pH‐sensitive polymeric micelles based on amphiphilic polypeptide as smart drug carriers

A series of amphiphilic diblock copolymers having poly(ethylene glycol) (PEG) as one block and a polypeptide as the other block were synthesized by ring‐opening polymerization using PEG‐amine as a macroinitiator. These polymers were characterized by ¹H‐NMR and gel permeation chromatography. The influence of the substitution ratio of tertiary amine‐containing groups on the pH sensitivity of the polymers was investigated in detail. Core/shell‐structured micelles were fabricated from these polymers using an organic solvent‐free method. pH‐ and concentration‐dependent micellization behaviors were investigated by dynamic light scattering and fluorescence microscopy. Micelles loaded with doxorubicin, selected as a model drug, showed restricted drug release at physiological pH but accelerated drug release at tumor extracellular pH. Collectively, our findings suggest that these pH‐sensitive micelles might have great potential for cancer therapy applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4175–4182     

Design and proof of reversible micelle‐to‐vesicle multistimuli‐responsive morphological regulations

Multistimuli‐responsive precise morphological control over self‐assembled polymers is of great importance for applications in nanoscience as drug delivery system. A novel pH, photoresponsive, and cyclodextrin‐responsive block copolymer were developed to investigate the reversible morphological transition from micelles to vesicles. The azobenzene‐containing block copolymer poly(ethylene oxide)‐b‐poly(2‐(diethylamino)ethyl methacrylate‐co‐6‐(4‐phenylazo phenoxy)hexyl methacrylate) [PEO‐b‐P(DEAEMA‐co‐PPHMA)] was synthesized by atom transfer radical polymerization. This system can self‐assemble into vesicles in aqueous solution at pH 8. On adjusting the solution pH to 3, there was a transition from vesicles to micelles. The same behavior, that is, transition from vesicles to micelles was also realizable on addition of β‐cyclodextrin (β‐CD) to the PEO‐b‐P(DEAEMA‐co‐PPHMA) solution at pH 8. Furthermore, after β‐CD was added, alternating irradiation of the solution with UV and visible light can also induce the reversible micelle‐to‐vesicle transition because of the photoinduced trans‐to‐cis isomerization of azobenzene units. The multistimuli‐responsive precise morphological changes were studied by laser light scattering, transmission electron microscopy, and UV–vis spectra. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Determination of paroxetine in serum treated with simple pretreatment by pre‐column high‐performance liquid chromatography using 4‐(5,6‐dimethoxy‐2‐phthalimidinyl)‐2‐methoxyphenylsulfonyl chloride as a fluorescent labeling reagent

The therapeutic drug monitoring of paroxetine could be used to optimize the pharmacological treatment of depressed patients. A simple and sensitive high‐performance liquid chromatography procedure was developed for the determination of paroxetine in serum. After simple pretreatment of serum (50 μL) with acetonitrile and o‐phthalaldehyde, paroxetine was derivatized with 4‐(5,6‐dimethoxy‐2‐phthalimidinyl)‐2‐methoxyphenylsulfonyl chloride at 70°C for 20 min in borate buffer (0.1 mol/L, pH 8.0) to produce a fluorescent product. The derivative was separated on a reversed‐phase column at 40°C for stepwise elution with (A) acetic acid (10 mmol/L) and (B) acetonitrile. The flow rate was 1.0 mL/min. The fluorescence intensity was monitored at excitation and emission wavelengths of 320 and 400 nm, respectively. The within‐day and day‐to‐day relative standard deviations were 3.0–3.4 and 2.7–8.3%, respectively. The detection limit of paroxetine was 8.3 fmol at a signal‐to‐noise ratio of 3. As the proposed method that only requires a small quantity of serum (50 μL) is simple, sensitive and reproducible, it would be useful for clinical and biochemical research as well as drug monitoring. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and Cellular Uptake of pH‐Dependent Fluorescent Single‐Wall Carbon Nanotubes

Fluorescent single‐wall carbon nanotubes (SWCNTs) were prepared by mixing cut SWCNTs with acridine orange (AO). The optical absorbance and fluorescence characteristics of AO–SWCNT conjugates display interesting pH‐dependent properties. Fluorescence microscopy in combination with transmission electron microscopy proves that AO–SWCNTs can enter HeLa cells and are located inside lysosomes. The endocytosis‐inhibiting tests show that the clathrin‐mediated endocytosis is a key step in the internalization process. The internalized AO–SWCNTs remain inside lysosomes for more than a week and have little effect on cell proliferation. These findings may be useful in understanding the SWCNT‐based intracellular drug delivery mechanism and help to develop new intracellular drug transporters.     

