Propylsuccinic Anhydride Research Articles

Improving interface interactions in PLA/HAP composites with hydroxyapatite surface modification

ABSTRACT PLA/HAP composites have attracted significant attention in material science, especially in the field of biomaterials. However, these composites have suffered from unfavorable interface interactions between PLA and HAP interfaces, which limits the applications . In this study, we aimed to improve the interface interactions of PLA/HAP composite by modifying the HAP surface. For this purpose, HAP particles were functionalized with three different silane modifying agents, including (3-Aminopropyl)trimethoxysilane (AMMO), (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and (3-triethoxysilyl)propylsuccinic anhydride (GF-20). The obtained modified HAP (m-HAP) were used to prepare PLA/m-HAP. Interface interactions of composites were characterized by Fourier transform infrared spectrophotometer (FT-IR) and differential scanning calorimetry (DSC). In addition, Vickers hardness tests were performed to reveal the effect of silane modifying agents on hardness before and after the in vitro degradation test.

Development of Methods for Specific Capture of Biological Targets on Aluminum Substrates: Application to Bacillus subtilis Spore Detection as a Model for Anthrax.

Many (if not most) biosensors rely on functional silane coatings as a first step toward covalent immobilization of specific capture molecules. While methods for silanization of silica (SiO2) surfaces are very well developed, less has been done to develop and characterize silanization methods for alternative substrates, such as alumina (Al2O3). In particular, the behavior of Al2O3 coatings grown on aluminum under ambient conditions has not been studied. To address this issue, we have tested solution-phase deposition of two silanes on Al2O3 (3-aminopropyl triethoxysilane and 3-triethoxysilyl)propylsuccinic anhydride) and their applicability to analyte-specific biosensing. Contact angle measurements and imaging via Scanning Electron Microsopy (SEM) were employed to characterize surfaces. We find that 3-aminopropyl triethoxysilane produces well-behaved films and demonstrate that this surface can undergo further reaction with glutaraldehyde followed by an anti-Bacillus subtilis antibody to yield functionalized Al2O3 surfaces capable of specific capture of B. subtilis spores (a model of B. anthracis, the causative organism of Anthrax). In contrast, 3-triethoxysilyl)propylsuccinic anhydride did not behave well with Al/Al2O3 under the reaction conditions tested. In addition to providing specific protocols for Al/Al2O3 functionalization, this work highlights the importance of surface chemistry assessment in the development of new sensors.

Toxicity of Modified Magnetite-Based Nanocomposites Used for Wastewater Treatment and Evaluated on Zebrafish (Danio rerio) Model.

Magnetite-based nanocomposites are used for biomedical, industrial, and environmental applications. In this study, we evaluated their effects on survival, malformation, reproduction, and behavior in a zebrafish animal model. Nanoparticles were synthesized by chemical coprecipitation and were surface-functionalized with (3-aminopropyl) triethoxysilane (APTES), L-cysteine (Cys), and 3-(triethoxysilyl) propylsuccinic anhydride (CAS). All these nanocomposites were designed for the treatment of wastewater. Zebrafish embryos at 8 h post-fertilization (hpf) and larvae at 4 days post-fertilization (dpf) were exposed to the magnetic nanocomposites Fe3O4 MNP (magnetite), MNP+APTES, MNP+Cys, MNP+APTES+Cys, and MNP+CAS, at concentrations of 1, 10, 100, and 1000 µg/mL. Zebrafish were observed until 13 dpf, registering daily hatching, survival, and malformations. Behavior was tested at 10 dpf for larvae, and reproduction was analyzed later in adulthood. The results showed that the toxicity of the nanocomposites used were relatively low. Exploratory behavior tests showed no significant changes. Reproduction in adults treated during development was not affected, even at concentrations above the OECD recommendation. Given the slight effects observed so far, these results suggest that nanocomposites at the concentrations evaluated here could be a viable alternative for water remediation because they do not affect the long-term survival and welfare of the animals.

