchical-aligned graphene array(G-GA)with ultralow thermal resistance is fabricated through 1st BFA and graphitization.During the 2nd BFA,the MXene-CNF crosslinking network with hydrogen-bond actions is used for encapsulating polyethylene glycol(PEG)onto the microlayers of the G-GA skeleton.Remarkably,the microlaminated GMP4 achieves a recorded TC of 34.05 W m^(-1) K^(-1),unprecedented EMI SE of 87.4 dB,and preferable enthalpy density of 179.4 J cm^(-3),along with leakage-free function,and eminent thermal durability.Furthermore,the GMP-loaded equipment is demonstrated for efficient microelectronics cooling and sustainable solar energy utilization.This work opens new avenues for multiscale designing multifunctional macro-composites,broadening the application prospects in advanced electronics and solar energy utilization systems.展开更多
Nitric oxide(NO)modulates several cancer-related physiological processes and has advanced the development of green methods for cancer treatment and integrated platforms for combination or synergistic therapies.Althoug...Nitric oxide(NO)modulates several cancer-related physiological processes and has advanced the development of green methods for cancer treatment and integrated platforms for combination or synergistic therapies.Although a nanoengineering strategy has been proposed to overcome deficiencies of NO gas or small NO donor molecules,such as short half-life,lipophilicity,non-selectivity,and poor stability,it remains challenging to prepare NO nanomedicines with simple composition,multiple functions and enhanced therapeutic efficacy.Herein,we build a liquid metal nanodroplet(LMND)-based NO nanogenerator(LMND@HSG)that is stabilized by a bioreducible guanylated hyperbranched poly(amido amine)(HSG)ligand.Mechanically,the tumor microenvironment specifically triggers a cascade process of glutathione elimination,reactive oxygen species(ROS)generation,and NO release.According to actual demand,the ROS and NO concentrations could be readily controlled by tuning the LMND and HSG feed amounts.Along with the intrinsic anticancer property of LMND(ROS-mediated apoptosis and anti-angiogenesis),LMND@HSG administration could further enhance tumor growth suppression compared with LMND and HSG alone.Fromthis study,leveraging LMND for NO gas therapy provides more possibilities for the prospect of LMND-based anticancer nanomedicines.展开更多
A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids...A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.展开更多
Axonal regeneration and ifber regrowth is limited in the adult central nervous system, but re-search over the last decades has revealed a high intrinsic capacity of brain and spinal cord circuits to adapt and reorgani...Axonal regeneration and ifber regrowth is limited in the adult central nervous system, but re-search over the last decades has revealed a high intrinsic capacity of brain and spinal cord circuits to adapt and reorganize after smaller injuries or denervation. Short-distance ifber growth and synaptic rewiring was found in cortex, brain stem and spinal cord and could be associated with restoration of sensorimotor functions that were impaired by the injury. Such processes of struc-tural plasticity were initially observed in the corticospinal system following spinal cord injury or stroke, but recent studies showed an equally high potential for structural and functional reorganization in reticulospinal, rubrospinal or propriospinal projections. Here we review the lesion-induced plastic changes in the propriospinal pathways, and we argue that they represent a key mechanism triggering sensorimotor recovery upon incomplete spinal cord injury. The for-mation or strengthening of spinal detour pathways bypassing supraspinal commands around the lesion site to the denervated spinal cord were identiifed as prominent neural substrate inducing substantial motor recovery in different species from mice to primates. Indications for the exis-tence of propriospinal bypasses were also found in humans after cortical stroke. It is mandatory for current research to dissect the biological mechanisms underlying spinal circuit remodeling and to investigate how these processes can be stimulated in an optimal way by therapeutic inter-ventions (e.g., ifber-growth enhancing interventions, rehabilitation). This knowledge will clear the way for the development of novel strategies targeting the remarkable plastic potential of pro-priospinal circuits to maximize functional recovery after spinal cord injury.展开更多
Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable s...Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone)(PCL) via Janus polymerization, which comprises cationic ring-opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl)oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)3)and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CLb-(CL-r-CO)) can be modulated by various RE(OTf)3. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)3 catalysts used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively, via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides, as confirmed by FTIR analyses. According to NMR and SEC analyses, copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures. The investigations on thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to sei住assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining onestep Janus polymerization and precise post-polymerization click reaction.展开更多
Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unl...Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.展开更多
In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for rin...In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for ring-opening(co)polymerizations.Second,a catalyst-free polycondensation mechanism was proposed for the production of polyesters with high molecular weights.Third,a co-assembly method that can fabricate films and coatings with controllable structures and properties on various substrates was demonstrated,providing a platform for the construction of novel surface coatings.Forth,facile methods for producing high-productivity poly(propylene carbonate)and semicrystalline polyester have been discovered.And linear non-conjugated polyesters exhibiting yellow-green clusteroluminescence were developed for the first time.Fifth,a supramolecular prodrug nano-assembly strategy has been developed for reactive nitrogen species potentiated chemotherapy.Sixth,a series of tough and stiff supramolecular hydrogels with shape memory properties have been used for information encryption.Seventh,reversible fusion and fission of wet-spun graphene oxide fibers has been successfully achieved.Eighth,three non-conjugated polypeptides were synthesized and the mechanism of clusteroluminescence was studied.Ninth,a series of conducting covalent organic frameworks with high electrical conductivity and carrier mobility have been used as high-performance chemiresistor,electrocatalyst,and organic field-effect transistor.Tenth,the exploration of non-fused electron acceptors,and their photostable mechanism are exemplified for developing high-performance,low-cost and eco-friendly polymer solar cells.Finally,gel-grown long-range ordering bulk-heterojunctions has achieved improved X-ray detector performance.展开更多
In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed an...In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed and synthesized facilely, exhibiting outstanding reactivity, thermalstability and productivity in different kinds of polymerization and cycloaddition reactions. Second, a variety of chalcogen(O, S, Se)-rich polymers had been synthesized via organocatalysis and fabricated to be the ionic conductive and photoluminescent materials. Third, diverse microenvironment-sensitive nanoparticles had been designed,and novel strategies had been realized, to enhance the therapeutic efficacy in cancer as well as biofilmassociated infections. Fourth, m6 A modification on cellular transcriptome-wide messenger RNA had been successfully mapped at single base resolution using a metabolic labeling method. Fifth, a hydrogel-based robot had been developed, showing swift locomotion as a response to dynamic light stimulations. Sixth,the conformation-size scaling law and the conformation evolution map of 2 D macromolecules in solution had been elucidated experimentally, in the single-layer graphene oxide model. Seventh, semitransparent polymer solar cells, promising as building-integrated photovoltaics, have been developed with the fine balance among power conversion efficiency, visible light transparency and infrared photon radiation rejection. Finally, long-range ordered bulk-heterojunctions of organic semiconductors had been achieved,and their superior optoelectronic properties and potential application in photoelectric conversion had been revealed. The related work progresses are reviewed in this paper.展开更多
Both terminated functional isotactic polypropylene (iPP) and block copolymers containing iPP segment are desirable for commercial applications. This paper provides a convenient, highly-efficient method to prepare hy...Both terminated functional isotactic polypropylene (iPP) and block copolymers containing iPP segment are desirable for commercial applications. This paper provides a convenient, highly-efficient method to prepare hydroxyl-terminated isotactic polypropylene (iPP-t-OH) and functional di-block copolymer containing the iPP segment through a combination of coordination polymerization and coupling reaction. The coordination polymerization was catalyzed by TiCI4/MgCI2/AIEt3 catalyst system using ZnEt2 as chain transfer agent. Further, the Zn-terminated iPP was oxidized and subsequently hydrolyzed to provide iPP-t-OH. Soxhlet extraction and 13C NMR were used to calculate the isotacticity of iPP-t-OH. The degree of polymerization and the number of hydroxyl groups at the chain end of iPP-t-OH were measured by GPC and 1H NMR. Despite the high molecular weight and heterogeneous reaction, iPP-t-OH is effectively linked with PEG-t-NCO to produce di-block copolymers. DSC analysis of the di-block copolymer shows an obvious decrease in Tm and To, which indicated that PEG was successfully linked to the terminal end of iPP.展开更多
