用聚乙二醇简便合成3-取代-1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶-2, 4-二酮

用聚乙二醇作为可溶性聚合物载体和相转移催化剂高效简单的合成了1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶类化合物。该合成路线为聚乙二醇与2, 3-吡啶二酸酐反应生成聚乙二醇支载的单酯1,接着1被转化成相应的聚乙二醇支载的酰基叠氮2,2经Curtius重排,与胺加成并同时关环给出目标产物,其总产率为84%-88%。     

聚乙二醇支持的2,5-二取代异噁唑啉衍生物的液相合成

介绍了通过1,3-偶极环加成合成2,5-二取代异噁唑啉衍生物的液相合成方法, 利用聚乙二醇(PEG)支持的烯烃与由醛肟制得的腈氧化物反应制备了多种异噁唑啉衍生物, PEG解脱后产物的产率和纯度均很高.     

Size controlled synthesis of Pd nanoparticles in water and their catalytic application in C-C coupling reactions

Catalytically active Pd nanoparticles have been synthesized in water by a novel reduction of Pd(II) with a Fischer carbene complex where polyethylene glycol (PEG) was used as stabilizer. PEG molecules wrap around the nanoparticles to impart stability and prevent agglomeration, yet leave enough surface area available on the nanoparticle for catalytic activity. Our method is superior to others in terms of rapid generation and stabilization of Pd nanoparticles in water with a cheap, readily available PEG stabilizer. The size of the nanoparticles generated can be controlled by the concentration of PEG in water medium. The size decreased with the increase in the PEG: Pd ratio. This aqueous nano-sized Pd is a highly efficient catalyst for Suzuki, Heck, Sonogashira, and Stille reaction. Water is used as the only solvent for the coupling reactions.     

Ammonium persulphate promoted synthesis of polyethylene glycol entrapped potassium tribromide and its application in acylation and bromination of some selective organic compounds

In this study, a new method of synthesis of polyethylene glycol supported potassium tribromide (PEG KBr3) and its application in acylation and bromination reactions are reported. Ammonium persulphate oxidizes KBr to the corresponding tribromide which is entrapped by polyethylene glycol leading to stable PEG KBr3. The reagent is proved to be highly efficient for the acylation of variety of alcohols and bromination of activated aromatic substrates. Themethod is a mild, one pot reaction and involves no use of toxic reagents.     

Efficient and Convenient Polyethylene Glycol (PEG)‐Mediated Synthesis of Spiro‐oxindoles

Polyethylene glycol (PEG) has been reported as an efficient and convenient medium for the three‐component synthesis for spiro‐oxindole.     

Liquid‐Phase Synthesis of 2‐Methyl‐2‐Aryloxypropanoic Acid Derivatives from Polyethylene Glycol) Supported 2‐Bromo‐2‐Methylpropanoate

An efficient liquid‐phase synthesis of 2‐methyl‐2‐aryloxypropanoic acid derivatives with good yields and high purity on soluble polyethylene glycol (PEG) has been developed by treatment of PEG‐bound 2‐bromo‐2‐methylpropanoate with phenoxides in the presence of a catalytic amount of NBu₄I and KI, and subsequent cleavage from the PEG.     

A Simple and Catalyst-Free One-Pot Synthesis of α-Aminophosphonates in Polyethylene Glycol

Abstract

A simple and efficient method has been developed for the one-pot synthesis of α-aminophosphonates using polyethylene glycol (PEG) as a green reaction media.     

选择性接聚乙烯醇枝聚醚氨酯的合成及其血液相容性

合成了α－甲基，ω－（２，３－环氧丙基）－聚乙二醇醚（Ⅱ）．经水解得到悬挂聚乙二醇（ＰＥＧ）枝的丙二醇－２，３（Ⅲ）．用二元醇（Ⅲ）为扩链剂制得了在硬链段上接有ＰＥＧ枝的聚醚氨酯（Ｈ－ＰＥＵ）．以四氢呋喃与少量大分子单体（Ⅱ）进行正离子开环共聚合制得每个链接有约１．３个ＰＥＧ枝的聚丁二醇（Ⅳ），用以合成了在软链段上接有ＰＥＧ枝的聚醚氨酯（Ｓ－ＰＥＵ）．ＥＳＣＡ及抗凝血性研究结果表明，不同位置接枝的ＰＥＵ，其表面都有明显的聚醚链段富集．Ｓ－ＰＥＵ抗凝血复钙时间只比未接枝者增长约２０％，而Ｈ－ＰＥＵ则增约一倍，比Ｓ－ＰＥＵ增约６０％．随ＰＥＧ最增大，复钙时间增长．     

Novel synthesis of N(4)-substituted 1,4-benzodiazepine-2,5-diones using poly(ethylene glycol) as soluble polymer support

An efficient method for the liquid-phase combinatorial synthesis of N4-substituted 1,4-benzodiazepine-2,5-diones has been developed. Poly(ethylene glycol) (PEG) stepwise reacted with bromoacetyl bromide, a primary amine and 2-azidobenzoic acid to give a potential PEG-bound dipeptide, which was reduced by NaI / acetic acid, along with concurrent cyclization and cleavage of the seven-membered heterocycle from the PEG support.     

