Compositional analysis of copoly (DL-lactic/glycolic acid) (PLGA) by pyrolysis-gas chromatography/mass spectrometry combined with one-step thermally assisted hydrolysis and methylation in the presence of tetramethylammonium hydroxide

Rapid and precise compositional analysis of copoly (DL-lactic/glycolic acid) (PLGA) was performed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) combined with one-step hydrolysis and methylation in the presence of tetramethylammonium hydroxide (TMAH). Pyrolysis of PLGA with TMAH gave two characteristic products, derivatives of DL-lactic acid and glycolic acid, which directly reflect the average molar composition of PLGA. The analytical results for PLGA samples with various compositional ratios were in good agreement with those obtained by 1H-NMR spectrometry, and the precision was satisfactory.     

The effect of glycolic acid monomer ratio on the emulsifying activity of PLGA in preparation of protein-loaded SLN

Our previous work demonstrated that lactic/glycolic acid copolymer (PLGA) was an efficient emulsifier for the primary w/o emulsion in the formulation of protein-loaded solid lipid nanoparticles (SLN) by w/o/w double emulsion-solvent evaporation technique. In this work, the effect of PLGA composition on the emulsifying activity was studied with PLGA of different lactic/glycolic acid ratios (90/10, 75/25, 50/50). The results demonstrated that the glycolic acid monomer ratio significantly affected the emulsifying activity of PLGA. Increasing the glycolic acid monomer ratio from 10% to 50% decreased the minimum PLGA content needed to produce stable w/o emulsions. With same PLGA contents, increase of the glycolic acid monomer ratio increased the stable time of the w/o emulsion, yielded smaller and narrower-distributed SLN, and enhanced the encapsulation efficiency and loading capacity.     

Characterization of a cross-linked DNA-Endonuclease VIII repair complex by electrospray ionization mass spectrometry

Electrospray mass spectrometry techniques were used to characterize components of the active site in Endonuclease VIII by identifying the amino acid sequence and the binding site for a tryptic peptide derived from Endo VIII in a cross-linked DNA-peptide complex. Endo VIII, a DNA repair enzyme with both glycosylase and lyase activities, was covalently bound to a thymidine glycol-containing oligodeoxynucleotide duplex by converting a transient Schiff base formed during the course of the glycosylase activity to a stable covalent bond by chemical reduction with sodium borohydride. After tryptic digestion of the initial product, the identification of the cross-linked peptide was deduced initially from the molecular mass of the tryptic product obtained by negative ion electrospray mass analysis. Nanospray tandem mass spectrometry (MS/MS) analysis of the tryptic product corroborated the molecular mass of the peptide fragment and verified the point of attachment to the oligomer, but failed to produce sufficient fragmentation to sequence the peptide completely. Direct evidence for the amino acid sequence of the peptide was obtained after enzymatic digestion of the DNA portion of the cross-linked DNA-peptide product and analysis by negative ion nanospray MS/MS. Examination of the ions from collision induced fragmentation disclosed that this substance was the N-terminal tryptic fragment of Endo VIII cross-linked to a portion of the oligomer, and that the N-terminal proline from Endo VIII was covalently bound to the residual deoxyribose moiety at the original location of the thymine glycol in the oligomer.     

Efficient intracellular delivery of rifampicin to alveolar macrophages using rifampicin-loaded PLGA microspheres: effects of molecular weight and composition of PLGA on release of rifampicin

Monodispersed PLGA microspheres containing rifampicin (RFP) have been prepared by solvent evaporation method using a Shirasu porous glass (SPG) membrane. The microspheres were spherical and their average diameter was about 2 microm. The loading efficiency of rifampicin was dependent on the molecular weight of PLGA. The higher loading efficiency was obtained by the usage of PLGA with the lower molecular weight, which may be caused by the interaction of the amino groups of rifampicin with the terminal carboxyl groups of PLGA. PLGA with the monomer compositions of 50/50 and 75/25, of lactic acid/glycolic acid, were used in this study. From rifampicin-loaded PLGA microspheres formulated using PLGA with the molecular weight of 20,000, rifampicin was released with almost constant rate for 20 days after the lag phase was observed for the initial 7 days at pH 7.4. On the other hand, from rifampicin-loaded PLGA microspheres formulated using PLGA with the molecular weight of 5000 or 10,000, almost 90% of rifampicin-loaded in the microspheres was released in the initial 10 days. Highly effective delivery of rifampicin to alveolar macrophages was observed by the usage of rifampicin-loaded PLGA microspheres. Almost 19 times higher concentration of rifampicin was found to be incorporated in alveolar macrophages when rifampicin-loaded PLGA microspheres were added to the cell culture medium than when rifampicin solution was added.     