Biocompatible and pH‐responsive triblock copolymer mPEG‐b‐PCL‐b‐PDMAEMA: Synthesis,self‐assembly,and application

A series of well‐defined amphiphilic triblock copolymers [polyethylene glycol monomethyl ether]‐block‐poly(ε‐caprolactone)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] (mPEG‐b‐PCL‐b‐PDMAEMA or abbreviated as mPEG‐b‐PCL‐b‐PDMA) were prepared by a combination of ring‐opening polymerization and atom transfer radical polymerization. The chemical structures and compositions of these copolymers have been characterized by Fourier transform infrared spectroscopy, ¹H NMR, and thermogravimetric analysis. The molecular weights of the triblock copolymers were obtained by calculating from ¹H NMR spectra and gel permeation chromatography measurements. Subsequently, the self‐assembly behavior of these copolymers was investigated by fluorescence probe method and transmission electron microscopy, which indicated that these amphiphilic triblock copolymers possess distinct pH‐dependent critical aggregation concentrations and can self‐assemble into micelles or vesicles in PBS buffer solution, depending on the length of PDMA in the copolymer. Agarose gel retardation assays demonstrated that these cationic nanoparticles can effectively condense plasmid DNA. Cell toxicity tests indicated that these triblock copolymers displayed lower cytotoxicity than that of branched polyethylenimine with molecular weight of 25 kDa. In addition, in vitro release of Naproxen from these nanoparticles in pH buffer solutions was conducted, demonstrating that higher PCL content would result in the higher drug loading content and lower release rate. These biodegradable and biocompatible cationic copolymers have potential applications in drug and gene delivery. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1079–1091, 2010     

Reduction and pH dual‐responsive block copolymers containing pendent p‐nitrobenzyl carbamate functionalities: Synthesis and self‐assembly behavior

We report on the preparation of reduction‐responsive amphiphilic block copolymers containing pendent p‐nitrobenzyl carbamate (pNBC)‐caged primary amine moieties by reversible addition–fragmentation chain transfer (RAFT) radical polymerization using a poly(ethylene glycol)‐based macro‐RAFT agent. The block copolymers self‐assembled to form micelles or vesicles in water, depending on the length of hydrophobic block. Triggered by a chemical reductant, sodium dithionite, the pNBC moieties decomposed through a cascade 1,6‐elimination and decarboxylation reactions to liberate primary amine groups of the linkages, resulting in the disruption of the assemblies. The reduction sensitivity of assemblies was affected by the length of hydrophobic block and the structure of amino acid‐derived linkers. Using hydrophobic dye Nile red (NR) as a model drug, the polymeric assemblies were used as nanocarriers to evaluate the potential for drug delivery. The NR‐loaded nanoparticles demonstrated a reduction‐triggered release profile. Moreover, the liberation of amine groups converted the reduction‐responsive polymer into a pH‐sensitive polymer with which an accelerated release of NR was observed by simultaneous application of reduction and pH triggers. It is expected that these reduction‐responsive block copolymers can offer a new platform for intracellular drug delivery. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1333–1343     

A pH‐sensitive water‐soluble N‐carboxyethyl chitosan/poly(hydroxyethyl methacrylate) hydrogel as a potential drug sustained release matrix prepared by photopolymerization technique

Biocompatible pH‐sensitive semi‐interpenetration polymeric network hydrogels (semi‐IPN) based on water‐soluble N‐carboxyethyl chitosan (CECS) and 2‐hydroxyethyl methacrylate (HEMA) were synthesized by the photopolymerization technique. pH‐sensitivity, cytotoxicity, morphology, mechanical property, and water state of hydrogel were investigated by a swelling test, methylthiazolydiphenyl‐tetrazolium bromide (MTT) assay, scanning electron microscopy (SEM), universal testing machine, and differential scanning calorimetry (DSC), respectively. The drug release studies were carried out using 5‐Flurouracil as the model drug. The results indicated that the hydrogels were sensitive to pH of the medium and its wet state had good mechanical properties. The results of cytotoxicity and prolonged drug release characteristics revealed the suitability of the hydrogels as drug delivery matrices. The release kinetics was evaluated by fitting the experimental data to standard release equations, and the best fit was obtained with the Higuchi model of the hydrogel. Copyright © 2008 John Wiley & Sons, Ltd.     

