Synergy of Polydopamine‑Assisted Additive Modification and Hierarchical‑Morphology Poly(Vinylidene Fluoride)Nanofiber Mat for Ferroelectric‑Assisted Triboelectric Nanogenerator

In the last decade,numerous physical modification methods have been introduced to enhance triboelectric nanogenerator(TENG)performance although they generally require complex and multiple fabrication processes.This study proposes a facile fabrication process for Poly(vinylidene fluoride)(PVDF)nanofiber(NF)mats incorporating additive and nonadditive physical modifications.Patterned PVDF NF mats are prepared by electrospinning using a metal mesh as the NF collector.As a negative triboelectric material,the TENG with the patterned PVDF NF mat exhibits superior performance owing to the engineered morphology of the contact layer.PVDF is crucial in TENGs owing to its superior ferroelectric properties and surface charge density when combined with specific electroceramics.Hence,the synergy of the physical modification methods is achieved by incorporating BaTiO3(BTO)nanoparticles(NPs)into the PVDF.By functionalizing BTO NPs with polydopamine,the TENG performance is further improved owing to the enhanced dispersion of NPs and improved crystallinity of the PVDF chains.Utilizing large NPs produces a nanopatterning effect on the NF surface,thereby resulting in the hierarchical structure of the NF mats.The source of the voltage signals from the TENG is analyzed using fast Fourier transform.

Synthesis and Properties of Novel Poly（amine ether）s

Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it＇s obvious that they show high glass transition temperatures （Tg〉200 ℃）, good thermal stability with high decomposition temperatures （TD〉500℃） and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers.

Effective adsorption of sulfate ions with poly(m-phenylenediamine) in aqueous solution and its adsorption mechanism

Sulfate adsorption by poly（m-phenylenediamine）s（PmPDs） with various oxidation states synthesized through chemically oxidative polymerization was investigated.Series of sorption experiments were conducted,and the adsorption mechanism and the relationship between oxidation state and adsorption performance were studied with the characterization of Fourier transform infrared spectroscopy（FTIR）,X-ray photoelectron spectroscopy（XPS）,pH tracking and energy calculation.The results show that the adsorption performance in acidic solution is improved with the decrease of oxidation state of poly（m-phenylenediamine）（PmPD）.The rate constant is as high as 425.5 mg/（g·min） in the short equilibrium time of 30 min.The estimated highest adsorptivity of sulfate ions is 95.1%.According to the Langmuir equation,the adsorbance is 108.5 mg/g.The sulfate desorption efficiency is about 95% and the accumulative adsorbance is up to 487.95 mg/g in 5 cycles.

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

NOVEL HYPERBRANCHED POLY(AMINE-ESTER) FILMS: PREPARATION, CHARACTERIZATION AND PROPERTIES

Crosslinked film of hyperbranched poly（amine-ester） （HPAE） was prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde （GA）. Atom force microscope （AFM） and scanning electron microscope （SEM） reveals that they have smooth surfaces, dense and homogenous matrices. It was found that the water static contact angle is smaller than 41.7°, the tensile strength is higher than 8.9 MPa, the elongation at break is higher than 5.1%, the swelling degree is higher than 42% in water, and the Bovine hemoglobin （Hb） adsorption is relatively low. These results indicate that the crosslinked HPAE films might have some potential applications in many areas.

Synthesis of poly(m-phenylenediamine) with improved properties and superior prospect for Cr(VI) removal

Chemically oxidative polymerization of m-phenylenediamine was improved through adding the weak alkaline, Na2CO3. Results show that the poly （m-phenylenediamine） （PmPD） possesses a weak solubility in acidic solution according to total organic carbon （TOC） that the TOC is less than 8 mg/L, which is much lower than the discharge standard （20 mg/L）. The TOC of the PmPD synthesized with NaOH can be as high as 120.9 mg/L. This very weak solubility of PmPD synthesized with Na2CO3 facilitates its application in water purification. The oxidation state of PmPD is decreased and the yield is increased with a maximum of 84%, promoting the concentration of Na2CO3 in the synthesis. Moreover, the Cr（VI） performance of PmPD was marvelously enhanced with Na2CO3 to improve the synthesis. The largest Cr（VI） adsorbance can reach as high as 666.8 mg/g, which is far more than the performance of other common adsorbents.