Mass spectral characteristics of okadaic acid and simple derivatives.

Electron ionization (EI), chemical ionization (CI) and fast-atom bombardment (FAB) mass spectra of the marine toxin okadaic acid and its synthetic methyl, pentafluorobenzyl, and trimethylsilyl ester and ether derivatives were generated. Several ionization conditions and ion-processing methods were used to obtain positive- and negative-ion conventional spectra and tandem (MS/MS) spectra. The EI and the positive-ion CI spectra provided fragment ions characteristic of the structure, and the negative-ion CI and FAB spectra provided molecular ions. The addition of alkali salts to the FAB matrix resulted in reduced fragmentation and the formation of intense alkali-metal-cationized molecules. Pentafluorobenzyl ester derivatives provided intense carboxylate ions under electron-capture ionization. Analytically useful MS/MS spectra were obtained by low-energy collision-induced decomposition of the carboxylate anion produced from the tetrasilylated pentafluorobenzylokadaate.     

In vitro evaluation of sustained release of risperidone‐loaded microspheres fabricated from different viscosity of PLGA polymers

The aim of this study was to fabricate different risperidone (RIS)–loaded poly(lactic‐co‐glycolic acid) microspheres (PLGA MS) with various viscosity of PLGA polymers and investigate the RIS release profiles. Risperidone‐loaded PLGA MS were fabricated via an oil/water–type emulsion solvent evaporation method, using ethyl acetate and benzil alcohol as the dispersed solvents. The PLGA (75:25) with the viscosity of 0.82, 0.93, and 1.10 dL/g was used in the fabrication. The morphology and the degradation of the RIS‐PLGA MS were investigated with a scanning electron microscope. The distribution states of RIS in the PLGA MS were studied with differential scanning calorimetry. The residual of ethyl acetate and benzil alcohol in the resulting MS was monitored with gas chromatography. The in vitro release profiles of RIS from PLGA MS were also studied. Scanning electron microscope photographs illustrated that the obtained PLGA MS were monodisperse spheres with an average diameter of 100 μm. Gas chromatography results suggested that no residual ethyl acetate was left in the final RIS‐PLGA MS, and the residue amount of benzil alcohol was about 1%. In vitro drug release profiles from the microsphere showed a substantially sigmoidal pattern of negligible initial burst up to 24 hours and minimal release (time lag) for 14 days. After the lag phase, slow release took a place up to 30 days, and then rapid release occurred sharply for about 2 weeks. The RIS release reached equilibrium around day 50. All release profiles showed the similar trend, and no significant difference was observed among these release profiles (P > .05). This phenomenon indicated that RIS‐loaded PLGA MS with the viscosity of 0.82 to 0.93 dL/g showed the optimal release behavior. However, no obvious differences were found among the MS obtained from the viscosity of 0.82 to 1.10 dL/g. These studies provided basis for the quality control in the industrial production of PLGA MS.     