Preparation and characterization of polyurethane rubber/polypropylene-based thermoplastics vulcanizates nanocomposites with succinic anhydride intercalated layered double hydroxide

Herein, a novel polypropylene/polyurethane rubber (PP/PUR) was prepared based on thermoplastics vulcanizates (TPV)/layered double hydroxide (LDH) nanocomposite in the presence of 3-(triethoxysilyl)propylsuccinic anhydride (SSA) intercalated LDH (SSA-LDH). The effect of SSA-LDH was explored on thermo-mechanical, thermal, morphological, rheological, and mechanical properties as well as gel content, compression set, X-ray photoelectron spectroscopy analysis, and cross-linking density (CLD) of TPV based on PP/PUR with the weight ratio of 40/60. It was found that the crystallization, tensile strength, gel content, cross-linking density, young’s modulus, elongation at break, melting point, and damping factor significantly changed with increasing SSA-LDH content in PUR/PP TPVs. The reasons could be attributed to cross-linking induced by SSA-LDH and curing agent Bis-(triethoxysilylpropyl) tetrasulfide (also called (Si-69)) that grafted onto PUR chains, resulting in good dispersion of fine PUR vulcanized particles into PP matrix. This claim was confirmed by studying the rheological properties through Rheometeric mechanical spectroscopy and dynamic-mechanical analysis. Field emission scanning electron microscope images confirmed the improved compatibility between PUR and PP by adding SSA-LDH. The gel content and CLD of TPV samples without SSA-LDH were 20% and 2.75 mol/mL, respectively, which showed a significant increment to 25.5% and 4.5 mol/L upon adding 5 wt. % SSA-LDH. The highest elongation at break, tensile strength, and young’s modulus were 525%, 16.5 MPa, and 210 MPa, respectively which were observed for TPV5.

Functionalization and Evaluation of Inorganic Adsorbents for the Removal of Cadmium in Wastewater.

This study presents the feasibility of using various functionalized substrates, Fe3O4 nanoparticles (NPs) and Al2O3 spheres, for the removal of Cd from aqueous solution. To improve the materials’ affinity to Cd, we explored four different surface modifications, namely (3-Aminopropyl) triethoxysilane (APTES), L-Cysteine (Cys) and 3-(triethoxysilyl) propylsuccinic anhydride (CAS). Particles were characterized by FTIR, FIB-SEM and DLS and studied for their ability to remove metal ions. Modified NPs with APTES proved to be effective for Cd removal with efficiencies of up to 94%, and retention ratios up to 0.49 mg of Cd per g of NPs. Batch adsorption experiments investigated the influence of pH, contact time, and adsorbent dose on Cd adsorption. Additionally, the recyclability of the adsorbent and its potential phytotoxicity and animal toxicity effects were explored. The Langmuir, Freundlich, pseudo-first-order and pseudo-second-order models were applied to describe the behavior of the Cd adsorption processes. The adsorption and desorption results showed that Fe3O4 NPs modified with APTES are promising low-cost platforms with low phytotoxicity for highly efficient heavy metal removal in wastewater.

Printed carbon based interface for protein immobilization

The aim of the investigations was to find a method of protein immobilisation in screen printed graphite layers. Three commonly used graphite powders were used to prepare conductive layers via screen printing. Several printing pastes with different carbon to polymer resin (polymethylmethacrylate) ratios were tested and the composition with the best electrical properties was selected for further investigations related to green fluorescent protein immobilisation. Six different procedures of protein immobilisation were examined including physical adsorption, electrochemical generation of carboxylic groups and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide activation, graphite functionalisation with succinic anhydride and graphite functionalisation with 3-(triethoxysilyl)propylsuccinic anhydride. Some of the functionalisation procedures were done before printing (functionalisation of graphite powders) and the others were done on printed and cured coatings. Printed graphite layers with immobilised green fluorescent proteins were studied with confocal fluorescent microscopy to assess the efficiency of the immobilisation procedures. The best results were observed for graphite functionalisation with succinic anhydride and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide activation of carboxylic groups.

Preparation of Polyhedral Oligomeric Silsesquioxanes Containing Carboxyl Side-Chain Groups and Isolation of a Cage-Like Octamer Using Clay Mineral

Abstract The hydrolytic condensation of 3-(triethoxysilyl)propyl succinic anhydride (TESPSA) in water using bulky base or acid catalysts such as tetra-n-butylammonium hydroxide (n-Bu4NOH) or trifluoromethanesulfonic acid, respectively, afforded mixtures containing polyhedral oligomeric silsesquioxanes (POSSs) as main products. The mixture obtained under basic conditions contained cage-like octamer (T8-POSS) and that from acidic conditions contained cage-like decamer (T10-POSS) and dodecamer (T12-POSS). On the other hand, polysilsesquioxanes with number average molecular weights of 1.25 × 104 or 1.43 × 104 were obtained when the hydrolytic condensation of TESPSA was performed in the presence of non-bulky base (sodium hydroxide) or acid (hydrochloric acid) catalysts, respectively, in water as a solvent. In addition, only T8-POSS could be isolated from the silsesquioxane mixture obtained via the hydrolytic condensation of TESPSA using n-Bu4NOH by sequential treatment with a clay mineral such as montmorillonite in water and acetone.