Molecular weight determination of a newly synthesized guanidinylated disulfide-containing poly(amido amine) by gel permeation chromatography

A cationic gene delivery vector, guanidinylated disulfide-containing poly(amido amine)(CARCBA), was synthesized by Michael addition reaction between N,N′-cystaminebisacrylamide(CBA) and guanidine hydrochloride(CAR). Gel permeation chromatography(GPC) was used to evaluate the molecular weight of synthesized CAR-CBA. Polyethyleneimine(PEI) with molecular weight of 25 kDa was adopted as a reference, and polyethylene glycols(PEG) with different molecular weights were used to establish a standard curve for determining the molecular weight of CAR-CBA. The effects of two critical factors, namely columns and eluents,on the molecular weight measurement of CAR-CBA were investigated to optimize the GPC quantitative method. The results showed that Ultrahydrogel columns(120, 250) and HAc–NaAc(0.5 M, pH 4.5) buffer solution were the optimal column and GPC eluent, respectively.The molecular weight of the synthesized CAR-CBA was analyzed by the optimized GPC method and determined to be 24.66 kDa.

Aliphatic Hyperbranched Poly(amido amine)s (PAMAMs): Preparation and Modification

A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and C_n types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and C_n monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to C_n, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers′ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to C_n. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.

Synthesis of the Biomimetic Polymer: Aliphatic Diamine and RGDS Modified Poly(d,l-lactic acid)

A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the acidity and auto-accelerating degradation of PDLLA during degradation and to improve its biospecificity and biocompatibility. The synthetic copolymer was characterized by FTIR, ^13C NMR and amino acid analyzer （AAA）.

Intracellular distribution and internalization pathways of guanidinylated bioresponsive poly(amido amine)s in gene delivery

Guanidinylated bioresponsive poly(amido amine)s polymers, CAR-CBA and CHL-CBA, weresynthesized by Michael-type addition reaction between guanidine hydrochloride(CAR) orchlorhexidine(CHL) and N,N-cystaminebisacrylamide(CBA). Previous studies have shownthat both polymers had high transfection efficiencies as gene delivery carriers. In this study,we investigated the nucleolus localization abilities and cellular internalization pathways ofthese two polymers in gene delivery. Each polymer condensed plasmid DNA(p DNA) andformed nanoparticle complexes, and then their transfection studies were performed inMCF-7 cells. Both complexes were found enriched in nucleolus after cellular transfection,and their transfection efficiencies were significantly improved when transfection was per-formed on MCF-7 cells arrested at M phase. The transfection efficiency of CAR-CBA-pDNAwas inhibited by chlorpromazine, and cell endosomes were disrupted after being exposedto CAR-CBA-pDNA. In regards to CHL-CBA-pDNA, its transfection efficiency was not affected by three types of endocytosis inhibitors used in the study, and CHL-CBA-pDNA showed no effect on endosomes. Cellular lactate dehydrogenase release and membrane morphology were changed after cells were transfected by the two complexes. The results indicated that both CAR-CBA and CHL-CBA polymers demonstrated good nucleolus localization abilities. It was beneficial for transfection when cells were arrested at M phase. CAR-CBA-pDNA cellular internalization was involved with clathrin-mediated endocytosis pathway, and escaping from endosomal entrapment, while the cellular uptake of CHL-CBA-pDNA occurs via clathrin-and caveolae-independent mechanism.