One‐step synthesis of poly(lactic‐co‐glycolic acid)‐g‐poly‐1‐vinylpyrrolidin‐2‐one copolymers

The radical polymerization of 1‐vinylpyrrolidin‐2‐one (NVP) in poly(lactic‐co‐glycolic acid) (PLGA) 50:50 at 100 °C leads to amphiphilic PLGA‐g‐PVP copolymers. Their composition is determined by FT‐IR spectroscopy. Thermogravimetric analyses agree with FT‐IR determinations. Saponification of the PLGA‐g‐PVP polyester portion allows isolating the PVP side chains and measuring their molecular weight, from which the average chain transfer constant (C_T) of the PLGA units is estimated. The MALDI‐TOF spectra of PVP reveal the presence at one chain end of residues of either glycolic acid‐ or lactic acid‐ or lactic/glycolic acid dimers, trimers and one tetramer, the other terminal being hydrogen. This unequivocally demonstrates that grafting occurred. Accordingly, the orthogonal solvent pair ethyl acetate—methanol, while separating the components of PLGA/PVP intimate mixtures, fails to separate pure PVP or PLGA from the reaction products. All PLGA‐g‐PVP and PLGA/PLGA‐g‐PVP blends, but not PLGA/PVP blends, give long‐time stable dispersions in water. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1919–1928     

Detection and characterization by mass spectrometry of radical adducts produced by linoleic acid oxidation

The formation of linoleic acid radical species under the oxidative conditions of the Fenton reaction (using hydrogen peroxide and Fe (II)) was monitored by FAB-MS and ES-MS using the spin trap 5,5-dimethyl-1-pyrrolidine-N-oxide, DMPO. Both the FAB and ES mass spectra were very similar and showed the presence of ions corresponding to carbon- and oxygen centered spin adducts (DMPO/L*, DMPO/LO*, and DMPO/LOO*). Cyclic structures, formed between the DMPO oxygen and the neighboring carbon of the fatty acid, were also observed. Electrospray tandem mass spectrometry of these ions was performed to confirm the proposed structure of these adducts. All MS/MS spectra showed an ion at m/z 114, correspondent to the [DMPO + H]+, and a fragment ion due to loss of DMPO (loss of 113 Da), confirming that they are DMPO adducts. ES-MS/MS spectra of alkoxyl radical adducts (DMPO/LO*) showed an additional ion at m/z 130 [DMPO - O + H]+, while ES MS/MS of peroxyl radical adducts (DMPO/LOO*) showed a fragment ion at m/z 146 [DMPO - OO + H]+, confirming both structures. Other fragment ions were observed, such as alkyl acylium radical ions, formed by cleavage of the alkyl chain after loss of water and the DMPO molecule. The identification of fragment ions observed in the MS/MS spectra of the different DMPO adducts suggests the occurrence of structural isomers containing the DMPO moiety both at C9 and C13. The use of ES tandem mass spectrometry, associated with spin trapping experiments, has been shown to be a valuable tool for the structural characterization of carbon and oxygen-centered spin adducts of lipid radicals.     

Effect of PLGA block molecular weight on gelling temperature of PLGA‐PEG‐PLGA thermoresponsive copolymers

Thermoresponsive, biodegradable polymeric hydrogel networks are used widely in medicinal applications. Poly(d ,l ‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(d ,l ‐lactic acid‐co‐glycolic acid) (PLGA‐PEG‐PLGA) triblock copolymers exhibit a sol–gel transition upon heating. The effect of PLGA block and PEG chain molecular weights (MWs) on the gelling temperature of polymer aqueous solution (20% w/w) is described. All polymer solutions convert into a hard gel within 2 °C of the gelling temperature. The release properties of the gels were displayed using paracetamol as a representative drug. A linear relation is described between the gelling temperature and PLGA block MW. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 35–39     

Synthesis of star‐shaped poly(D,L‐lactic acid‐alt‐glycolic acid)‐b‐poly(L‐lactic acid) with the poly(D,L‐lactic acid‐alt‐glycolic acid) macroinitiator and stannous octoate catalyst

