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A novel electrically conductive and biodegradable composite made of polypyrrole nanoparticles and polylactide.

A novel electrically conductive biodegradable composite material made of polypyrrole (PPy) nanoparticles and poly(d,l-lactide) (PDLLA) was prepared by emulsion polymerization of pyrrole in a PDLLA solution, followed by precipitation. The composite was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. The electrical stability of the composite containing 5 wt% PPy was investigated in a cell culture environment for 1000 h with 100 mV DC applied voltage. Fibroblasts were cultured on the composite membranes and were stimulated with various DC currents. The PPy particles formed aggregations and constituted microdomains and networks embedded in the PDLLA. With the 1-17% increase in the PPy content, the conductivity of the composite increased by six orders of magnitude. The surface resistivity of the PPy/PDLLA membrane with 3% PPy was as low as 1x10(3) Omega/square. The electrical stability was significantly better in the PPy/PDLLA composite than in the PPy-coated polyester fabrics. For the composite with 5% PPy, the test membrane retained 80% and 42% of the initial conductivity in 100 and 400 h, respectively, following the addition of the MEM solution, compared to 5% and 0.1% for the PPy-coated polyester fabrics. Under 100 mV, a composite membrane 3.0x2.5x0.03cm3 in size and containing 5% PPy sustained a biologically meaningful electrical conductivity in a typical cell culture environment for 1000 h. The growth of fibroblasts was up regulated under the stimulation of medium range intensity of DC current.

Adult↗

Effects of crystallization of polyhydroxyalkanoate blend on surface physicochemical properties and interactions with rabbit articular cartilage chondrocytes.

As a new member of polyhydroxyalkanoate (PHA) family, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) has better mechanical properties compared with poly(3-hydroxybutyrate) (PHB). Still, many properties of PHBHHx and its blend with PHB may be exploited for a wide range of applications, such as tissue engineering and drug delivery. In this study, PHBHHx was found to be completely miscible with PHB in their blends. Crystallization behavior of these polyester blends played an important role in determination of the surface physicochemical properties including surface free energy, chemical states and polarity, and could subsequently govern the cellular responses. Interaction between PHB and PHBHHx influenced the non-dispersion surface free energy component, which governed the total surface free energy. It was shown that the blend with a 1:1 ratio of PHB/PHBHHx possessed the highest surface free energy, which was the most optimal material for chondrocytes adhesion. After 24 h, the amount of chondrocytes adhered on films of PHB/PHBHHx (1:1) was 2.1 x 10(4)cells/cm(2), 5-times more compared with that on the PHB films (0.4 x 10(4)cells/cm(2)). The polarity of the blends increased with decreasing crystallinity. After 8 days of cultivation, the chondrocytes attached on PHB films were surrounded by both collagen II and collagen X, the amount of extracellular collagen X decreased with increasing polarity contributed by increasing PHBHHx content in the blend, while chondrocytes changed shapes from spherical to flat with increasing polarity. It indicated that endochondral ossification of chondrocytes was remarkably influenced by the crystallinity of the polyesters.

3-Hydroxybutyric Acid↗

A Nd:YAG laser-microperforated poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-basal membrane matrix composite film as substrate for keratinocytes.

Epithelia cultured for the treatment of ulcers, burns and for gene therapy applications require a flexible biomaterial for growth and transplantation that is adaptable to body contours. We tested several materials and found that a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) polyester provided support for keratinocytes, although adhesion to this material proved to be suboptimal. Since epithelia adhere to the mesoderm through basal membranes, we engineered a basal membrane surrogate by preparing composites of PHBHV with basal membrane matrix (BMM). To allow cell migration into injuried areas the polyester film was micromachined to insert high-density micropores through a Nd:YAG laser ablation process. These flexible composites provided firm attachment for keratinocytes from the outer root sheath of human hair allowing keratinocyte migration through micropores. Films of microperforated PHBHV-BMM may be of use for the replacement of diseased or injured skin epithelia.

Biocompatible Materials↗

The persistence of human scalp hair on clothing fabrics.