Effect of Nanochannel Size of Surface Treated Thru-Hole Alumina Membrane in Rejection of Polar Molecules

This paper presents the effect of nanochannel size of surface treated thru-hole alumina membrane in rejection of polar molecules. Polar molecules of methyl blue in a methyl blue aqueous solution were rejected by the equivalent charge of a surface-treated thru-hole alumina membrane. Thru-hole alumina membranes, having four different nanochannel diameters, were fabricated by the two-step aluminum anodic oxidation and wet-etching processes. Surface of the fabricated thru-hole alumina membrane was negatively charged using 3-(triethoxysilyl) propylsuccinic anhydride (TEPSA), which includes a carboxyl group. A methyl blue aqueous solution of 10 μM, which possessed negative charge, was injected through a negatively charged thru-hole alumina membrane to investigate its rejection ability. In the experiment using pristine thru-hole alumina membrane, it was observed that the methyl blue molecules passed through the nanochannel of the thru-hole alumina membrane, except for the molecules that were adsorbed to the surface of alumina membrane. In contrast, 95.2% of the methyl blue molecules were rejected by the electrical repulsive force of the surface-treated thru-hole alumina membrane. Also, efficient methyl blue rejection rate of nearly 96% was maintained in proper nanochannel diameter range of 150 to 200 nm.

Long-period fiber grating sensor for detection of viruses

Fast and reliable detection of viruses, including those specific to bacteria – bacteriophages – is crucial in clinical and veterinary practice, during biotechnological processes, and in basic research. In this paper, a highly sensitive long-period fiber grating (LPFG) label-free immunosensor is described for the detection of T7 bacteriophages. The LPFGs were tuned up to their highest refractive index sensitivity at the dispersion turning point of higher order cladding modes. The simple and reliable fiber surface functionalization was performed using 3-(triethoxysilyl)propylsuccinic anhydride to covalently bind anti-T7 antibodies. The T7 phage detection was possible by tracing the shift of the resonance wavelength in the LPFG transmission spectrum caused by the increase of the thickness and density of the bio-overlay, in particular induced by antigen-antibody interactions. The obtained sensor was selective and the limit of detection was lower than 5×103PFU/mL. Moreover, regeneration of the sensor surface by removing all organic layers was demonstrated. The regeneration procedure can reduce the costs of production and give the possibility for performing other measurements on the same LPFG structure. The applied procedure enabled real-time measurements and can be easily extended for the detection of other viruses.

Pentane-1,2-dicarboxylic acid functionalized spherical MCM-41: A simple and highly selective heterogeneous ligand for the adsorption of Fe3+ from aqueous solutions

Pentane-1,2-dicarboxylic acid functionalized spherical MCM-41 nanoparticles (DA-MCM-41) were prepared by a two step modification process started from the hydrothermal synthesis of mesoporous spherical silica particles. 3-(triethoxysilyl)propylsuccinic anhydride (TEPSA) was immobilized over spherical MCM-41 after the surfactant removal by calcination and the proceeding hydrolysis shaped the DA-MCM-41. The synthesized materials were well characterized by various spectroscopic analyses. As a potential application, DA-MCM-41 was effectively utilized for the removal of Fe3+ from aqueous solutions containing various metal ions. The adsorption using DA-MCM-41 was found to have 100% mole and weight selectivities for Fe3+ from aqueous solution containing Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ ions at pH 2, 3, 4 and 5. The material also exhibited 100% mole and weight selectivities for Fe3+ from metal ion mixture containing Li+, Na+, Ca2+ and Mg2+ along with the previously mentioned heavy metals at pH 2 and 3. Interestingly, at pH 4, 5 and 6 the alkali and alkaline earth metals adversely affected the mole and weight selectivities of Fe3+ ions. The reusability test revealed that the DA-MCM-41 can recycle for at least five consecutive cycles without losing the adsorption ability considerably. Also the ligand has excellent adsorption and binding abilities towards Fe3+ from the mixture.

A simple two-step silane-based (bio-) receptor molecule immobilization without additional binding site passivation

Immobilizing (bio-) receptor moleculesvia3-(triethoxysilyl)propylsuccinic anhydride makes subsequent binding site blocking dispensable, while maintaining receptor specificity for target analytes.

Selective covalent immobilization of ferritin on alumina.