Two types of three‐arm and four‐arm, star‐shaped poly(D,L ‐lactic acid‐alt‐glycolic acid)‐b‐poly(L ‐lactic acid) (D,L ‐PLGA50‐b‐PLLA) were successfully synthesized via the sequential ring‐opening polymerization of D,L ‐3‐methylglycolide (MG) and L ‐lactide (L ‐LA) with a multifunctional initiator, such as trimethylolpropane and pentaerythritol, and stannous octoate (SnOct₂) as a catalyst. Star‐shaped, hydroxy‐terminated poly(D,L ‐lactic acid‐alt‐glycolic acid) (D,L ‐PLGA50) obtained from the polymerization of MG was used as a macroinitiator to initiate the block polymerization of L ‐LA with the SnOct₂ catalyst in bulk at 130 °C. For the polymerization of L ‐LA with the three‐arm, star‐shaped D,L ‐PLGA50 macroinitiator (number‐average molecular weight = 6800) and the SnOct₂ catalyst, the molecular weight of the resulting D,L ‐PLGA50‐b‐PLLA polymer linearly increased from 12,600 to 27,400 with the increasing molar ratio (1:1 to 3:1) of L ‐LA to MG, and the molecular weight distribution was rather narrow (weight‐average molecular weight/number‐average molecular weight = 1.09–1.15). The ¹H NMR spectrum of the D,L ‐PLGA50‐b‐PLLA block copolymer showed that the molecular weight and unit composition of the block copolymer were controlled by the molar ratio of L ‐LA to the macroinitiator. The ¹³C NMR spectrum of the block copolymer clearly showed its diblock structures, that is, D,L ‐PLGA50 as the first block and poly(L ‐lactic acid) as the second block. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 409–415, 2002     

A novel preparation method for microspheres by glycerol modified solid‐in‐oil‐in‐water multi‐emulsion

Biodegradable material poly(D, L ‐lactic‐co‐glycolic) acid (PLGA) plays an important role in drug‐sustained release systems. Here, we describe a glycerol modified solid‐in‐oil‐in‐water (m‐S/O/W) emulsion method for PLGA microspheres, in order to encapsulate proteins in PLGA by utilizing dextran glassy particles to protect the proteins from denaturing, unfolding, and aggregation during preparation and new external water phase to prevent the inner dextran glassy particles from leaking into the external water phase. External water phase containing 20, 40, 60, 80% glycerol showed that proteins released faster and more completely with increased glycerol content. According to their varied release profiles, microspheres of different formulations could be used to encapsulate vaccines or for delivering proteins over long‐term. Copyright © 2009 John Wiley & Sons, Ltd.     

改性纳米羟基磷灰石/PLGA复合材料的制备及生物活性

以低聚乳酸接枝改性的羟基磷灰石纳米粒子(op-HA)和聚丙交酯-乙交酯(PLGA)制备的生物可降解纳米复合材料(op-HA/PLGA)为研究对象, 采用FTIR, TGA, ESEM和EDX分析其接枝反应、接枝率、表面形貌和钙磷沉积情况, 通过在材料膜表面接种兔成骨细胞进行体外培养, 采用荧光染色、NIH Image J图像分析和Real-time PCR综合评价细胞在材料表面的形态、黏附面积比、增殖能力和基因表达水平, 以此评价新型骨修复纳米复合材料op-HA/PLGA的表面性质和生物活性. 研究结果表明, op-HA的表面接枝率为8.3%, 掺入至PLGA后可形成富含钙磷的粗糙表面, 促进成骨细胞的黏附、扩展和增殖, 提高Ⅰ型胶原蛋白(Collagen-Ⅰ)、骨形态蛋白-2(BMP-2)和骨连接蛋白(Osteonectin)的基因表达水平, 提高材料的钙磷沉积能力. op-HA/PLGA具有良好的细胞相容性和成骨活性.     

Synthesis,Characterization and Application of Poly(lactic-co-glycolic acid) with a Mass Ratio of Lactic to Glycolic Segments of 52/48

Poly(lactic-co-glycolic acid)(PLGA) is one of the most representative degradable copolymers and promising drug carriers. In the current paper, the PLGAs with a lactic acid/ glycolic acid(LA/GA) molar ratio of 52/48 and various molecular weights were prepared by a melting method. The molecular weight, molecular weight distribution, and thermal stability were determined by ¹H NMR and thermogravimetric analysis methods. The results demonstrated that PLGAs with the fixed LA/GA molar ratio(52/48), different molecular weights, and narrow molecular weight distribution could be obtained by solely altering the reaction time. The PLGA films were prepared, and their properties including micro-structure, mechanical property, in-vitro cytotoxicity, and biodegradability were characterized. In combination with the homogeneous microstructures and mechanical properties, the drug-loading and releasing properties of PLGA_3.2 films were investigated. The results show that PLGA_3.2 film with an LA/GA molar ratio of 52/48 is a promising curcumin carrier.     