Marine biofouling is a worldwide challenge that needs to be solved urgently.Poly(dimethylsiloxane)(PDMS)-based fouling release coatings with low surface free energy(SFE)could effectively inhibit bio-fouling.Neverthele...Marine biofouling is a worldwide challenge that needs to be solved urgently.Poly(dimethylsiloxane)(PDMS)-based fouling release coatings with low surface free energy(SFE)could effectively inhibit bio-fouling.Nevertheless,their poor mechanical durability,adhesive strength,and antifouling performance under static conditions significantly limit their applications.Herein,a novel mechanically robust Al_(2)O_(3)-PDMS-Cu composite coating with strong adhesive strength and remarkable antifouling performance was developed.The Al_(2)O_(3)-PDMS-Cu coating loaded with a small amount of Cu was fabricated by infiltrating PDMS into plasma-sprayed micro/nano-scaled porous Al_(2)O_(3)-Cu coating.Results showed that the fabri-cation of this Al_(2)O_(3)-PDMS-Cu coating did not alter the surface hydrophobicity and SFE of PDMS signif-icantly,thus presenting little influence on its inherent fouling release property.After rigorous abrasion test,the Al_(2)O_(3)-PDMS-Cu coating presented remarkably improved surface hydrophobicity due to the ex-posure of micro/nano structure,rather than falling offas that of PDMS coating.The combination of excel-lent abrasion resistance and one order of magnitude higher adhesive strength and hardness than PDMS coating contributed to the outstanding mechanical robustness of Al_(2)O_(3)-PDMS-Cu coating.Additionally,the antifouling assays against marine bacteria adhesion(95%reduction rate for Escherichia coli.(E.coli))and algae attachment(96%and 94%reduction rates for Chlorella and Phaeodactylum tricornutum(P.tricor-nutum),respectively after 21 days of incubation)demonstrated the superior antifouling performance of the Al_(2)O_(3)-PDMS-Cu coating.Thus,a high-performance Al_(2)O_(3)-PDMS-Cu antifouling coating with excellent mechanical robustness and long-term antifouling performance was achieved via the combination of me-chanical durability of Al_(2)O_(3)skeleton and the dual-functional antifouling strategy,i.e.,the fouling release property of PDMS and fouling resistance of Cu.展开更多
Semitransparent organic solar cells(ST-OSCs)have the potentials to open promising applications that differ from those of conventional inorganic ones,such as see-through power windows with both energy generation and he...Semitransparent organic solar cells(ST-OSCs)have the potentials to open promising applications that differ from those of conventional inorganic ones,such as see-through power windows with both energy generation and heat insulation functions.However,to achieve so,there remain significant challenges,especially for balancing critical parameters,such as power conversion efficiency(PCE),average visible transparency(AVT)and low energy infrared photon radiation rejection(IRR)to realize the full potentials of ST-OSCs.Herein,we demonstrate the new design of ST-OSCs through the rational integration of organic materials,transparent electrode and infrared photon reflector in one device.With the assistance of optical simulation,new ST-OSCs with precise layout exhibit state-of-art performance,with near 30%AVT and PCE of 7.3%,as well as an excellent IRR of over 93%(780-2500 nm),representing one of best multifunctional ST-OSCs with promising perspective for window application.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
BACKGROUND Accurate condition assessment is critical for improving the prognosis of neonatal respiratory distress syndrome(RDS),but current assessment methods for RDS pose a cumulative risk of harm to neonates.Thus,a ...BACKGROUND Accurate condition assessment is critical for improving the prognosis of neonatal respiratory distress syndrome(RDS),but current assessment methods for RDS pose a cumulative risk of harm to neonates.Thus,a less harmful method for assessing the health of neonates with RDS is needed.AIM To analyze the relationships between pulmonary ultrasonography and respiratory distress scores,oxygenation index,and chest X-ray grade of neonatal RDS to identify predictors of neonatal RDS severity.METHODS This retrospective study analyzed the medical information of 73 neonates with RDS admitted to the neonatal intensive care unit of Liupanshui Maternal and Child Care Service Center between April and December 2022.The pulmonary ultrasonography score,respiratory distress score,oxygenation index,and chest Xray grade of each newborn before and after treatment were collected.Spearman correlation analysis was performed to determine the relationships among these values and neonatal RDS severity.RESULTS The pulmonary ultrasonography score,respiratory distress score,oxygenation index,and chest X-ray RDS grade of the neonates were significantly lower after treatment than before treatment(P<0.05).Spearman correlation analysis showed that before and after treatment,the pulmonary ultrasonography score of neonates with RDS was positively correlated with the respiratory distress score,oxygenation index,and chest X-ray grade(ρ=0.429–0.859,P<0.05).Receiver operating characteristic curve analysis indicated that pulmonary ultrasonography screening effectively predicted the severity of neonatal RDS(area under the curve=0.805–1.000,P<0.05).CONCLUSION The pulmonary ultrasonography score was significantly associated with the neonatal RDS score,oxygenation index,and chest X-ray grade.The pulmonary ultrasonography score was an effective predictor of neonatal RDS severity.展开更多
基金Technology Development Program of Jilin Province(YDZJ202201ZYTS640)the National Key Research and Development Program of China(2022YFB4200400)funded by MOST+4 种基金the National Natural Science Foundation of China(52172048 and 52103221)Shandong Provincial Natural Science Foundation(ZR2021QB024 and ZR2021ZD06)Guangdong Basic and Applied Basic Research Foundation(2023A1515012323,2023A1515010943,and 2024A1515010023)the Qingdao New Energy Shandong Laboratory open Project(QNESL OP 202309)the Fundamental Research Funds of Shandong University.