Dual Photo‐ and pH‐Responsive Supramolecular Nanocarriers Based on Water‐Soluble Pillar[6]arene and Different Azobenzene Derivatives for Intracellular Anticancer Drug Delivery

Two novel types of supramolecular nanocarriers fabricated by the amphiphilic host–guest inclusion complex formed from water‐soluble pillar[6]arene ( WP6 ) and azobenzene derivatives G1 or G2 have been developed, in which G1 is structurally similar to G2 but has an extra phenoxy group in its hydrophobic region. Supramolecular micelles can be initially formed by WP6 with G1 , which gradually transform into layered structures with liquid‐crystalline properties, whereas stable supramolecular vesicles are obtained from WP6 and G2 , which exhibit dual photo‐ and pH‐responsiveness. Notably, the resulting WP6 ? G2 vesicles can efficiently encapsulate anticancer drug mitoxantrone (MTZ) to achieve MTZ‐loaded vesicles, which maintain good stability in a simulated normal physiological environment, whereas in an acid environment similar to that of tumor cells or with external UV irradiation, the encapsulated drug is promptly released. More importantly, cytotoxicity assay indicates that such vesicles have good biocompatibility and the MTZ‐loaded vesicles exhibit comparable anticancer activity to free MTZ, especially with additional UV stimulus, whereas its cytotoxicity for normal cells was remarkably reduced. Flow cytometric analysis further confirms that the cancer cell death caused by MTZ‐loaded vesicles is associated with apoptosis. Therefore, the dual pH‐ and UV‐responsive supramolecular vesicles are a potential platform for controlled release and targeted anticancer drug delivery.     

A Synthetic Amino Acid Residue Containing A New Oligopeptide‐Based Photosensitive Fluorescent Organogel

A synthetic amino acid (with a stilbene residue in the main chain) containing a tripeptide‐based organogelator has been discovered. This peptide‐based synthetic molecule 1 self‐assembles in various organic solvents to form an organogel. The gel has been thoroughly characterized by using various microscopic techniques including field‐emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X‐ray diffraction (XRD), UV‐visible and fluorescence spectroscopy, and rheology. Morphological investigations using FESEM and AFM show a nanofibrillar network structure. Interestingly, the organogel is photoresponsive and a gel–sol transition occurred by irradiating the gel with UV light of 365 nm for 2 h as shown by the UV and fluorescence study. This photoresponsive fluorescent gel holds promise for new peptide‐based soft materials with interesting applications.     

Dual crosslinked pH‐ and temperature‐sensitive hydrogel beads for intestine‐targeted controlled release

Novel drug‐loaded hydrogel beads for intestine‐targeted controlled release were developed by using pH‐ and temperature‐sensitive carboxymethyl chitosan‐graft‐poly(N,N‐diethylacrylamide) (CMCTS‐g‐PDEA) hydrogel as carriers and vitamin B₂ (VB₂) as a model drug. The hydrogel beads were prepared based on Ca²⁺ ionic crosslinking in acidic solution and formed dual crosslinked network structure. The structure of hydrogel and morphology of drug‐loaded beads were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The study about swelling characteristics of hydrogel beads indicated that the beads had obvious pH‐ and temperature‐sensitivity. In vitro release studies of drug‐loaded beads were carried out in pH 1.2 HCl buffer solution and pH 7.4 phosphate buffer solution at 37°C, respectively. The results indicated that the dual crosslinked method could effectively control the drug release rate under gastrointestinal tract (GIT) conditions, which was superior to traditional single crosslinked beads. In addition, the effects of grafting percentage, pH value, and temperature on the release behavior of the VB₂ were investigated. The drug release mechanism of CMCTS‐g‐PDEA drug‐loaded beads was analyzed by Peppa's potential equation. According to this study, the dual crosslinked hydrogel beads based on CMCTS‐g‐PDEA could serve as suitable candidate for drug site‐specific carrier in intestine. Copyright © 2009 John Wiley & Sons, Ltd.     

