Effect Of Polymer Molecular Weight Research Articles

Biodegradable Poly(2-Dimethylamino Ethylamino)Phosphazene for In Vivo Gene Delivery to Tumor Cells. Effect of Polymer Molecular Weight

PurposePreviously, we have shown that complexes of plasmid DNA with the biodegradable polymer poly(2-dimethylamino ethylamino)phosphazene (p(DMAEA)-ppz) mediated tumor selective gene expression after intravenous administration in mice. In this study, we investigated the effect of p(DMAEA)-ppz molecular weight on both in vitro and in vivo tumor transfection, as well as on complex induced toxicity.Materials and Methodsp(DMAEA)-ppz with a broad molar mass distribution was fractionated by preparative size exclusion chromatography. Polyplexes consisting of plasmid DNA and the collected polymer fractions were tested for biophysical properties, (cyto)toxicity and transfection activity.ResultsFour p(DMAEA)-ppz fractions were collected with weight average molecular weights ranging from 130 to 950 kDa, and with narrow molecular mass distributions (Mw/Mn from 1.1 to 1.3). At polymer-to-DNA (N/P) ratios above 6, polyplexes based on these polymers were all positively charged (zeta potential 25–29 mV), and had a size of 80–90 nm. The in vitro cytotoxicity of the polyplexes positively correlated with polymer molecular weight. The in vitro transfection activity of the different polyplexes depended on their N/P ratio, and was affected by the degree of cytotoxicity, as well as the colloidal stability of the different polyplexes. Intravenous administration of polyplexes based on the high molecular weight polymers led to apparent toxicity, as a result of polyplex-induced erythrocyte aggregation. On the other hand, administration of polyplexes based on low molecular weight p(DMAEA)-ppz’s (Mw 130 kDa) did not show signs of toxicity and resulted in tumor selective gene expression.ConclusionPolymer molecular weight fractionation enabled us to optimize the transfection efficiency/toxicity ratio of p(DMAEA)-ppz polyplexes for in vitro and in vivo tumor transfection.

Comparison of the effectiveness of four different crosslinking agents with hyaluronic acid hydrogel films for tissue‐culture applications

AbstractThe effectiveness of four different reagents, glutaraldehyde (GTA), 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide (EDC), poly(ethyelene glycol) diglycidyl ether (EX 810), and divinyl sulfone (DVS) as crosslinkers for cast hyaluronic acid (HA) films has been evaluated. Films were prepared by casting from solution and exposed to solutions of the crosslinkers in acetone–water solution. Swelling in water and in phosphate buffered saline (PBS) was then used to assess the effectiveness of the crosslinkers. GTA‐crosslinked films were found to be of low stability compared with those treated with EDC, EX 810, and DVS. Results suggest that instability in GTA‐crosslinked materials arises in part from residual acid catalyst. The effects of polymer molecular weight are not uniform. With GTA‐crosslinked film produced from higher molecular weight HA swells more, and this is attributed to reduced diffusion of the crosslinker, but with EDC, the opposite effect is observed, implying some additional molecular weight dependent mechanism. Differential scanning calorimetry and dynamic mechanical thermal analysis results suggest that there are no significant structural difference between the gels for each crosslinker system and only the crosslink density and moisture content alters the transitions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Morphological and chemical modifications and plume ejection following UV laser ablation of doped polymers: Dependence on polymer molecular weight

This work investigates the effect of polymer molecular weight ( M W) on the morphological and chemical modifications and on the plume ejection of doped polymethyl methacrylate (PMMA), and polystyrene (PS) films following irradiation at 248 nm. Micro-bubbles develop in the irradiated films of the low absorbing PMMA-based substrates. The extent and kinetics of the observed morphological changes are respectively larger and last longer in the low M W polymer, as evidenced by optical microscopy and real-time monitoring of transmission of a CW laser. The changes observed in the Raman spectra upon irradiation indicate that degradation occurs to a higher extent in larger M W polymers. Laser induced fluorescence (LIF) probing of the plume reveals the presence of NapH and PhenH products from, respectively, NapI- and PhenI-doped films and a slower ejection process in the plume of low M W polymer. For highly absorbing PS, a less dramatic dependence on M W is observed. Results are discussed in the framework of the bulk photothermal model, according to which ejection requires a critical number of bonds to be broken.

Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 19. Preparation and Characterization of Films of Quaternized Poly(4‐vinylpyridine)‐silica

AbstractQuaternized poly(4‐vinylpyridine) (QPVP) has been incorporated as an anion exchanger into sol‐gel derived silica films for use in a spectroelectrochemical sensor. The preparation, characteristics and performance of these films are described. The films, which are spin‐coated onto the surface of a planar optically transparent electrode, are optically transparent and uniform. Scanning electron microscopy and spectroscopic ellipsometry have been used to examine film structure, thickness and optical properties. These films have been shown both spectroscopically and electrochemically to preconcentrate ferrocyanide, a model analyte for the sensor. The films can be regenerated for multiple measurements by exposure to 1 M KNO3. The effects of polymer molecular weight and storage conditions on film performance are described. The overall response of this film is comparable to the poly(dimethyldiallylammonium chloride)‐silica films previously used for this sensor.

Estradiol loaded PLGA nanoparticles for oral administration: Effect of polymer molecular weight and copolymer composition on release behavior in vitro and in vivo

The present investigation was aimed at optimization of estradiol loaded PLGA nanoparticulate formulations resulting in improved oral bioavailability and sustained release of estradiol by varying the molecular weight and copolymer composition of PLGA. Nanoparticles were prepared following emulsion–diffusion–evaporation method employing didodecyldimethyl ammonium bromide (DMAB) as stabilizer. The effect of polymer molecular weight and copolymer composition on particle properties and release behavior ( in vitro and in vivo) has been reported. Drug release in vitro decreased with increase in molecular weight and lactide content of PLGA. Zero order release was obtained with low molecular weight (14,500 and 45,000 Da) PLGA, while high molecular weight (85,000 and 213,000 Da) and different copolymer compositions followed square root of time (Higuchi's pattern) dependent release. The bioavailability of estradiol from nanoparticles was assessed in male Sprague Dawley (SD) rats at a dose of 1 mg estradiol/rat. The in vivo performance of the nanoparticles was found to be dependent on the particle size, polymer molecular weight and copolymer composition. The C max of drug in the plasma was dependent on the polymer molecular weight and composition while particle size was found to influence the duration of release, suggesting smaller is better. The histopathological examination revealed absence of any inflammatory response with the formulations prepared of low/high molecular weight or high lactide content polymers for the studied period. Together, these results indicate that nanoparticulate formulations are ideal carriers for oral administration of estradiol having great potential to address the dose related issues of estradiol.

Investigation on process parameters of electrospinning system through orthogonal experimental design

AbstractElectrospinning is a very simple and versatile method of creating polymer‐based high‐functional and high‐performance nanofibers. But most of the investigations are not systematic and describe the electrospinning process without quantitative accuracy. Inconsistent and even opposite results have been reported, which has hindered the consistent interpretation of the experiments. Orthogonal experimental method was used to investigate qualitative and quantitative correlations between fiber characteristics (diameters and morphologies) and the processing and materials parameters. Uniform fibers can be obtained without any beads by proper selection of the processing parameters, and a lower glass transition temperature was observed for electrospun fibers than that of native polymer. Results of statistical analysis showed that significant influences were observed for polymer molecular weight and solution concentration on fiber diameters, and there were significant effects of polymer molecular weight, solution concentration, and solvent system on fiber morphologies. Meanwhile, solution concentration and polymer molecular weight, and polymer molecular weight and solvent system had obvious interaction effects. Regression analysis revealed quantitative relations of fiber diameters and beads percent, that is, Y1 = 72.8X1 − 8.1X2 + 138.8, Y2 = −3.2X1 + 0.4X2 + 60.5, where Y1 is fiber diameter (nm), Y2 beads percent (%), X1 solution concentration (%, w/w), and X2 polymer molecular weight (kDa). Validation test showed that the experimental values of fiber size and beads percent were in good agreement with the calculated ones. Based on these results, optimal conditions could be obtained for predetermined diameters and morphologies for electrospun fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3105–3112, 2007