文摘Recently published in Joule,Feng Liu and colleagues from Shanghai Jiaotong University reported a record-breaking 20.8%power conversion efficiency in organic solar cells(OSCs)with an interpenetrating fibril network active layer morphology,featuring a bulk p-in structure and proper vertical segregation achieved through additive-assisted layer-by-layer deposition.This optimized hierarchical gradient fibrillar morphology and optical management synergistically facilitates exciton diffusion,reduces recombination losses,and enhances light capture capability.This approach not only offers a solution to achieving high-efficiency devices but also demonstrates the potential for commercial applications of OSCs.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金Supported by National Natural Science Foundation of China:8247464082174488+1 种基金Natural Science Foundation of Shanghai:22ZR1461500Shanghai Key Laboratory for Acupuncture Mechanism and Acupoint Function:21DZ2271800。
文摘Objective Previous studies indicated a close correlation between manual acupuncture(MA)analgesia and the mobilization of extracellular adenosine triphosphate(ATP)at the acupoints.This study attempted to investigate whether this relationship is altered with the manipulation patterns of MA.Additionally,we further testified whether these two events parallelly varied with different frequencies of electroacupuncture(EA).Methods Male SD rats were randomly divided into four groups:blank group,model group,MA group,and EA group.MA group was further divided into four sub-groups:standard MA,sham MA,lifting-thrusting MA,and shallow MA.Similarly,EA group was categorized based on current frequency into 2 Hz,2–100 Hz,100 Hz,and ARL67156+100 Hz sub-groups.For the behavioral tests,each group comprised 4–8 rats;for extracellular ATP assessment,each group consisted of 3–6 rats.Complete Freund’s adjuvant(CFA)was injected into the left ankle joint cavity to create an acute adjuvant arthritis(AA)model.A 20-minute session of either MA at left Zusanli(ST36)or EA at bilateral ST36 was administered on AA rats.Thermal hyperalgesia of the hind paw was determined.Extracellular ATP in the interstitial space at ST36(inters.ATP)was extracted using microdialysis and quantified via a luciferase-luciferin assay.Results Modeling induced tenderness at ST36(P<0.001)and higher ATP mobilization(P<0.05)in response to MA.Both standard MA(P<0.001)and lifting-thrusting manipulation(P<0.001)exhibited a remarkable analgesic effect,which was not observed with sham MA,deep insertion plus retention.Verum MA(P<0.001)rather than sham intervention,significantly elevated inters.ATP levels.Notably,shallow MA,penetrating the skin layer and needling with twirling-rotating,demonstrated analgesia and increasing inters.ATP level(P<0.05).Regarding EA,treatments at frequencies of 2 Hz(P<0.01),2–100 Hz(P<0.05),and 100 Hz(P<0.05)significantly alleviated pain.Only the 2–100 Hz(P<0.05)and 100 Hz(P<0.01)interventions,particularly in the latter,potentiated ATP mobilization.Preventing ATP hydrolysis dampened the analgesic effects of the standard MA and 100 Hz EA.Conclusion There is a general correlation between ATP mobilization at the acupoint and the analgesic effect of MA and EA.However,the underlying mechanisms related to shallow MA and 2 Hz EA remain to be elucidated.
基金funded by National Natural Science Foundation of China(No.12172092,82174488,and 82305416)Shanghai Key Laboratory of Acupuncture Mechanism and Acupoint Function(No.21DZ2271800)+1 种基金Shanghai Municipal Science and Technology Commission(No.23YF1418300)Scientific Research Project on Traditional Chinese Medicine of Shanghai Municipal Health Commission—Youth Guidance Category(No.2022QN018).
文摘Objective The analgesic effect of acupuncture has been widely accepted.Nevertheless,the mechanism behind its analgesic effect remains elusive,thus impeding the progress of research geared toward enhancing the analgesic effect of acupuncture.This paper investigated the role of acupuncture needle surface textures on acupuncture’s analgesic effect by creating four experimental acupuncture needles with different patterns of surface augmentation.Methods Four types of acupuncture needles with different surface textures(the lined needle,circle needle,sandpaper needle,and threaded needle)were designed.Additionally,the force/torque measurement system used a robot arm and mechanical sensor to measure the force on the needle during insertion and manipulation.To perform acupuncture analgesia experiments,four experimental acupuncture needles and a normal needle were inserted into the Zusanli(ST36)acupoint of rats with inflammatory pain.By comparing the force and torque and the analgesic efficacy of the different acupuncture needles,these experiments tested the role of acupuncture needle body texture on acupuncture analgesia.Results The analgesic effects of different acupuncture needle body textures varied.Specifically,the force required to penetrate the skin with the lined needle was not greater than that for the normal needle;however,the needle with inscribed circles and the sandpaper-roughened needle both required greater force for insertion.Additionally,the torque of the lined needle reached 2×10^(-4)N·m under twisting manipulation,which was four times greater the torque of a normal needle(5×10^(-5)N·m).Furthermore,the lined needle improved pain threshold and mast cell degranulation rate compared to the normal needle.Conclusion Optimizing the texture of acupuncture needles can enhance acupuncture analgesia.The texture of our experimental acupuncture needles had a significant impact on the force needed to penetrate the skin and the torque needed to manipulate the needle;it was also linked to variable analgesic effects.This study provides a theoretical basis for enhancing the analgesic efficacy of acupuncture through the modification of needles and promoting the development of acupuncture therapy.