Phenylboronic Acid Appended Pyrene‐Based Low‐Molecular‐Weight Injectable Hydrogel: Glucose‐Stimulated Insulin Release

A pyrene‐containing phenylboronic acid (PBA) functionalized low‐molecular‐weight hydrogelator was synthesized with the aim to develop glucose‐sensitive insulin release. The gelator showed the solvent imbibing ability in aqueous buffer solutions of pH values, ranging from 8–12, whereas the sodium salt of the gelator formed a hydrogel at physiological pH 7.4 with a minimum gelation concentration (MGC) of 5 mg mL^?1. The aggregation behavior of this thermoreversible hydrogel was studied by using microscopic and spectroscopic techniques, including transmission electron microscopy, FTIR, UV/Vis, luminescence, and CD spectroscopy. These investigations revealed that hydrogen bonding, π–π stacking, and van der Waals interactions are the key factors for the self‐assembled gelation. The diol‐sensitive PBA part and the pyrene unit in the gelator were judiciously used in fluorimetric sensing of minute amounts of glucose at physiological pH. The morphological change of the gel due to addition of glucose was investigated by scanning electron microscopy, which denoted the glucose‐responsive swelling of the hydrogel. A rheological study indicated the loss of the rigidity of the native gel in the presence of glucose. Hence, the glucose‐induced swelling of the hydrogel was exploited in the controlled release of insulin from the hydrogel. The insulin‐loaded hydrogel showed thixotropic self‐recovery property, which hoisted it as an injectable soft composite. Encouragingly, the gelator was found to be compatible with HeLa cells.     

Self‐assembled graphene oxide–gelatin nanocomposite hydrogels: Characterization,formation mechanisms,and pH‐sensitive drug release behavior

Novel physically crosslinked graphene oxide (GO)‐gelatin nanocomposite hydrogels were obtained by self‐assembly. The hydrogels with various ratios of GO to gelatin were prepared, and characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy. The static and dynamic rheological properties of the hydrogels were investigated, along with the underlying hydrogel formation mechanisms. The storage modulus of the hydrogels (containing 98–98.5 wt % water) reached 114.5 kPa, owing to the relatively strong physical bonding (i.e., hydrogen bonding and electrostatic forces) between GO and gelatin. Drug release tests showed that the drug release from the hydrogel was pH‐dependent, with 96% of the model drug released in a neutral environment, compared to 28% released in an acidic medium. These hydrogels could have potential in pH‐sensitive drug delivery. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 356–367     

Dual‐responsive supramolecular self‐assembly of inclusion complex of an azobenzene‐ended poly(ε‐caprolactone) with a water‐soluble pillar[6]arene and its application in controlled drug release

Dual photo‐ and pH‐responsive polymeric vesicles are constructed from a host–guest complex between a water‐soluble pillar[6]arene and an azobenzene ended functionalized poly(ε‐caprolactone). Reversible morphological transitions between vesicles and solid aggregates are achieved upon repeated UV stimulus and pH stimulus. Moreover, the polymeric vesicles present excellent cytocompatibility toward HepG2 cells and can be further applied for controlled release of a hydrophilic model drug, DOX?HCl. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2477–2482     

Synthesis and characterization of PNIPAM‐b‐(PEA‐g‐PDEA) double hydrophilic graft copolymer