This study reports the persistence behaviour of human scalp hairs under a number of different circumstances. The effects of artificial dyeing of hairs, the presence or absence of roots and different types of fabrics on the persistence of hair on a variety of garments were investigated. The garments were made from cotton, polycotton, cotton/acrylic, polyester and wool. The results indicated that neither artificial dyes nor the presence or absence of roots had statistically significant effects on the persistence of hair. In contrast, the type of fabric had a major impact and it was found that, generally, hairs persist longer on rougher fabrics. The rate of loss of hairs from non-woollen fabrics during normal wear was found to follow an exponential decay curve. In contrast, the rate of loss from the woollen garments was quite linear, indicating a constant, even loss, and thus suggests that a different process is involved in the persistence of hairs on woollen garments from that on non-woollen garments. The speed at which hair was lost from fabrics decreased in the order polyester, cotton/acrylic, polycotton, cotton, smooth wool, rough wool, so that wool gives the best chance of recovering samples of hair. Due to the uniqueness of each case, it is advised that caution be used when making any interpretations and before drawing any conclusions.

Clothing↗

Plastic substrates based separation channels in electromigration techniques.

Three types of plastic materials (polyester, polyurethane and polymethylmethacrylate) were tested as materials for manufacturing separation columns (polyester and polyurethane capillaries were used) or separation channels (polymethylmethacrylate) in the chip format. A set of 11 fluorescein isothiocyanate amino acid derivatives was used as the test mixture. Using alpha-cyclodextrin additive to the background electrolyte in the case of the chip separation was also tested. The main problem with all plastic separation media was the selectivity of the separation. The best results, practically identical with bare fused silica capillary, were obtained with the polymethylmethacrylate chip, provided that alpha-cyclodextrin in a concentration 40 mmol/l was added to the background electrolyte. An important observation was that in SDS containing background electrolyte all the plastic materials used exhibited a distinct electroosmotic flow, which was ascribe to the sorption of the negatively charged constituents of the background electrolyte to the capillary wall. Regarding the order in which the individual components of the test mixture were brought to the detector only a single change was observed. Histidine migrated in the polystyrene and polymethylmethacrylate separation channels more slowly than in the bare silica or polyurethane based capillaries.

Electrophoresis, Capillary↗

Preparation and characterization of nanocomposite polyurethane.

Polyurethane/nanosilica composites were prepared using polyester polyol/nanosilica composite resins obtained from in situ polymerization or blending methods and investigated by Fourier transform infrared spectra (FTIR), dynamical mechanical analysis (DMA), transmittance electron microscopy (TEM), contact angle measurement, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM), respectively. It was found that more polyester segments had chemically bonded with silica particles during in situ polymerization than during blending, introducing nanosilica increased the Tgs of polyurethanes, and different preparation methods and different particle sizes caused various impact on Tg. Contact angle measurement and XPS analyses indicated that nanosilica tended to move towards the surfaces and interfaces of polyurethane coats, decreasing the free energies of the surfaces and interfaces, but the nanosilica particles were just observed at interfaces not surfaces by AFM.

Nanostructures↗

Class II composite restorations with metallic and translucent matrices: 2-year follow-up findings.

OBJECTIVE: The aim of this randomized, clinical study was to evaluate the performance of composite restorations placed with two matrix and wedge systems after a 2-year follow-up. METHODS: Twenty-three patients were selected, and received at least two Class II restorations, one with metallic matrix and wooden wedge and other with polyester matrix and reflective wedge. One dentist placed all the 109 restorations. All cavities were restored using Single Bond and P-60 (3M ESPE), according to manufacturer's instructions. In the metal matrix group, polymerization was performed from occlusal, and in the polyester group, through the reflective wedge. Restorations were evaluated at baseline and after 12 and 24 months by the modified USPHS criteria, and data were analyzed with Mann-Whitney and Wilcoxon Signed Rank tests (alpha=0.05). RESULTS: Fifteen subjects and 78 restorations were re-evaluated after 24 months. A significant decrease in the quality of cervical adaptation and proximal contacts by radiographic evaluation was evidenced (p<0.05), but no differences between the two matrix systems were detected (p>0.05). In the clinical evaluation there were no significant differences between matrices after 2 years (p>0.05). A compromising of marginal adaptation, marginal staining and proximal contacts aspects for both matrix systems was evidenced, and restorations placed with translucent matrices showed loss of color stability (p<0.05). CONCLUSIONS: Whereas restorations presented some clinical aspects somewhat compromised after 2 years, the matrix and wedge systems evaluated showed similar clinical performance.