基金Project supported by the National Natural Science Foundation of China(52172008,51872255)the Key Research and Development Project of Zhejiang Province(2021C01174)。
文摘Eu^(2+)doped fluorosilicate glass-ceramics containing BaF_(2) nanocrystals have high potential as spectral conversion materials for organic solar cells.However,it is difficult to realize the efficient design of BaF_(2):Eu^(2+)doped fluorosilicate glass and to vividly observe the glass microstructure in experiment through traditional trial-and-error glass preparation method.BaF_(2):Eu^(2+)doped fluorosilicate glassceramics with high transparency,and high photoluminescence(PL)performance were predicted,designed and prepared via molecular dynamics(MD)simulation method.By MD simulation prediction,self-organized nanocrystallization was realized to inhibit the abnormal growth of nanocrystals due to[AlO_(4)]tetrahedra formed in the fluoride-oxide interface.The introduction of NaF reduces the effective phonon energy of the glass because Na+will prompt Al^(3+)to migrate from the fluoride phase to the silicate phase and interface.The local environment of Eu^(2+)is optimized by predicting the doping concentration of EuF_(3) and 2 mol%EuF3 is the best concentration in this work.Glass-ceramics sample GC2Eu as spectral conversion layer was successfully applied on organic solar cells to obtain more available visible phonons with a high photoelectric conversion efficiency(PCE).This work confirms the guidance of molecular dynamics simulation methods for fluorosilicate glasses design.
基金supported by the Foundation Research Project of Kaili University(No.2025ZD007)the National Key Research and Development Program of China(No.2021YFB3801503)the Joint Research Program of Shaoxing University and Shaoxing Institute,Zhejiang University(No.2023LHLG006),China.
文摘The presence of chirality,a fundamental attribute found in nature,is of great significance in the field of pharmaceutical science.Chiral drugs are unique in that their molecular structure is non-superimposable on its mirror image.This stereoisomerism significantly impacts the functionality,metabolic pathway,effectiveness,and safety of chiral medications.The enantiomers of chiral drugs can exhibit diverse pharmacological effects in the human body.As a result,it is essential to separate and purify chiral drugs effectively.Despite the abundance of reports on chiral drug separation membranes,there is a dearth of comprehensive reviews.This paper aims to fill this gap by providing a thorough review from a materials perspective,with a focus on the design and construction of chiral drug separation membranes.Furthermore,it systematically analyzes the separation mechanisms employed by these membranes.The paper also delves into the challenges and prospects related to chiral drug separation membranes,with the intention of imparting valuable insights for further research and development in this field.
基金supported by the National Natural Science Foundation of China(Nos.52325302 and 52173012)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SZ-FR005)。
文摘Achieving continuous motions typically requires dynamic external stimuli for cyclic deformation,or crafted geometries with intricate modules to form a self-regulated feedback loop upon static stimulation.It is still a grand challenge to realize self-sustained motion in soft robots subject to unchanging environment,without complex geometry or a control module.In this work,we report soft robots based on an anisotropic cylindrical hydrogel showing self-regulated,continuous rolling motions under constant light irradiation.The robots are animated by mirror-symmetry-breaking induced by photothermal strain gradient.The self-sustained motion is attributed to the fast and reversible deformation of the gel and the autonomous refresh of the irradiated region during the rolling motion.The hydrogel robots can reach a rolling speed of 1.27 mm·s^(-1)on a horizonal surface and even climb a ramp of 18°at a speed of 0.57 mm·s^(-1)in an aqueous environment.Furthermore,the hydrogel robots can overcome an obstacle,with rolling direction controllable through irradiation angle of the light and local irradiation on selective regions.This work suggests a facile strategy to develop hydrogel robots and may provide unforeseen inspirations for the design of self-regulated soft robots by using other intelligent materials.