A series of well‐defined double hydrophilic graft copolymers, consisting of poly(N‐isopropylacrylamide)‐b‐poly(ethyl acrylate) (PNIPAM‐b‐PEA) backbone and poly(2‐(diethylamino)ethyl methacrylate) (PDEA) side chains, were synthesized by successive atom transfer radical polymerization (ATRP). The backbone was firstly prepared by sequential ATRP of N‐isopropylacrylamide and 2‐hydroxyethyl acrylate at 25 °C using CuCl/tris(2‐(dimethylamino)ethyl)amine as catalytic system. The obtained diblock copolymer was transformed into macroinitiator by reacting with 2‐chloropropionyl chloride. Next, grafting‐from strategy was employed for the synthesis of poly(N‐isopropylacrylamide)‐b‐[poly(ethyl acrylate)‐g‐poly(2‐(diethylamino)ethyl methacrylate)] (PNIPAM‐b‐(PEA‐g‐PDEA)) double hydrophilic graft copolymer. ATRP of 2‐(diethylamino)ethyl methacrylate was initiated by the macroinitiator at 40 °C using CuCl/hexamethyldiethylenetriamine as catalytic system. The molecular weight distributions of double hydrophilic graft copolymers kept narrow. Thermo‐ and pH‐responsive micellization behaviors were investigated by fluorescence spectroscopy, ¹H NMR, dynamic light scattering, and transmission electron microscopy. Unimolecular micelles with PNIPAM‐core formed in acidic environment (pH = 2) with elevated temperature (≥32 °C); whereas, the aggregates turned into vesicles in basic surroundings (pH ≥ 7.2) at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5638–5651, 2008     

Efficient synthesis of ionic triblock copolyesters and facile access to charge‐reversal hybrid micelles

Novel carboxyl‐ and amino‐functionalized copolyesters, based on poly(ε‐caprolactone)‐block‐poly(butylene fumarate)‐block‐poly(ε‐caprolactone), were efficiently synthesized via Michael‐type thiol‐ene click chemistry. The resulting amphiphilic copolyesters with controllable molecular weights and abundant positively or negatively charged groups could spontaneously form pH‐sensitive micelles in aqueous solutions, as confirmed by transmission electron microscopy, dynamic light scattering, fluorescence probing technique, and zeta potential analyses. Importantly, charge‐reversal hybrid micelles can be obtained by co‐assembly of carboxyl‐ and amino‐functionalized copolyesters. The surface charges of hybrid micelles reversed rapidly from negative to positive at isoelectric point via protonation of surface carboxyl and amino groups. Interestingly, the hybrid micelles showed apparent pH‐triggered Nile red‐release behavior in acidic condition resembling tumor intracellular environment, which is fairly desirable for drug delivery. Our work indicates that co‐assembly is a facile but efficient way to prepare charge‐reversal micelles, which have great potential to be used as intelligent drug delivery systems for cancer therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1259–1267     

Photo‐ and pH‐Responsive Polycarbonate Block Copolymer Prodrug Nanomicelles for Controlled Release of Doxorubicin

Photo/pH dual‐responsive amphiphilic diblock copolymers with alkyne functionalized pendant o‐nitrobenzyl ester group are synthesized using poly(ethylene glycol) as a macroinitiator. The pendant alkynes are functionalized as aldehyde groups by the azide‐alkyne Huisgen cycloaddition. The anticancer drug doxorubicin (DOX) molecules are then covalently conjugated through acid‐sensitive Schiff‐base linkage. The resultant prodrug copolymers self‐assemble into nanomicelles in aqueous solution. The prodrug nanomicelles have a well‐defined morphology with an average size of 20–40 nm. The dual‐stimuli are applied individually or simultaneously to study the release behavior of DOX. Under UV light irradiation, nanomicelles are disassembled due to the ONB ester photocleavage. The light‐controlled DOX release behavior is demonstrated using fluorescence spectroscopy. Due to the pH‐sensitive imine linkage the DOX molecules are released rapidly from the nanomicelles at the acidic pH of 5.0, whereas only minimal amount of DOX molecules is released at the pH of 7.4. The DOX release rate is tunable by applying the dual‐stimuli simultaneously. In vitro studies against colon cancer cells demonstrate that the nanomicelles show the efficient cellular uptake and the intracellular DOX release, indicating that the newly designed copolymers with dual‐stimuli‐response have significant potential applications as a smart nanomedicine against cancer.     