Adolescent↗

The crystal structure of polyhydroxybutyrate depolymerase from Penicillium funiculosum provides insights into the recognition and degradation of biopolyesters.

Polyhydroxybutyrate is a microbial polyester that can be produced from renewable resources, and is degraded by the enzyme polyhydroxybutyrate depolymerase. The crystal structures of polyhydroxybutyrate depolymerase from Penicillium funiculosum and its S39 A mutant complexed with the methyl ester of a trimer substrate of (R)-3-hydroxybutyrate have been determined at resolutions of 1.71 A and 1.66 A, respectively. The enzyme is comprised of a single domain, which represents a circularly permuted variant of the alpha/beta hydrolase fold. The catalytic residues Ser39, Asp121, and His155 are located at topologically conserved positions. The main chain amide groups of Ser40 and Cys250 form an oxyanion hole. A crevice is formed on the surface of the enzyme, to which a single polymer chain can be bound by predominantly hydrophobic interactions with several hydrophobic residues. The structure of the S39A mutant-trimeric substrate complex reveals that Trp307 is responsible for the recognition of the ester group adjacent to the scissile group. It is also revealed that the substrate-binding site includes at least three, and possibly four, subsites for binding monomer units of polyester substrates. Thirteen hydrophobic residues, which are exposed to solvent, are aligned around the mouth of the crevice, forming a putative adsorption site for the polymer surface. These residues may contribute to the sufficient binding affinity of the enzyme for PHB granules without a distinct substrate-binding domain.

Amino Acid Sequence↗

InterGard silver bifurcated graft: features and results of a multicenter clinical study.

OBJECTIVES: Recent research in vascular surgery has focused on development of infection-resistant prosthetic grafts. This article describes the results of a multicenter study to evaluate safety, patency, and infection rates after implantation of the InterGard Silver bifurcated polyester graft coated with collagen and silver. METHODS: Between October 2000 and February 2002, 289 consecutive patients were implanted with a collagen and silver acetate-coated polyester bifurcated graft at 16 French vascular surgery centers. Mean patient age was 65.3 +/- 10.9 years. The indication for prosthetic bypass was aortic aneurysm in 160 patients (55.4%) and symptomatic aortoiliac occlusive disease in 129 (44.6%). All but four patients received prophylactic antibiotic therapy. Patency was assessed at 30 days, 1 year, 2 years, and 3 years, primarily by duplex scan. RESULTS: Two patients (0.7%) died during the first 30 days. Median duration of hospitalization was 11 days. The Kaplan-Meier survival rate at 3 years was 85.7% +/- 4.1%. Primary and secondary patency rates at 3 years were 94.9% +/- 2.6% and 97.5% +/- 1.8%. Thrombectomy was performed successfully in seven patients, and a major amputation was required in two patients with patent grafts. Postoperative complications, including 39 nosocomial infections, were observed in 107 patients (37.0%). Eleven patients presented with 12 wound infections that were classified Szilagyi grade I in eight cases, grade II in two cases, and grade III with graft infection in two cases (0.7%). Among the 149 patients undergoing aortofemoral bypass, eight (5.4%) presented with wound infection, including two graft infections (1.3%). Among the 140 patients undergoing aortoiliac bypass, only three patients (2.1%) presented wound infection and none with graft infection (P = .15). Three (16.7%) of 18 patients who had undergone previous femoral revascularization and eight (3%) of 271 patients without previous femoral revascularization presented with wound infection. This difference was statistically significant (P = .03), with a relative risk of 5.6 (95% confidence interval [CI], 1.6 to 19.5). Five (11.9%) of 42 diabetic patients and six (2.4%) of 247 nondiabetic patients presented with wound infection. This difference was also statistically significant (P = .01), with a relative risk of 3.4 (95% CI, 1.7 to 6.9). Lymphorrhea or lymphocele developed in the groin of 25 patients (8.6%) with negative culture. CONCLUSION: This multicenter prospective study shows that the InterGard Silver graft is safe with no side effects. The primary patency rate was excellent, and the graft infection rate was low, despite a high incidence of nosocomial infections.