基金support from the National Natural Science Foundation of China(No.21878218)the Tianjin Research Innovation Project for Postgraduate Students(No.2023KJ262)+2 种基金the State Grid Corporation of China’s Research Program(No.5419-202019385A)the Fundamental Research Funds for the Central Universities(No.92320006)the Tianjin Key Science and Technology Program(No.18ZXSZSF00030)。
文摘Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change materials.Here,we report a tiramisu-like composite(GMP),where the typical“crust-and-cheese”hierarchical structure is replicated by an innovative two-step bidirectional freezing assembly(BFA)and compressive densification.Hierarchical-aligned graphene array(G-GA)with ultralow thermal resistance is fabricated through 1st BFA and graphitization.During the 2nd BFA,the MXene-CNF crosslinking network with hydrogen-bond actions is used for encapsulating polyethylene glycol(PEG)onto the microlayers of the G-GA skeleton.Remarkably,the microlaminated GMP4 achieves a recorded TC of 34.05 W m^(-1) K^(-1),unprecedented EMI SE of 87.4 dB,and preferable enthalpy density of 179.4 J cm^(-3),along with leakage-free function,and eminent thermal durability.Furthermore,the GMP-loaded equipment is demonstrated for efficient microelectronics cooling and sustainable solar energy utilization.This work opens new avenues for multiscale designing multifunctional macro-composites,broadening the application prospects in advanced electronics and solar energy utilization systems.
基金the National Natural Science Foundation of China(22075114,32371434,82301630)the Natural Science Foundation of Jiangsu Province(BK20211034)the financial support from Jiangsu Provincial Medical Key Laboratory(Key Laboratory of Nuclear Medicine).
文摘Nitric oxide(NO)modulates several cancer-related physiological processes and has advanced the development of green methods for cancer treatment and integrated platforms for combination or synergistic therapies.Although a nanoengineering strategy has been proposed to overcome deficiencies of NO gas or small NO donor molecules,such as short half-life,lipophilicity,non-selectivity,and poor stability,it remains challenging to prepare NO nanomedicines with simple composition,multiple functions and enhanced therapeutic efficacy.Herein,we build a liquid metal nanodroplet(LMND)-based NO nanogenerator(LMND@HSG)that is stabilized by a bioreducible guanylated hyperbranched poly(amido amine)(HSG)ligand.Mechanically,the tumor microenvironment specifically triggers a cascade process of glutathione elimination,reactive oxygen species(ROS)generation,and NO release.According to actual demand,the ROS and NO concentrations could be readily controlled by tuning the LMND and HSG feed amounts.Along with the intrinsic anticancer property of LMND(ROS-mediated apoptosis and anti-angiogenesis),LMND@HSG administration could further enhance tumor growth suppression compared with LMND and HSG alone.Fromthis study,leveraging LMND for NO gas therapy provides more possibilities for the prospect of LMND-based anticancer nanomedicines.
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+2 种基金Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Fundamental Research Funds for the Central Universities (2009QNA4040)the Foundation for the Author of National Excellent Doctoral Dissertation of China (No.200527)
文摘A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.
文摘Axonal regeneration and ifber regrowth is limited in the adult central nervous system, but re-search over the last decades has revealed a high intrinsic capacity of brain and spinal cord circuits to adapt and reorganize after smaller injuries or denervation. Short-distance ifber growth and synaptic rewiring was found in cortex, brain stem and spinal cord and could be associated with restoration of sensorimotor functions that were impaired by the injury. Such processes of struc-tural plasticity were initially observed in the corticospinal system following spinal cord injury or stroke, but recent studies showed an equally high potential for structural and functional reorganization in reticulospinal, rubrospinal or propriospinal projections. Here we review the lesion-induced plastic changes in the propriospinal pathways, and we argue that they represent a key mechanism triggering sensorimotor recovery upon incomplete spinal cord injury. The for-mation or strengthening of spinal detour pathways bypassing supraspinal commands around the lesion site to the denervated spinal cord were identiifed as prominent neural substrate inducing substantial motor recovery in different species from mice to primates. Indications for the exis-tence of propriospinal bypasses were also found in humans after cortical stroke. It is mandatory for current research to dissect the biological mechanisms underlying spinal circuit remodeling and to investigate how these processes can be stimulated in an optimal way by therapeutic inter-ventions (e.g., ifber-growth enhancing interventions, rehabilitation). This knowledge will clear the way for the development of novel strategies targeting the remarkable plastic potential of pro-priospinal circuits to maximize functional recovery after spinal cord injury.
基金financially supported by the National Natural Science Foundation of China (No. 21871232)Zhejiang Provincial Natural Science Foundation of China (No. LR15B040001)
文摘Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone)(PCL) via Janus polymerization, which comprises cationic ring-opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl)oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)3)and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CLb-(CL-r-CO)) can be modulated by various RE(OTf)3. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)3 catalysts used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively, via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides, as confirmed by FTIR analyses. According to NMR and SEC analyses, copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures. The investigations on thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to sei住assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining onestep Janus polymerization and precise post-polymerization click reaction.