Effect of Hyperbranched Poly(amine-ester) Grafted Nano-SiO_2 on Reinforcement and Toughness of PVC

Nano-SiO2 was modified using silane coupling agent （KH-550） and hyperbranched poly（amine-ester） respectively, and Poly（vinyl chloride） （PVC）/modified nano-SiO2 composites were made by melt-blending. The composites＇ structures andmechanical properties were characterized by transmission electron microscopy（TEM）, sanning electronic microscopy（SEM） and electronic universal testing machine. The results. show that nano-SiO2 grafted by hyperbranched poly （amine-ester） increases obviously in dispersion in PVC matrix, and mechanical properties of PVC are effectively improved. Moreover, it was found that mechanical properties of PVC/nano-SiO2 composites reach the best when weight percent of nano-SiO2 in PVC matrix is 1%. Compared with crude PVC, the tensile strength of hyperbranched poly （amine-ester） grafted nano-SiO2/ PVC composite increases by 24.68 % and its break elongation, flexural strength and impact strength increase by 15.73%, 4.07% and 1 841.84%, respectively. Moreover, the processing of the composites is improved.

Application of Tertiary Amine Cationic Polyacrylamide with High Cationic Degree in Salt-free Dyeing of Reactive Dyes

Tertiary amine cationic polyacrylamide with high cationization degree was used as a new cationic agent to pretreat cotton with dip-pad-bake method. The obtained cationic cotton was dyed with reactive dyes in the ab-sence of electrolyte. The effects of the characteristics of the cationic agent and the pretreatment conditions on dye-ability of reactive dye were investigated. The results showed that the fixation and K/S values of the reactive dyes on the cationic cotton were improved compared with those on the untreated one in the presence of salt. Tests on fast-ness properties of the dyed cotton and fabric quality of the pretreated cotton were carried out and the results showed that wash and rub fastness of the salt-free dyeing were both satisfactory. And anti-crease property,tensile and tear strength,and handling of the cationic cotton were also good compared with that of the untreated one.

New Phase Transfer Agent for Dye: Application for Hyperbranched Poly (ester-amine)

Hydrophilic hyperbranched poly(ester-amine) (HPEA) synthesized from diethanolamine and methyl acrylate was used as phase transfer agent for the first time to transfer methyl orange (MO) from water into chloroform. This process was quantified by UV-Vis spectra. A possible mechanism was put forward based on the formation of amphiphilic aggregates.

SYNTHESIS OF NOVEL BI-FUNCTIONAL COPOLYMER BEARING STERICALLY HINDERED PHENOL AND HINDERED AMINE GROUPS VIA RING-OPENING METATHESIS POLYMERIZATION

Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl_2(=CHPh)(PCy_3)_2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol(SHP)and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),~1H-NMR and differen...

Poly(amaranth) film based sensor for resolution of dopamine in the presence of uric acid:A voltammetric study

The electropolymerized film of amaranth was prepared on the surface of graphite pencil electrode（GPE） using cyclic voltammetric technique.This poly（amaranth） film coated electrode exhibited an excellent electrocatalytic activity towards the detection of dopamine（DA） in the presence of uric acid（UA） in 0.2 mol/L phosphate buffer solution at pH 7.0.The effect of interference study was carried out using differential pulse voltammetric technique.The poly（amaranth） modified GPE was applied for the detection of DA in dopamine injection with satisfactory results.

Cu^(I)/amine仿生催化胺选择性氧化生成腈的反应机理研究

胺的有氧氧化是有机合成中应用广泛的过程之一,其产物腈类化合物在医药、农药和香料等重要中间体被广泛应用。通过密度泛函理论(DFT)在分子水平上对Cu^(I)/amine仿生催化体系选择性氧化胺生成腈的详细反应机理、抗衡离子及溶剂对反应活性的控制因素进行了详细分析,发现机理分为两步进行:第一步为生成关键活性亚胺中间体(5)过程,该过程存在单核(PathⅠ)和双核(PathⅡ)反应路径,计算结果表明两条路径均为可能路径,并以单核机理(PathⅠ)路径为主导路径;第二步为生成腈过程,该过程存在两条可能路径(Path A和Path B),能量跨度模型分析表明Path B为优势路径,δE=16.6 kcal/mol,TOF=4.14 s^(-1)。此外,还发现抗衡离子I^(–)的存在明显降低了反应路径的能垒,而溶剂则对反应能垒没有明显影响。