Minimizing the surface effect of PDMS–glass microchip on polymerase chain reaction by dynamic polymer passivation

AbstractPolydimethyl siloxane (PDMS)–glass microchip has a very strong surface effect on polymerase chain reaction (PCR), leading to a very poor PCR yield. In the work reported here, practical dynamic passivation of surfaces of PDMS–glass microchip using polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) was achieved using a conventional thermocycler. The passivation procedure was cost‐effective and easy to conduct. The effects of polymer molecular weight and polymer concentration on tube PCR efficiency were investigated primarily to prescreen out suitable polymers and polymer concentrations in the PCR mixture. The result from tube PCR indicated that both PEG and PVP could affect the performance of Taq polymerase. A final concentration of 0.025% (w/v) or 0.4% (w/v) polymer in the PCR mixture can enhance the tube PCR, while 1% (w/v) polymer was found to inhibit the reaction. PEG was more effective in tube PCR, although PVP performed better in chip PCR. Instead of employing the polymer directly in the PCR mixture, i.e. the conventional in situ passivation approach, another approach of dynamic passivation by pre‐injecting polymers into the microchip achieved better performance. The efficiency of pre‐passivation was found to follow the order: PVP10000>PVP55000, PEG8000> PEG10000>PEG400. After pre‐passivation with PVP10000, PVP55000 and PEG8000, the PCR efficiency can recover to 93%, 86% and 83%, respectively, of that obtained from tube PCR. Copyright © 2006 Society of Chemical Industry

Structural Investigations of Silica Polyamine Composites: Surface Coverage, Metal Ion Coordination, and Ligand Modification

Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of “free amines”. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake studies show increases in Cu(II) capacity and/or an improvement in Cu(II) mass-transfer kinetics. The effect of polymer molecular weight upon Cu(II) capacity was investigated for each polyamine. Substantial differences in Cu(II) capacity between 50 000 MW poly(vinylamine) (PVA) and >1000 MW PVA were evident. Similar differences between 25 000 MW poly(ethyleneimine) (PEI) and 1200 MW PEI were found. The mass-transfer kinetics was shown to be improved for composites prepared using a large fraction of MTCS in the reagent silane mixture. This resulted in substantial improvements in the 10% breakthrough Cu(II) capacity for PVA (50 000 MW). PEI composites were further modified to form an amino−acetate ligand. The impact of the MTCS:CPTCS silane ratio on the acetate ligand loading and ultimately on the Cu(II) capacity at pH = 2 was investigated. A ratio of 12.5:1 was shown to result in an acetate modified PEI composite with a Cu(II) capacity 140% of the Cu(II) capacity of the same composite prepared with “CPTCS only”.

Flight path of electrospun polystyrene solutions: Effects of molecular weight and concentration

The behavior of the solution jet during electrospinning is a consequence of the balance between electrical, surface tension, and viscoelastic forces. Solution rheology, which is known to have a significant effect on the structure of the electrospun polymer, may also affect jet evolution and breakdown. In this study, the effect of polymer molecular weight and concentration on the behavior of polystyrene solution jet was investigated using high speed camera (2000 frames/s). The results indicate that the degree of elongational flow, bending instability, and jet branching depends on polymer molecular weight and concentration. It was observed that jet thinning and solidification may occur at different distances from the capillary when the rheological conditions are varied.