Aged↗

The results of in situ prosthetic replacement for infected aortic grafts.

BACKGROUND: Treatment of aortic graft infection with graft excision and axillofemoral bypass may carry an increased risk of limb loss, aortic stump blowout, and pelvic ischemia. A review of patients with aortic graft infection treated with in situ prosthetic graft replacement was undertaken to determine if mortality, limb loss, and reinfection rates were improved with this technique. METHODS: The clinical data of 25 patients, 19 males and 6 females, with a mean age of 68 years (range 35 to 83), with aortic graft infection, treated between January 1, 1989, and December 31, 1998, by in situ prosthetic graft replacement were reviewed. Follow-up was complete in the 23 surviving patients and averaged 36 months (range 4 to 103). RESULTS: Twenty aortofemoral, 3 aortoiliac, and 2 straight aortic graft infections were treated with excision and in situ replacement with standard polyester grafts in 16 patients (64%), or with rifampin-soaked collagen or gelatin-impregnated polyester grafts in 9 patients (36%). Fifteen patients (60%) had aortic graft enteric fistulas, 8 patients (32%) had abscesses or draining sinuses, and 2 patients (8%) had bacterial biofilm infections. Thirty-day mortality was 8% (2 of 25). There were no early graft occlusions or amputations. There was one late graft occlusion. There were no late amputations. The reinfection rate was 22% (5 grafts). All reinfections occurred in patients operated upon for occlusive disease. Only one reinfection occurred in the rifampin-soaked graft group (11% versus 29%, P = NS). Reinfection tended to be lower in patients with aortoenteric fistulas and without abscess. Autogenous tissue coverage provided statistically significant protection against reinfection. There were no late deaths related to in situ graft infection. CONCLUSIONS: Patients treated with in situ graft replacement had an 8% mortality and 100% limb salvage rate. Reinfection rates were similar to those of extra-anatomic bypass, but a trend of lower reinfection rates with rifampin-impregnated grafts was apparent. Patients with aortoenteric fistula and without abscess appear to be well treated by the technique of in situ prosthetic grafting and autogenous tissue coverage.

Abscess↗

Ventricular containment as an adjunctive procedure in ischemic caridomyopathy: early results.

BACKGROUND: Ventricular containment with custom-made polyester mesh is an evolving technique that has been studied in experimental animals with heart failure with good results. METHODS: Five patients with symptomatic heart failure and ischemic cardiomyopathy were enrolled in a Phase I study, and underwent ventricular containment with custom-made polyester mesh along with coronary artery bypass grafting. Four patients had additional ventricular reconstruction of large myocardial scars. RESULTS: All patients were in NYHA functional class III at the time of their operation with a mean ejection fraction of 27.4%+/-6.6%. There were no deaths. Mean postoperative ejection fraction was 35.1%+/-12.6% (p = 0.16). Left ventricular end-diastolic diameter fell from 63.2+/-1.6 mm preoperatively to 50.6+/-5 mm, postoperatively (p = 0.004). There was no evidence of diastolic dysfunction or pericardial constriction on intra- or postoperative echocardiography. At a mean follow-up of 180 days all patients were in NYHA class I with no readmissions for heart failure. Repeat coronary angiography at 6 months revealed patent grafts in all patients. CONCLUSIONS: Ventricular containment with a customized mesh may be performed safely as an adjunct to conventional cardiac operation in patients with symptomatic heart failure. Longer follow-up with an expansion of the study will help delineate the long-term effects of this therapy.

Cardiac Surgical Procedures↗

Evidence for cross-linking in tomato cutin using HR-MAS NMR spectroscopy.

Cutin is a polyester biopolymer component of plant leaf and fruit cuticles, most often associated with waxes and cuticular polysaccharides, and sometimes with another aliphatic biopolymer called cutan. Insolubility of these cuticular biopolymers has made it difficult to apply traditional analytical techniques for structure determination, because most techniques providing molecular level details require solubility. By using the relatively new technique of one and two-dimensional high-resolution magic angle spinning (HR-MAS) NMR spectroscopy, with added information from solid-state 13C NMR spectroscopy, detailed through-bond connectivities and assignments are made for cutin from Lycopersicon esculentum (tomato) fruit. Based on the data obtained, tomato cutin is found to be predominantly an aliphatic polyester with some olefinic and aromatic moieties, consistent with previous studies that employed various degradative approaches. Aside from esters, there are free primary and secondary alcohol groups, as well as free fatty acids. A significant finding is the presence of alpha-branched fatty acids/esters. Mid-chain hydroxyls appear to be generally unesterified, but esters of mid-chain hydroxyls have been identified. The alpha-branched fatty acids/esters and esters of mid-chain hydroxyls could point towards cross-linking.