The stable o‐phthalaldehyde‐ferrocene/6‐ferrocenyl‐1‐hexanethiol pre‐column derivatization high‐performance liquid chromatography of dimethylarginine by novel dual fluorescence and electrochemical detector

Monomethylarginine, asymmetric dimethylarginine and symmetric dimethylarginine were separated on a Wakopak Combi ODS with an acetonitrile–100 mm potassium phosphate buffer (pH 7.0; 1:1, v/v). Dimethylarginines were derived from o‐phthalaldehyde for the fluorescence detector and from 6‐ferrocenyl‐1‐hexanethiol for the electrochemical detector. The detection limits of the dimethylarginines in spiked plasma were 0.3–0.5 pmol by electrochemical detection and 1–2 pmol by fluorescence detection. The detection limits were improved over 30 times by electrochemical detection and 10 times by fluorescence detection compared with previous reports. In previous derivatization liquid chromatography, the reaction solutions, o‐phthalaldehyde, 2‐mercaptethanol and dimethylarginines were unstable and required quick derivatization at 4°C. By our proposed pre‐column methods, the dimethylarginines were derivatized at room temperature and the fluorescent products were stable for 6 h. The manipulation performance was greatly advanced compared with previous LC reports. This is the first report on stable and sensitive dimethylarginines by dual detection. The selectivity was also improved by dual detection. The proposed method was applied to preliminary monitoring of dimethylargines in plasma and urine. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and Characterization of pH‐Sensitive Positive‐charge Silica Nanoparticles for Oral Anionic Drug Delivery

The objective of this study is to utilize the pH sensitivity of modified mesoporous silica nanoparticles (MSN) for oral drug delivery. In the first time, a pH‐sensitive ionic liquid was synthesized through the quaternization of 3‐aminopropyltrimethoxysilane (3‐ATMS) with sodium monochloroacetate (SMCA). Then, silica nanoparticle was modified by this pH‐sensitive ionic liquid and converted to a pH‐sensitive positive‐charge silica nanoparticle (PCSN). The nanoparticle was characterized by FTIR and SEM. Naproxen as anionic drug molecules was entrapped in this pH‐sensitive positive‐charge silica nanoparticles (PCSN) and the in vitro release profiles were established separately in both (SGF, pH 1) and (SIF, pH 7.4).     

Pyrazole‐substituted Near‐infrared Cyanine Dyes Exhibit pH‐dependent Fluorescence Lifetime Properties

Near‐infrared heptamethine cyanine dye is functionalized with pyrazole derivatives at the meso‐position to induce pH‐dependent photophysical properties. The presence of pyrazole unsubstituted at ¹N‐position is essential to induce pH‐dependent fluorescence intensity and lifetime changes in these dyes. Replacement of meso‐chloro group of cyanine dye IR820 with ¹N‐unsubstituted pyrazole resulted in the pH‐dependent fluorescence lifetime changes from 0.93 ns in neutral media to 1.27 ns in acidic media in DMSO. Time‐resolved emission spectra (TRES) revealed that at lower pH, the pyrazole consists of fluorophores with two distinct lifetimes, which cor‐responds to pH‐sensitive and non‐pH‐sensitive species. In contrast, ¹N‐substituted pyrazoles do not exhibit pH response, suggesting excited state electron transfer as the mechanism of pH‐dependent fluorescence lifetime sensitivity for this class of compounds.     

Imidazolium‐modified clay‐based ABS nanocomposites: a comparison between melt‐blending and solution‐sonication processes

Acrylonitrile–butadiene–styrene (ABS) nanocomposites containing imidazolium‐modified montmorillonite have been prepared by melt‐blending (MB) and solution‐sonication in order to study the effects of processing on the morphology and properties of the polymer/clay composites. The structure‐property relationships of the prepared composites have been studied by means of X‐ray diffraction (XRD), transmission electron microscopy (TEM), mechanical testing, dynamic‐mechanical analyses (DMA), thermal gravimetrical analyses (TGA), fluorescence probe confocal microscopy, and fluorescence spectroscopy (FS). X‐Ray and TEM show that both nanocomposites have a mixed intercalated/exfoliated structure. Fluorescence probe confocal microscopy reveals that the sonicated sample has a more homogeneous dispersion: this result is confirmed by the values of elongation at break and flexural elastic modulus measured for the composites. Fluorescence spectroscopy has also been used to investigate the distribution of clay in the composites and results indicate that clay layers in ABS are preferentially located in the styrene‐acrylonitrile (SAN) phase, independent of the dispersion process used. Published in 2008 by John Wiley & Sons, Ltd.