Mannose‐Modified Serum Exosomes for the Elevated Uptake to Murine Dendritic Cells and Lymphatic Accumulation

The surface of bovine serum‐derived exosomes (EXOs) are modified with α‐d ‐mannose for facile interaction with mannose receptors on dendritic cells (DCs) and for efficient delivery of immune stimulators to the DCs. The surface of the EXOs is modified with polyethylene glycol (PEG) without particle aggregation (≈50 nm) via the incorporation of 1,2‐distearoyl‐sn‐glycero‐3‐phosphoethanolamine (DSPE) into the lipid layer of the EXO, compared to chemical conjugation by N‐hydroxysuccinimide activated PEG (NHS‐PEG). PEG modification onto the exosomal surface significantly decreases the non‐specific cellular uptake of the EXOs into the DCs. However, the EXOs with mannose‐conjugated PEG‐DSPE (EXO‐PEG‐man) exhibit excellent intracellular uptake into the DCs and boost the immune response by the incorporation of adjuvant, monophosphoryl lipid A (MPLA) within the EXO. After an intradermal injection, a higher retention of EXO‐PEG‐man is observed in the lymph nodes, which could be used for the efficient delivery of immune stimulators and antigens to the lymph nodes in vivo.     

High-performance polyethylene glycol-coated solid-phase microextraction fibers using sol-gel technology

The sol-gel method is applied for the preparation of solid-phase microextraction (SPME) fibers. An electron microscopy experiment suggested a porous structure for Superox-4 (polyethylene glycol, PEG) coating. SPME-GC analyses provided evidence that the sol-gel fibers have some advantages, such as high velocities of mass transfer, efficient extraction rates. high thermal stability, long life span, and spacious range of application for both polar and non-polar analytes. Efficient SPME-GC analyses of benzene-toluene-ethylbenzene-xylenes, phenols, phthalic diesters, naphthalene congeners and pesticides were achieved using sol-gel-coated PEG fibers.     

Efficient and Convenient Preparation of Water-Soluble Fullerenol

An efficient and convenient preparation of fullerenols was described. With polyethylene glycol (PEG) 400 as catalyst, fullerenols were conveniently synthesized via the direct reaction of fullerene with aqueous NaOH. By control of reaction conditions, either water-soluble C60 fullerenol or water-insoluble C60 fullerenol could be obtained selectively.     

Squaric Acid Mediated Chemoselective PEGylation of Proteins: Reactivity of Single‐Step‐Activated α‐Amino Poly(ethylene glycol)s

The covalent attachment of poly(ethylene glycol) (PEG) to therapeutically active proteins (PEGylation) has become an important method to deal with the pharmacological difficulties of these polypeptides, such as short body‐residence times and immunogenicity. However, the derivatives of PEG used for PEGylation lack further functional groups that would allow the addition of targeting or labeling moieties. Squaric acid diethyl ester was used for the chemoselective single‐step activation of poly(ethylene glycol)s into the respective ester amides. The resultant selective protein‐reactive poly(ethylene glycol)s were investigated with respect to their selectivity towards amino acid residues in bovine serum albumin (as a model protein). The presented procedure relies on a robust two‐step protocol and was found to be selective towards lysine residues; the activated polyethers are efficient and stoichiometric PEGylation agents with a remarkable hydrolytic stability over a period of several days. By adjusting the pD value of the conjugation mixture, the chemoselectivity of the activated PEGs towards the α‐ and ε‐amino groups of lysine methyl ester was effectively changed.     

Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 1: The Influence of the Grafting

Iron oxide nanoparticles (NPs) with a diameter 21.6 nm were coated with poly(maleic acid-alt-1-octadecene) (PMAcOD) modified with grafted 5,000 Da poly(ethyelene glycol) (PEG) or short ethylene glycol (EG) tails. The coating procedure utilizes hydrophobic interactions of octadecene and oleic acid tails, while the hydrolysis of maleic anhydride moieties as well as the presence of hydrophilic PEG (EG) tails allows the NP hydrophilicity. The success of the NP coating was found to be independent of the degree of grafting which was varied between 20 and 80% of the -MacOD-units, but depended on the length of the grafted tail. The NP coating and hydrophilization did not occur when the modified copolymer contained 750 Da PEG tails independently of the grafting degree. To explain this phenomenon the micellization of the modified PMAcOD copolymers in water was analyzed by small angle x-ray scattering (SAXS). The PMAcOD molecules with the grafted 750 Da PEG tails form compact non-interacting disk-like micelles, whose stability apparently allows for no interactions with the NP hydrophobic shells. The PMAcOD containing the 5,000 Da PEG and EG tails form much larger aggregates capable of an efficient coating of the NPs. The coated NPs were characterized using transmission electron microscopy, dynamic light scattering, ζ-potential measurements, and thermal gravimetry analysis. The latter method demonstrated that the presence of long PEG tails in modified PMAcOD allows the attachment of fewer macromolecules (by a factor of ~20) compared to the case of non-modified or EG modified PMAcOD, emphasizing the importance of PEG tails in NP hydrophilization. The NPs coated with PMAcOD modified with 60% (towards all -MAcOD- units) of the 5,000 PEG tails bear a significant negative charge and display good stability in buffers. Such NPs can be useful as magnetic cores for virus-like particle formation.     