Effect of Molecular Weight on the Morphological Modifications Induced by UV Laser Ablation of Doped Polymers

This work investigates the effect of polymer molecular weight (M(W)) on the surface morphology of poly(methyl methacrylate) (PMMA) and polystyrene (PS) films doped with iodonaphthalene (NapI) and iodophenanthrene (PhenI) following irradiation in air at 248 nm. In agreement with previous studies, irradiation of PMMA at 248 nm results in surface swelling and bubble formation within the irradiated bulk. Most importantly, the size of bubbles varies sensitively for the different M(W) values, with larger bubbles being formed for the low M(W) systems. Nevertheless, the maximum swelling attains higher values for the high M(W) values (when compared at the corresponding ablation threshold of the systems). Real-time monitoring of transmission of a probing beam shows that morphological changes last longer in the low M(W) polymer. Melting, consistent with a thermal mechanism, occurs, and enough evidence is gathered to provide direct support for the bulk photothermal model, according to which ejection requires that a critical number of bonds is broken. In particular, the observed different morphological effects can be ascribed to the interplay of two factors, namely, of the much more efficient decomposition of the low M(W) polymer to gaseous products and of the dependence of the mechanical polymer properties on M(W). For PS at 308 nm, the changes parallel the ones for PMMA at 248 nm. In contrast, at the strongly absorbed 248 nm, the morphological processes in PS show a less dramatic dependence on M(W). In all, these results are of direct importance for the optimization of laser processing schemes and applications (e.g., tissue processing, laser deposition, laser restoration, etc.).

Surface Modification of CdSe and CdSe/ZnS Semiconductor Nanocrystals with Poly(N,N-dimethylaminoethyl methacrylate)

We report passivation of CdSe and CdSe/ZnS nanocrystals (NCs) with poly(N,N-dimethylaminoethyl methacrylate) (PDMA) through a ligand exchange process. We present the results from various techniques that were used to verify that ligand exchange occurred, including 1H NMR, 31P NMR, and changes in solubility/colloidal properties, hydrodynamic radius, and photoluminescence. We have examined the effect of polymer molecular weight on the surface passivation and quantum yields of the NCs. As additional evidence for the binding of the polymer to the surface of the NC, we were able to modify the polymer chemically to render the NC−polymer moiety water-soluble.

Effects of end group polarity and molecular weight on the lower critical solution temperature of poly(N‐isopropylacrylamide)

AbstractThe lower critical solution temperatures (LCSTs) for mass fractionated samples of poly(N‐isopropylacrylamide) (PNIPAM) were studied to determine the effect of polymer molecular weight on the LCST using a high throughput temperature gradient apparatus. PNIPAM fractions prepared by a conventional radical polymerization using azoisobutyronitrile (AIBN) as the initiator had LCSTs that were largely invariant with molecular weight or dispersity. Only slight deviations were noted with lower molecular weight samples. An 18‐kDa sample had a 0.6 °C higher LCST. A 56‐kDa sample had a 0.2 °C higher LCST. PNIPAM derivatives prepared with a triphenylmethyl (trityl) functionalized azo initiator were also prepared and mass fractionated. These samples' LCSTs were identical to those of PNIPAM samples prepared using AIBN initiation when higher molecular weight samples were compared. The trityl‐containing PNIPAM fractions' LCSTs varied when the molecular weight decreased below 100 kDa. Acidolysis of the trityl end groups provided a third set of PNIPAM derivatives whose LCST differed only with samples with Mw values < 60 kDa. These results show there is no effect of molecular weight on LCST until the degree of polymerization is such that end group structure becomes significant. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1492–1501, 2006

Formulation and pharmacodynamic evaluation of captopril sustained release microparticles

Cellulose propionate (CP) microparticles containing captopril (CAP) were prepared by solvent evaporation technique. The effects of polymer molecular weight, polymer composition and drug : polymer ratios on the particle size, flow properties, morphology, surface properties and release characteristics of the prepared captopril microparticles were examined. The anti-hypertensive effect of the selected CAP formulation in comparison with aqueous drug solution was also evaluated in vivo using hypertensive rats. The formulation containing drug : polymer blend ratio 1 : 1.5 (1 : 1 low : high molecular weight CP), namely F7, was chosen as the selected formulation with regard to the encapsulation efficiency (75.1%), flow properties (θ = 24°, Carr index = 5%, Hausner ratio = 1.1, packing rate = 0.535) and release characteristics. Initial burst effect was observed in the release profile of all examined formulations. DSC and SEM results indicated that the initial burst effect could be attributed to dissolution of CAP crystals present on the surface or embedded in the superficial layer of the matrix. The release kinetics of CAP from most microparticle formulations followed diffusion mechanism. After oral administration of the selected microparticle formulation (F7) to hypertensive rats, systolic blood pressure decreased gradually over 24 h compared to reference drug solution. These results may suggest the potential application of cellulose propionate microparticles as a suitable sustained release drug delivery system for captopril