Selective and specific covalent immobilization and simultaneous suppression of nonspecific adsorption of the protein ferritin (FN) on the surfaces of polycrystalline α-alumina colloidal particles and single α-alumina crystals is demonstrated. FN immobilization is obtained by using a classical immobilization route and by combining either the organic silane 3-(triethoxysilyl)propylsuccinic anhydride (TESPSA) or (3-aminopropyl)triethoxysilane (APTES) with the zero-length cross linking system N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS). The combination of APTES or TESPSA with EDC/NHS leads to a stable FN binding via amide bonds. However, the authors demonstrate that the TESPSA-EDC/NHS system enables an overall higher amount of covalent immobilization and a simultaneous suppression of nonspecific FN adsorption. After TESPSA functionalization negatively charged carboxylic groups are formed and can at the same time both electrostatically repel the overall negatively charged FN proteins and react with EDC/NHS for FN covalent immobilization. Moreover, the authors show that by specifically controlling the FN concentration during the immobilization reaction, the molecule distribution and density of bound FN can be easily tuned. The approach presented enables to selectively immobilize FN at mild conditions on substrates with different geometries and is therefore relevant for the fabrication of biomimetic nanomaterials and two-dimensional FN arrays.

Growth and Migration of BALB/3T3 Fibroblast Cells on Nano-engineered Silica Beads Surface

In this study, the behavior of cells on the modified surface, and the correlation between the modified substrates and the response of cells is described. A close-packed layer of nano-sized silica beads was prepared on a coverslip, and the adhesion, proliferation, and migration of BALB/3T3 fibroblast cells on the silica layer was monitered. The 550 nm silica beads were synthesized by the hydrolysis and condensation reaction of tetraethylorthosilicate in basic solution. The amine groups were introduced onto the surfaces of silica particles by treatment with 3-aminopropyltrimethoxysilane. The close-packed layer of silica beads on the coverslip was obtained by the reaction of the amine-functionalized silica beads and the (3-triethoxysilyl)propylsuccinic anhydride treated coverslip. BALB/3T3 fibroblast cells were loaded on bare glass, APTMS coated glass, and silica bead coated glass with the same initial cell density, and the migration and proliferation of cells on the substrates was investigated. The cells were fixed and stained with antibodies in order to analyze the changes in the actin filaments and nuclei after culture on the different surfaces. The motility of cells on the silica bead coated glass was greater than that of the cells cultured on the control substrate. The growth rate of cells on the silica bead coated glass was slower than that of the control. Because the close-packed layer of silica beads gave an embossed surface, the adhesion of cells was very weak compared to the smooth surfaces. These results indicate that the adhesion of cells on the substrates is very important, and the actin filaments might play key roles in the migration and proliferation of cells. The nuclei of the cells were shrunk on the weakly adhered surfaces, and the S1 stage in which DNA is duplicated in the cell dividing processes might be retarded. As a result, the rate of proliferation of cells was decreased compared to the smooth surface of the control. In conclusion, the results described here are very important in the understanding of the interaction between implanted materials and biosystems.

Anhydride modified silica nanoparticles: Preparation and characterization

The paper describes modification of colloid silica nanoparticles, using 3-(triethoxysilyl)propylsuccinic anhydride (TESPSA) as a reagent. Anhydride groups were grafted to the silica surface by an interaction of the surface silanol Si–OH groups with reactive ethoxy groups of TESPSA. Elemental analysis, FTIR and 1H NMR spectroscopy were employed to characterize silica nanoparticles before and after surface modification. It was demonstrated that only fifty percent of silica surface silanol groups are involved in the reaction with TESPSA. Size distribution of nanoparticles determined by atomic force microscopy (AFM) technique shows that nanoparticles preserve their size upon modification. TESPSA-modified silica nanoparticles can be used as polyfunctional curing agent for epoxy resin.

Preparation and properties of polyimide–silica hybrid films with conjugation of the polyimide and silica by a sol–gel process using 3-(triethoxysilyl)propyl succinic anhydride

New polyimide–silica hybrid materials were prepared using the polyamic acid synthesized by copolymerization of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 4,4′-oxydianiline (ODA) and an A 2A′-type tri-functional amine, 1,1-bis(4-(aminophenoxy)phenyl)-1-(4-(4-amino-2-trifluoromethylphenoxy)phenyl)ethane (1) (BTDA:ODA:1 = 7:6:1 in the molar). 3-(Triethoxysilyl)propyl succinic anhydride(TESSA) was reacted with amino groups in polyamic acid to introduce ethoxysilyl moiety which act as conjugation site for silica. The polyimide–silica hybrid films were prepared by a sol–gel reaction of tetraethoxysilane (TEOS) in a solution of the polyamic acid, followed by thermal imidation. Self-standing films were obtained with up to 50 wt.% silica, and transparent films were obtained at up to 40 wt.% silica. Dynamic-mechanical and mechanical analyses were carried out to examine the properties of hybrid films.