Comparison of mass spectrometric techniques for generating molecular weight information on a class of ethoxylated oligomers

The results of fast atom bombardment (FAB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), matrix-assisted laser desorption/ionization (MALD/I), electrospray ionization (ESI), and field desorption (FD) analyses of ethoxylated oligomers of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfynol^® 104) were compared.Each of these desorption mass spectrometry (MS) techniques can produce spectra of unfragmented cationized oligomers. From the observed ion series we calculate average molecular weight information. We have compared the results of mass spectrometric analyses of a series of ethoxylated Surfynol surfactants. Our data indicate that FAB, ToF-SIMS, MALDI/I, and ESI produce similar results for the lower molecular weight species, but that as the average molecular weight increases FAB and SIMS produce slightly lower results than MALD/I and FD. This could be due to increased fragmentation. ESI produced a result similar to FAB and SIMS for the highest average molecular weight material. Further experiments compare the mass spectral results with gas chromatographic quantitative data. Although gas chromatography is not expected to accurately analyze the higher mass oligomers, we observe significant differences in intensities of the short-chain oligomers (especially the 0- and 1-mers) when compared to the desorption mass spectrometer results. These differences may reflect poor cationization efficiency for very short oligomer chains in the mass spectrometric analyses.     

Direct analysis in real time mass spectrometry (DART‐MS) of highly non‐polar low molecular weight polyisobutylenes

Low molecular weight polyisobutylenes (PIB) with chlorine, olefin and succinic acid end‐groups were studied using direct analysis in real time mass spectrometry (DART‐MS). To facilitate the adduct ion formation under DART conditions, NH₄Cl as an auxiliary reagent was deposited onto the PIB surface. It was found that chlorinated adduct ions of olefin and chlorine telechelic PIBs, i.e. [M + Cl]^? up to m/z 1100, and the deprotonated polyisobutylene succinic acid [M? H]^? were formed as observed in the negative ion mode. In the positive ion mode formation of [M + NH₄]⁺, adduct ions were detected. In the tandem mass (MS/MS) spectra of [M + Cl]^?, product ions were absent, suggesting a simple dissociation of the precursor [M + Cl]^? into a Cl^? ion and a neutral M without fragmentation of the PIB backbones. However, structurally important product ions were produced from the corresponding [M + NH₄]⁺ ions, allowing us to obtain valuable information on the arm‐length distributions of the PIBs containing aromatic initiator moiety. In addition, a model was developed to interpret the oligomer distributions and the number average molecular weights observed in DART‐MS for PIBs and other polymers of low molecular weight. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and NMR Characterization of Multi‐hydroxyl End‐groups PEG and PLGA‐PEG Barbell‐like Copolymers

Multi‐hydroxyl end‐groups poly(ethylene glycol) (PEG) was prepared from PEG and epichlorohydrin. Then, PEG‐supported poly(lactic‐ran‐glycolic acid) (PLGA)_n‐PEG‐(PLGA)_n (n=1, 2, 4) linear‐dendritic barbell‐like copolymers were synthesized through direct polycondensation under bulk condition from the multi‐hydroxyl end‐groups PEG, lactic acid and glycolic acid. Arm numbers were varied, with 2, 4 and 8, by using bis‐, tetra‐, and octa‐hydroxyl end‐groups PEG, respectively. The chemical structures, absolute number‐average molecular weight, the monomer units per single arm and the molar ratio of hydroxyl acid monomer units of the (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were analyzed by NMR spectroscopy. The result indicated that the structures of the multi‐hydroxyl end‐groups PEG and (PLGA)_n‐PEG‐(PLGA)_n barbell‐like copolymers were consistent with design. Compared with the theoretical values, molecular weights determined by ¹H‐NMR end‐group analysis gave reasonably consistent values, but the values determined by gel permeation chromatography (GPC) were considerably less than theoretical values. The results indicated that (PLGA)_n‐PEG‐(PLGA)_n copolymers have linear‐dendritic structures.     