Preparation and characterization of eco-friendly poly(p-phenylenediamine) and its composite with chitosan for removal of copper ions from aqueous solutions

Poly(p-phenylenediamine)/chitosan (PPPDA/Chi) composite was prepared by in situ chemical oxidative polymerization of p-phenylenediamine (PPPDA) into chitosan (Chi) using ammonium persulphate (APS) as an oxidant. PPPDA and PPPDA/Chi composite were characterized by FT-IR spectra and SEM before and after copper loading. In batch adsorption method, the maximum removal of copper was experienced when 1 g/L of PPPDA and PPPDA/Chi composite dosages were used at pH 5.0 for PPPDA and 6.0 for PPPDA/Chi composite for 360 min for both sorbents. PPPDA showed adsorption capacity qemax of 650 mg/g whereas its composite achieved qemax of 573 mg/g. The experimental data correlate well with the Freundlich isotherm equation and the pseudo-second order kinetic model. The Cu(II), loaded PPPDA and its composite can be efficiently reused for as many as four cycles. The Cu(II)-loaded sorbents showed high antibacterial efficiency against Gram-positive and Gram-negative bacteria than their unloaded forms.

Effects of potassium lactate on sensory attributes,bacterial community succession and biogenic amines formation in Rugao ham

To deepen the understanding in the effect of potassium lactate on the sensory quality and safety of Rugao ham,sensory attributes,physicochemical parameters,total volatile basic nitrogen(TVBN),microorganism community and biogenic amines of Rugao ham manufactured with different potassium lactate levels(0%,0.5%,1%,2%)were investigated;the relationship between microbial community and the formation of TVBN and biogenic amines was further evaluated.With the increase of potassium lactate from 0%to 2%,the increased sensory scores and the decreased total aerobic bacterial count and TVBN were observed;the abundance of Staphylococcus increased,while the content of Halomonas decreased.LDA effect size(LEf Se)and correlations analysis showed that Staphylococcus equorum and Lactobacillus fermentum could be the key species to improve sensory scores and decrease biogenic amines and TVBN.Metabolic pathway analysis further showed that amino acids metabolism and nitrogen metabolism were mainly involved in decreasing TVBN and biogenic amines in the treatment of 2%potassium lactate.

SYNTHESIS OF NEW AROMATIC POLY(AMIDE IMIDE)S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N- dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Tg) are in the range of 301-327°C, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 'C.

One-pot Synthesis of MoO_(3)/PI Composite with Enhanced Photocatalytic Performance for Oxidative Coupling of Amines to Imines

Organic-inorganic MoO_(3)/PI(MoPI)composites were prepared using a simple one-pot thermal copolymerization method.The resulting composites exhibited enhanced photocatalytic activity for the selective oxidation of benzylamine to N-benzylidene benzylamine(N-BDBA)in ambient air under simulated solar light irradiation compared to pristine MoO_(3) or polyimide(PI).In particular,the MoPI composite with a 0.3:1 molar ratio of Mo to melamine,referred to as MoPI-0.3,demonstrated the best performance in the photo-oxidation of benzylamine,achieving a benzylamine conversion of 95%with a N-BDBA selectivity exceeding 99%after 3 h irradiation.The enhanced photocatalytic activity of the MoPI-0.3 catalyst was attributed to the formation of a direct Z-scheme heterojunction between MoO_(3) and PI,facilitating more efficient separation of the photoinduced electrons and holes.Additionally,the MoPI-0.3 composite maintained considerably high activity over four consecutive cycles,highlighting its good stability and recyclability.Furthermore,the MoPI-0.3 composite could photo-oxidize benzylamine derivatives and heterocyclic amines to their corresponding imines,demonstrating the universal applicability of this composite catalyst.