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+3 种基金the Fundamental Research Funds for the Central Universities (2009QNA4040)Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Foundation for the Author of National Excellent Doctoral Disser-tation of China (No.200527)China Postdoctoral Science Foundation (No.20100471707)
文摘Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.
基金the support from the SCI-TECH Academy of Zhejiang University。
文摘In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for ring-opening(co)polymerizations.Second,a catalyst-free polycondensation mechanism was proposed for the production of polyesters with high molecular weights.Third,a co-assembly method that can fabricate films and coatings with controllable structures and properties on various substrates was demonstrated,providing a platform for the construction of novel surface coatings.Forth,facile methods for producing high-productivity poly(propylene carbonate)and semicrystalline polyester have been discovered.And linear non-conjugated polyesters exhibiting yellow-green clusteroluminescence were developed for the first time.Fifth,a supramolecular prodrug nano-assembly strategy has been developed for reactive nitrogen species potentiated chemotherapy.Sixth,a series of tough and stiff supramolecular hydrogels with shape memory properties have been used for information encryption.Seventh,reversible fusion and fission of wet-spun graphene oxide fibers has been successfully achieved.Eighth,three non-conjugated polypeptides were synthesized and the mechanism of clusteroluminescence was studied.Ninth,a series of conducting covalent organic frameworks with high electrical conductivity and carrier mobility have been used as high-performance chemiresistor,electrocatalyst,and organic field-effect transistor.Tenth,the exploration of non-fused electron acceptors,and their photostable mechanism are exemplified for developing high-performance,low-cost and eco-friendly polymer solar cells.Finally,gel-grown long-range ordering bulk-heterojunctions has achieved improved X-ray detector performance.
基金support from the SCI-TECH Academy of Zhejiang University。
文摘In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed and synthesized facilely, exhibiting outstanding reactivity, thermalstability and productivity in different kinds of polymerization and cycloaddition reactions. Second, a variety of chalcogen(O, S, Se)-rich polymers had been synthesized via organocatalysis and fabricated to be the ionic conductive and photoluminescent materials. Third, diverse microenvironment-sensitive nanoparticles had been designed,and novel strategies had been realized, to enhance the therapeutic efficacy in cancer as well as biofilmassociated infections. Fourth, m6 A modification on cellular transcriptome-wide messenger RNA had been successfully mapped at single base resolution using a metabolic labeling method. Fifth, a hydrogel-based robot had been developed, showing swift locomotion as a response to dynamic light stimulations. Sixth,the conformation-size scaling law and the conformation evolution map of 2 D macromolecules in solution had been elucidated experimentally, in the single-layer graphene oxide model. Seventh, semitransparent polymer solar cells, promising as building-integrated photovoltaics, have been developed with the fine balance among power conversion efficiency, visible light transparency and infrared photon radiation rejection. Finally, long-range ordered bulk-heterojunctions of organic semiconductors had been achieved,and their superior optoelectronic properties and potential application in photoelectric conversion had been revealed. The related work progresses are reviewed in this paper.
基金supported by the National Natural Science Foundation of China(No.51173157)National High-Tech R&D Program of China(No.2012AA040305)the Major State Basic Research Programs(No.2011CB606001)
文摘Both terminated functional isotactic polypropylene (iPP) and block copolymers containing iPP segment are desirable for commercial applications. This paper provides a convenient, highly-efficient method to prepare hydroxyl-terminated isotactic polypropylene (iPP-t-OH) and functional di-block copolymer containing the iPP segment through a combination of coordination polymerization and coupling reaction. The coordination polymerization was catalyzed by TiCI4/MgCI2/AIEt3 catalyst system using ZnEt2 as chain transfer agent. Further, the Zn-terminated iPP was oxidized and subsequently hydrolyzed to provide iPP-t-OH. Soxhlet extraction and 13C NMR were used to calculate the isotacticity of iPP-t-OH. The degree of polymerization and the number of hydroxyl groups at the chain end of iPP-t-OH were measured by GPC and 1H NMR. Despite the high molecular weight and heterogeneous reaction, iPP-t-OH is effectively linked with PEG-t-NCO to produce di-block copolymers. DSC analysis of the di-block copolymer shows an obvious decrease in Tm and To, which indicated that PEG was successfully linked to the terminal end of iPP.
基金the National Natural Science Foun-dation of China(No.52001280)the China Postdoctoral Science Foundation(No.2020M682339).