Investigations of the fragmentation pathways of benzylpyridinium ions under ESI/MS conditions

Benzylpyridinium ions are often used as ‘thermometer ions’ in order to evaluate the internal energy distribution of the ions formed in sources of mass spectrometers. However, the detailed fragmentation pathways of these parent ions were not well established. In particular, fragmentation involving a rearrangement (RR) process may be influencing the simulated distribution curves. In a previous study, we suggested that such RR actually occurred under electrospray ionization/mass spectrometry (ESI/MS) and fast atom bombardment/mass spectrometry (FAB/MS) experiments. Here, we present a systematic study of different substituted benzylpyridinium ions. Theoretical calculations showed that RR fragmentation leading to substituted tropylium ions could occur under ‘soft ionization’ conditions, such as ESI or FAB. Experimental results obtained under gas‐phase reactivity conditions showed that some substituted benzylpiridinium compounds actually undergo RR fragmentations under ESI/MS conditions. Mass‐analyzed kinetic experiments were also carried out to gain information on the reaction pathways that actually occur, and these experimental results are in agreement with the reaction pathways theoretically proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

Sol–gel transition behavior of biodegradable three‐arm and four‐arm star‐shaped PLGA–PEG block copolymer aqueous solution

Two types of temperature‐sensitive biodegradable three‐arm and four‐arm star‐shaped poly(DL ‐lactic acid‐co‐glycolic acid‐b‐ethylene glycol) (3‐arm and 4‐arm PLGA–PEG) were successfully synthesized via the coupling reaction of 3‐arm and 4‐arm PLGA and α‐monocarboxyl‐ω‐monomethoxypoly(ethylene glycol) (CMPEG). In dilute aqueous solutions, star PLGA–PEGs showed the temperature‐ and concentration‐dependent formation and aggregation of micelles over specific concentration and specific temperature. With increasing the molecular weight and the relative hydrophobicity of hydrophobic PLGA block, critical micelle temperature (CMT) decreased. Aqueous solution of 4‐arm PLGA–PEG started to form micelles at lower temperature and showed sharper temperature‐dependent growth in micelle size. These results are due to the enhanced hydrophobicity of PLGA block. On the other hand, at high concentration, two types of 3‐arm and 4‐arm PLGA–PEG showed sol–gel–sol transition behavior as the temperature was increased. The 3‐arm and 4‐arm PLGA–PEG showed sol–gel transition at higher polymer concentrations (above 24 wt %) than the PEG–PLGA–PEG triblock copolymer. As the molecular weight and the relative hydrophobicity of PLGA block increased, the critical gel concentration (CGC) decreased. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 888–899, 2006     

MS/MS in structural analysis of an oviposition-deterring pheromone

A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH₃OH]⁺ and [M + H]⁺ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]⁺) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]^– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach.     

A quaternary composite fiber membrane for guided tissue regeneration

This work reported a novel composite fiber membrane containing poly(1actic‐co‐glycolic acid)/six‐armed poly(ε‐caprolactone)/hydroxylapatite‐grafted poly(l ‐lactide)/Pluronic F‐108 (PLGA/SAPCL/HA‐g‐PLLA/PF‐108) produced by electrospinning. SAPCL, HA‐g‐PLLA, and PF‐108 could be well blended with PLGA to make fibers. Fibrous surface and diameter had little difference in morphology with the change of fibrous component. Compared with simple PLGA, PLGA/SAPCL, or PLGA/SAPCL/HA‐g‐PLLA fiber membrane, the quaternary composites not only showed the improved mechanics stability but also possessed better hydrophilicity. The quaternary membrane was conductive to accelerate degradation and maintained nice bioactivity. It was not cytotoxicity. These results suggest that the composite fiber membrane may be qualified as guided bone regeneration substrate. Copyright © 2015 John Wiley & Sons, Ltd.