Biopolymers↗

Biochemical and genetic analysis of PHA synthases and other proteins required for PHA synthesis.

Polyhydroxyalkanoic acids (PHA) represent a complex class of storage polyesters that are synthesized by a wide range of different gram-positive and gram-negative bacteria as well as by some Archaea and that are deposited as insoluble cytoplasmic inclusions. PHA synthases, which are the key enzymes for PHA biosynthesis, have been characterized in much detail. At present 42 PHA synthase structural genes from 38 different bacteria have been cloned, and from 30 genes the nucleotide sequences were obtained. The strategies successfully employed to clone these genes and the current knowledge on the organization of the PHA synthase genes and other genes encoding proteins related to PHA metabolism will be compiled. In addition, the primary structures of the 30 PHA synthases were aligned and analyzed with respect to highly conserved amino acids and biochemical features. The direction, in which research should proceed, in order to increase our knowledge on biosynthesis of PHAs and to utilize this knowledge for the development of technically and economically feasible processes for the production of these polyesters will be outlined.

Acyltransferases↗

Platelet adhesion to commercial and modified polymer materials in animals under psychological stress and in a no-stress condition.

It is well known that stressful stimuli change blood functions and that protein and platelet parameters are altered in humans and animals subjected to stress. We have examined the influence of psychological stress on the morphological responses of platelets on commercially available materials [polyester (VP), fluoropassivated polyester (VPF), non-woven benzylic ester of hyaluronic acid (Hyaff11)] and on materials synthesised (PUPA) and/or surface modified by sulphation (Hyaff11S) or by immobilisation of the anticoagulant molecules heparin and sulphated hyaluronic acid (PUPA-Heparin, PUPA-HyalS, HyalS-PET). Moreover, the anticoagulant activity (i.e. thrombin inactivation) of the materials was analysed. In the no-stress condition, the surfaces with a low degree of platelet adhesion were Hyaff11S, HyalS-PET, PUPA-Heparin and PUPA-HyalS. Hyaff11, PET and PUPA had the highest number of adherent platelets within the series. VP and VPF exhibited an intermediate behaviour. The exposure of animals to stress induced a dramatic change in platelet number and morphology on PET, HyalS-PET, PUPA, PUPA-HyalS and Hyaff11: there was a higher degree of platelet adhesion, increased platelet spreading and the appearance of pseudopodia. In VP, VPF, Hyaff11S and PUPA-Heparin, there were no changes in platelet adhesion in stress conditions with respect to the no-stress condition; the latter two materials, the only ones able to prolong thrombin time, had a very low number of adherent platelets.

Animals↗

Polyhydroxyalkanoate (PHA) scaffolds with good mechanical properties and biocompatibility.

Blending microbial polyesters polyhydroxyalkanoates containing polyhydroxybutyrate (PHB) and poly(hydroxybutyrate-co-hydroxyhexanoate) (PHBHHx) were turned into films and scaffolds. The films made from blending polyesters showed that the elongation to break of the blending PHBHHx/PHB film increased from 15% to 106% when PHBHHx content in the blend increased from 40% to 60%. Scaffolds made of PHBHHx/PHB consisting of 60 wt% PHBHHx showed strong growth and proliferation of chondrocytes on the blending materials under scanning electron microscope. Energy dispersive X-ray analysis of the extra cellular matrix on the scaffolds demonstrated a high level of calcium and phosphorus elements in a molar ratio of Ca/P at 1.66, this is approximately equal to that of natural material hydroxyapatite which has a Ca/P ratio of 1.67. This suggested that the chondrocyte cells grown on PHBHHx/PHB scaffolds presented effective physiological function for generation of cartilage.

3-Hydroxybutyric Acid↗

Application of macromolecular additives to reduce the hydrolytic degradation of polyurethanes by lysosomal enzymes.