文摘Marine biofouling is a worldwide challenge that needs to be solved urgently.Poly(dimethylsiloxane)(PDMS)-based fouling release coatings with low surface free energy(SFE)could effectively inhibit bio-fouling.Nevertheless,their poor mechanical durability,adhesive strength,and antifouling performance under static conditions significantly limit their applications.Herein,a novel mechanically robust Al_(2)O_(3)-PDMS-Cu composite coating with strong adhesive strength and remarkable antifouling performance was developed.The Al_(2)O_(3)-PDMS-Cu coating loaded with a small amount of Cu was fabricated by infiltrating PDMS into plasma-sprayed micro/nano-scaled porous Al_(2)O_(3)-Cu coating.Results showed that the fabri-cation of this Al_(2)O_(3)-PDMS-Cu coating did not alter the surface hydrophobicity and SFE of PDMS signif-icantly,thus presenting little influence on its inherent fouling release property.After rigorous abrasion test,the Al_(2)O_(3)-PDMS-Cu coating presented remarkably improved surface hydrophobicity due to the ex-posure of micro/nano structure,rather than falling offas that of PDMS coating.The combination of excel-lent abrasion resistance and one order of magnitude higher adhesive strength and hardness than PDMS coating contributed to the outstanding mechanical robustness of Al_(2)O_(3)-PDMS-Cu coating.Additionally,the antifouling assays against marine bacteria adhesion(95%reduction rate for Escherichia coli.(E.coli))and algae attachment(96%and 94%reduction rates for Chlorella and Phaeodactylum tricornutum(P.tricor-nutum),respectively after 21 days of incubation)demonstrated the superior antifouling performance of the Al_(2)O_(3)-PDMS-Cu coating.Thus,a high-performance Al_(2)O_(3)-PDMS-Cu antifouling coating with excellent mechanical robustness and long-term antifouling performance was achieved via the combination of me-chanical durability of Al_(2)O_(3)skeleton and the dual-functional antifouling strategy,i.e.,the fouling release property of PDMS and fouling resistance of Cu.
基金funded by Ministry of Science and Technology(No.2017YFA0206600)National Natural Science Foundation of China(Nos.21722404,21674093,21734008,21761132001 and 91633301)+2 种基金International Science and Technology Cooperation Program of China(ISTCP,No.2016YFE0102900)supported by the Fundamental Research Funds for the Central Universities(No.2018XZZX002-16)support by Zhejiang Natural Science Fund for Distinguished Young Scholars(No.LR17E030001)。
文摘Semitransparent organic solar cells(ST-OSCs)have the potentials to open promising applications that differ from those of conventional inorganic ones,such as see-through power windows with both energy generation and heat insulation functions.However,to achieve so,there remain significant challenges,especially for balancing critical parameters,such as power conversion efficiency(PCE),average visible transparency(AVT)and low energy infrared photon radiation rejection(IRR)to realize the full potentials of ST-OSCs.Herein,we demonstrate the new design of ST-OSCs through the rational integration of organic materials,transparent electrode and infrared photon reflector in one device.With the assistance of optical simulation,new ST-OSCs with precise layout exhibit state-of-art performance,with near 30%AVT and PCE of 7.3%,as well as an excellent IRR of over 93%(780-2500 nm),representing one of best multifunctional ST-OSCs with promising perspective for window application.
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Guizhou Provincial Science and Technology Department,Technology Achievement Application and Industrialization Plan,Applied Fundamental Research,No.Qianke Synthetic Fruit[2022]004.
文摘BACKGROUND Accurate condition assessment is critical for improving the prognosis of neonatal respiratory distress syndrome(RDS),but current assessment methods for RDS pose a cumulative risk of harm to neonates.Thus,a less harmful method for assessing the health of neonates with RDS is needed.AIM To analyze the relationships between pulmonary ultrasonography and respiratory distress scores,oxygenation index,and chest X-ray grade of neonatal RDS to identify predictors of neonatal RDS severity.METHODS This retrospective study analyzed the medical information of 73 neonates with RDS admitted to the neonatal intensive care unit of Liupanshui Maternal and Child Care Service Center between April and December 2022.The pulmonary ultrasonography score,respiratory distress score,oxygenation index,and chest Xray grade of each newborn before and after treatment were collected.Spearman correlation analysis was performed to determine the relationships among these values and neonatal RDS severity.RESULTS The pulmonary ultrasonography score,respiratory distress score,oxygenation index,and chest X-ray RDS grade of the neonates were significantly lower after treatment than before treatment(P<0.05).Spearman correlation analysis showed that before and after treatment,the pulmonary ultrasonography score of neonates with RDS was positively correlated with the respiratory distress score,oxygenation index,and chest X-ray grade(ρ=0.429–0.859,P<0.05).Receiver operating characteristic curve analysis indicated that pulmonary ultrasonography screening effectively predicted the severity of neonatal RDS(area under the curve=0.805–1.000,P<0.05).CONCLUSION The pulmonary ultrasonography score was significantly associated with the neonatal RDS score,oxygenation index,and chest X-ray grade.The pulmonary ultrasonography score was an effective predictor of neonatal RDS severity.