Different methods for surface modification of hydrophilic particulates with polymers

Three different methods of attaching polymers to sand are compared: in situ graft polymerization, chemical grafting of preformed polymers, and admicellar polymerization which uses a surfactant template. Sample characterization includes Raman spectroscopy, gravimetric analysis, contact angle measurements, and high solids rheology tests. In all cases, the presence of polymer on the surface was confirmed, but differences in terms of amount of polymer adsorbed, surface chemistry, and interparticle friction were found. The effect of polymer molecular weight for the chemically grafted material was studied as well. An optimum molecular weight around 600,000 g/mol was found for maximum friction reduction in preformed poly(vinylpyrrolidone)-modified sand samples.

Effect of Polymer Molecular Weight on the Polymer/Surfactant Interaction

A thermodynamic analysis of the interaction between fourteen different molar mass poly(ethylene oxide)s (PEO) and sodium dodecyl sulfate (SDS) based on the measured surfactant-binding isotherms is given. The surfactant-binding isotherms were determined by the potentiometric method in the presence of 0.1 M inert electrolyte (NaBr). It was found that there is no PEO/SDS complex formation if M(PEO) < 1000. In the molecular weight range 1000 < M(PEO) < 8000, the critical aggregation concentration (cac) and the surfactant aggregation number are decreasing as the polymer molecular weight increases. The saturated bound surfactant amount is proportional to the number concentration of the polymer in this molecular weight range. If M(PEO) exceeds approximately 8000, the cac does not depend on the polymer molar mass, and the saturated bound amount of the surfactant becomes proportional to the mass concentration of the polymer. It was also observed that independently of the polymer molecular weight the surfactant aggregation number increases as the equilibrium surfactant monomer concentration increases from the cac to the critical micellar concentration (cmc). Finally, it was demonstrated that only one polymer molecule is involved in the complex formation independently of the polymer molecular weight.

Transfection efficiency of chitosan vectors: Effect of polymer molecular weight and degree of deacetylation

Chitosans of defined molecular weight (Mw 10–213 kDa) and degree of deacetylation (DD 46–88%) were synthesized, complexed with pEGFP-C2 plasmid into nanoparticles (NP) and evaluated for cellular uptake and transfection efficiency in the A549 cell model. DNA condensation of > 90% was achieved at the N/P ratio of 6, independent of the chitosan Mw and DD. However, chitosan vectors of lower Mw or DD were less efficient at retaining the DNA upon dilution, and consequentially, less capable of protecting the condensed DNA from degradation by DNase and serum components. A549 cellular uptake of the NP was also significantly reduced by decreasing the Mw or DD of the chitosan vector. These factors contributed to the low transfection efficiencies for chitosan vectors of low Mw or DD. There was good correlation between transfection efficiency, cellular uptake and zeta potential of the NP, suggesting that cellular uptake mediated by electrostatic interactions with the cell membrane preceded efficient transfection. NP produced with chitosan of Mw 213 kDa and DD of 88% showed the highest zeta potential (+ 23 mV), cellular uptake (4.1 μg/mg protein) and transfection efficiency (12.1%), while chitosan vector with Mw of 213 kDa and DD of 46% showed the lowest cellular uptake (0.4 μg/mg protein) and transfection efficiency (0.05%). Confocal microscopy images suggested that the chitosan-complexed DNA successfully escaped from the endo-lysosomal compartment for nuclear translocation and expression. Intracellular DNA disassembly appeared to occur at different locations depending on the retentive capacity of the chitosan vector.