PEG 400 promoted nucleophilic substitution reaction of halides into organic azides under mild conditions

Abstract

Polyethylene glycol 400 (PEG 400) has been demonstrated as an efficient and eco-friendly reaction medium for the preparation of organic azides from structurally diverse halides by nucleophilic substitution reaction with NaN₃ under mild conditions. The advantages of this protocol are: operational simplicity, environmental safety, broad substrate scope, excellent functional group tolerance, and short reaction time. The PEG 400 can be recovered and reused.     

Synergistic effects of PEG and MWCNTs on crystallization behavior of PLLA

This work reported the crystallization behaviors of poly(L ‐lactide) (PLLA) with the presence of polyethylene glycol (PEG) and/or functionalized multiwalled carbon nanotubes (FMWCNTs). The crystallization behaviors occurred in the different conditions, including nonisothermal, isothermal and during the annealing process, were analyzed comparatively using differential scanning calorimetry, wide angle X‐ray diffraction, and polarized optical microscope. The results show that PEG as an efficient plasticizer of PLLA enhances the mobility of PLLA chain segments, which leads to the decrease of glass transition temperature and the enhancement of crystallization ability of PLLA. FMWCNTs as a nucleating agent of PLLA crystallization promote the crystallization of PLLA apparently. With the presence of PEG and FMWCNTs, the crystallization of PLLA is well improved in all conditions, indicating the synergistic effects of PEG and FMWCNTs on PLLA crystallization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 520–528, 2010     

嵌段共聚酯的合成研究

采用直接酯化法合成了一系列含间苯二甲酸的PEIT－PEG嵌段共聚酯,研究了聚合时间,聚合效率及聚酯的特性粘度与产物中间苯二甲酸含量及共聚酯分子量的关系,得出适于纺丝工艺及工业化生产的共聚酯分子量和间苯二甲酸的含量。     

Degradable Molybdenum Oxide Nanosheets with Rapid Clearance and Efficient Tumor Homing Capabilities as a Therapeutic Nanoplatform

Molybdenum oxide (MoOx) nanosheets with high near‐infrared (NIR) absorbance and pH‐dependent oxidative degradation properties were synthesized, functionalized with polyethylene glycol (PEG), and then used as a degradable photothermal agent and drug carrier. The nanosheets, which are relatively stable under acidic pH, could be degraded at physiological pH. Therefore, MoOx‐PEG distributed in organs upon intravenous injection would be rapidly degraded and excreted without apparent in vivo toxicity. MoOx‐PEG shows efficient accumulation in tumors, the acidic pH of which then leads to longer tumor retention of those nanosheets. Along with the capability of acting as a photothermal agent for effective tumor ablation, MoOx‐PEG can load therapeutic molecules with high efficiencies. This concept of inorganic theranostic nanoagent should be relatively stable in tumors to allow imaging and treatment, while being readily degradable in normal organs to enable rapid excretion and avoid long‐term retention/toxicity.     

Efficient One-Step Passivation of Polyurethane Using Transurethanization

The uncontrolled accumulation of biological materials on the surface of medical devices through protein adsorption or cell adhesion causes adverse biological reactions in the living host system, leading to complications. In this study, poly(ethylene glycol) (PEG) is successfully grafted onto polyurethane (PU) surfaces by using a new strategy through a simple and efficient transurethanization reaction. The PEG hydroxyl group is deprotonated and then reacted with the PU surface to provide antiadhesive hydrophilic surfaces in a single step. Surface analysis techniques proved the grafting to be efficient and the formation of a hydrophilic polymeric layer at the surface of PU. Biological assays showed that the surface modification induced lower protein adsorption, cell, platelet, and bacterial adhesion than untreated surfaces, showing a potential for biomedical applications.     

Soluble polymer-supported synthesis of 5-arylidene thiazolidinones and pyrimidinones using a novel traceless linker strategy

An efficient method for the soluble polymer-supported synthesis of 5-arylidene thiazolidinones and pyrimidinones using aniline as a traceless linker was described. Aldehyde substrates were attached to the polyethylene glycol (PEG)-bound aniline via an imine linkage, and after the subsequent PEG-promoted Suzuki coupling reaction for the diversification, Knoevenagel condensation was readily employed as the cleavage strategy.