Of the various polymers used in medical devices, polyurethanes have been relatively successful because of their acceptable mechanical and biological properties. However, over the past decade, increasing concerns have arisen in relation to long-term biostability of polyurethanes when exposed to the harsh environment of the human body. Lysosomal enzymes released from inflammatory cells have been proposed to be important mediators in the degradation of biomedical polyurethanes. In order to increase the biostability of polyurethanes to lysosomal enzymes, a series of surface-modifying macromolecules (SMMs) were synthesized in this work and then combined into a base polyurethane to reduce the material's susceptibility to hydrolysis. X-ray photoelectron spectroscopy (XPS) studies showed that the SMMs were enriched within the upper 10 nm of the surface. In vitro biodegradation test results indicated that the degradation of a polyester-urea-urethane could be inhibited by the new SMM surface. It was also found that different SMM formulations provided varying degrees of inhibition against the biodegradation of the polyester-urea-urethane. Certain formulations of the SMMs were shown to be physically incompatible with the polyurethane and distorted surface morphology to the extent that biodegradation was enhanced.

Biodegradation, Environmental↗

Polyhydroxyalkanoates, biopolyesters from renewable resources: physiological and engineering aspects.

Polyhdroxyalkanoates (PHAs), stored as bacterial reserve materials for carbon and energy, are biodegradable substitutes to fossil fuel plastics that can be produced from renewable raw materials. PHAs can be produced under controlled conditions by biotechnological processes. By varying the producing strains, substrates and cosubstrates, a number of polyesters can be synthesized which differ in monomer composition. By this means, PHAs with tailored interesting physical features can be produced. All of them are completely degradable to carbon dioxide and water through natural microbiological mineralization. Consequently, neither their production nor their use or degradation have a negative ecological impact. After a historical review, possibilities for the synthesis of novel PHAs applying different micro-organisms are discussed, and pathways of PHA synthesis and degradation are shown in detail for important PHA producers. This is followed by a discussion of the physiological role of the accumulation product in different micro-organisms. Detection, analysis, and extraction methods of PHAs from microbial biomass are shown, in addition to methods for polyester characterization. Strategies for PHA production under discontinuous and continuous regimes are discussed in detail in addition to the use of different cheap carbon sources from the point of view of different PHA producing strains. An outlook on PHA production by transgenic plants closes the review.

Bacteria↗

Plasma protein adsorption on biodegradable microspheres consisting of poly(D,L-lactide-co-glycolide), poly(L-lactide) or ABA triblock copolymers containing poly(oxyethylene). Influence of production method and polymer composition.

Biodegradable particulate systems have been considered as parenteral drug delivery systems. The adsorption of plasma proteins on micro- and nanoparticles is determined by the surface properties and may, in turn, strongly influence the biocompatibility and biodistribution of both carriers. In the present study the influence of the polymer composition and the production method of microspheres on the in vitro plasma protein adsorption were investigated using two-dimensional electrophoresis (2-DE). Microparticles were prepared from poly(l-lactide) (l-PLA), poly(d,l-lactide-co-glycolide) (PLGA), and ABA triblock copolymers containing hydrophilic poly(oxyethylene) (B-blocks) domains connected to hydrophobic polyesters (A-blocks). Two different microencapsulation methods were employed, namely the w/o/w emulsion solvent evaporation method and the spray-drying technique. It could be demonstrated that the polymer composition and, especially, the encapsulation technique, influenced the interactions with plasma proteins significantly. For example, the percentages of several apolipoproteins in the plasma protein adsorption patterns of spray-dried PLGA- and l-PLA-particles were distinctly higher when compared to the adsorption patterns of the particles produced by the w/o/w-technique. Some adsorbed proteins were found to be characteristic or even specific for particles produced by the same method or consisting of identical polymers. Polyvinyl alcohol used as stabilizer in the w/o/w-technique may decisively influence the surface properties relevant for protein adsorption. The plasma protein adsorption on particles composed of ABA copolymers was drastically reduced when compared to microspheres made from pure polyesters. The adsorption patterns of ABA-particles were dominated by albumin. The plasma protein adsorption patterns detected on the different microspheres are likely to affect their in vivo performance as parenteral drug delivery systems.

Adsorption↗