Complexation of well-controlled low-molecular weight polyelectrolytes with antisense oligonucleotides

The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ (DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG, but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON.

Structure–function relationships of gene delivery vectors in a limited polycation library

A library of 13 polylysine- graft-imidazoleacetic acid conjugates was synthesized to examine the collective effects of polymer molecular weight, side chain substitution, and DNA:polymer ratio on cytotoxicity, transfection efficiency, and polycation–DNA interaction. In general, the relationships between the physicochemical characteristics and the gene transfer capabilities of these polycations appear nonlinear. The in vitro cytotoxicity of these polymers decreased, while total protein expression increased, with decreasing molecular weight and increasing imidazole content. Flow cytometry experiments indicated, however, that an increase in marker gene expression does not always correlate with the total number of cells transfected, even when similar polymer structures are used for transfection. The maximum level of luciferase gene expression was mediated by transfection with a low molecular weight, high imidazole content (9400 M w, 95 mol% imidazole) polymer. The extent of DNA condensation, as determined by ethidium bromide fluorescence quenching, also decreased with decreasing polymer molecular weight and increasing imidazole content. Relative binding affinity between DNA and the polycations, measured via competitive binding in the presence of a synthetic polyanion, decreased with decreasing polymer molecular weight; however, the relative affinity also appeared to increase with increasing imidazole, suggesting that electrostatic contributions are not solely responsible for DNA–polycation binding interactions. This limited library and corresponding structure/function analysis forms the foundation upon which larger, more comprehensive polycationic libraries can be designed and evaluated to further understand how polycation transfection reagents function.

Shake gels based on Laponite–PEO mixtures: effect of polymer molecular weight

Disc-shaped clay particles (Laponite) with a thickness of 1 nm and a diameter of 25 nm were bridged into a physical gel (shake gel) by poly(ethylene oxide) (PEO) chains under shear. The shake gels formed transformed again into a liquid when the shear stopped. The critical concentrations of Laponite and PEO required for the shake gel formation were determined. The results show that the molecular weight of the polymer chains significantly affects the critical concentrations, as well as the mechanical properties of gels. Shake gels form under certain concentrations of Laponite and PEO, corresponding to a critical surface coverage value n PEO of the Laponite particles by the polymer chains. The value of n PEO decreases as the molecular weight of PEO is increased. It was shown that strong gels with a relaxation time longer than 30 min form if the polymer molecular weight is in the range of 2 × 105−3 × 105 g/mol.

Poly(lactide-co-glycolide) microspheres as a moldable scaffold for cartilage tissue engineering

This study demonstrates the use of biodegradable poly(lactide-co-glycolide) (PLG) microspheres as a moldable scaffold for cartilage tissue engineering. Chondrocytes were delivered to a cylindrical mold with or without PLG microspheres and cultured in vitro for up to 8 weeks. Cartilagenous tissue formed using chondrocytes and microspheres maintained thickness, shape, and chondrocyte collagen type II phenotype, as indicated by type II collagen staining. The presence of microspheres further enhanced total tissue mass and the amount of glycosaminoglycan that accumulated. Evaluation of microsphere composition demonstrated effects of polymer molecular weight, end group chemistry, and buffer inclusion on tissue-engineered cartilage growth. Higher molecular weight PLG resulted in a larger mass of cartilage-like tissue formed and a higher content of proteoglycans. Cartilage-like tissue formed using microspheres made from low molecular weight and free carboxylic acid end groups did not display increases in tissue mass, yet a modest increased proteoglycan accumulation was detected. Microspheres comprised of PLG with methyl ester end groups yielded a steady increase in tissue mass, with no real increase in matrix accumulation. The microencapsulation of Mg(OH)2 had negative effects on tissue mass and matrix accumulation. The data herein reflect the potential utility of a moldable PLG-chondrocyte system for tissue-engineering applications.