Towards the Determination of Surface Energy at the Nanoscale: A Further Assessment of the AFM-Based Approach

Towards the validation of the atomic force microscopy-based approach to the determination of surface energy at the nanometer scale, this paper explores the applicability of the technique by comparing atomic force microscopy-derived surface energy values with those from conventional contact angle measurements from a range of self-assembled organosilane structures ((3-aminopropyl)triethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride and trimethoxy(propyl)silane) and also from films of an ultra-low-surface-energy polymer, poly(1H,1H,2H,2H-perfluorodecyl methacrylate). The close agreement between the two sets of data indicates the validity of the AFM method, while unique attributes are indicated by the high resolution (ca. 1000 atoms) that is inherent to the approach and by the capability to study materials that are not compatible with the probing liquids used for goniometric determinations.

Plate Capture Assay of Fluorescent Oligonucleotide Duplex Reporter−Transcription Factor Complexes

We previously developed prototype oligodeoxyribonucleotide (ODN) duplex fluorescence energy transfer (FRET) reporters for optical sensing of NF-κB transcription factor. We report here a plate-binding assay designed for optimizing the above reporters. Nitrilotriacetate-bearing plates were prepared by using sequential (1) aminosilylation; (2) carboxylation; (3) coupling of Nα,Nα-bis(carboxymethyl)-L-lysine or, alternatively, by replacing steps 1 and 2 by treating the glass with 3-(triethoxysilyl)propylsuccinic anhydride. FRET reporters were obtained by covalent linking of Cy5.5 (fluorescence donor) and IRdye800CW (fluorescence acceptor) to complementary ODN strands encoding a high-affinity p50 binding site. Recombinant 6 × His tagged NF-κB p50 was used for immobilizing the protein on glass plates via linked NTA-Ni(II) groups. Imaging and quantification of the fluorescence intensity in the wells was performed in two channels (700 and 800 nm) using a near-infrared scanning device with microscopic resolution. The fluorescence intensity of the ODN duplex reporter was detectible in the plates at the concentration of 5 pM. NF-κB p50-ODN reporter interaction was studied by measuring the ratio of 700 nm (donor) to 800 nm (acceptor) fluorescence intensities. Using the plate assay, we were able to measure p50-mediated interference with FRET at low density of plate binding.

Magnetic nanoparticles with functional silanes: evolution of well-defined shells from anhydride containing silane.

Modification of iron oxide nanoparticles (NPs) synthesized by high temperature solvothermal routes is carried out using two silanes: (i) N-(6-aminohexyl)-aminopropyltrimethoxysilane (AHAPS) where only one end of the molecule reacts with the surface Fe-OH groups and (ii) 3-(triethoxysilyl)propylsuccinic anhydride (SSA) where both ends are reactive with Fe-OH. Depending on the NP synthesis protocol, the amount of surface OH groups on the NPs may differ, however, for all the cases presented here, the comparatively low OH group density prevents a high density of AHAPS coverage, yielding NP aggregates instead of single particles in aqueous solutions. Alternatively, use of SSA containing two terminal functionalities, anhydride and siloxy, which are both reactive towards the NP surface, results in the formation of discrete dense polymeric shells, providing stability of individual NPs in water. The mechanism of the SSA shell formation is discussed. The evolution of the chemical transformations leads to shells of different thickness and density, yet this evolution can be halted by hydrolysis, after which the NPs are water soluble, negatively charged and exhibit excellent stability in aqueous media.

Nanocomposites based on epoxy resin and silicon dioxide particles

The cure of an epoxy resin (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate) in the presence of silica nanoparticles modified by 3-(triethoxysilyl)propylsuccinic anhydride has been studied. Optimal conditions for the preparation of optically transparent polymer nanocomposites with increased glass transition temperatures are determined. The glass transition temperatures of the above nanocomposites are 50–70°C higher than those of the unfilled epoxy resin synthesized under the same conditions (100°C).

Functionalization of poly(ethylene terephthalate) in the melt state: Chemical and rheological aspects

AbstractThis article deals with a new way of improving the melt viscosity of linear poly(ethylene terephthalate) (PET) chains through the reaction of the PET end groups (alcohol and acid) with new chain extenders, 3‐(triethoxysilyl)propylsuccinic anhydride (ASSI) and 3‐glycidoxypropyltrimethoxysilane, during the melt processing of PET. The reactions, investigated with model compounds monomethylterephthalate and triethylene glycol monomethylether for PETCOOH and OH end groups, respectively, by multinuclear NMR spectroscopy (1H, 13C, and 29Si), provided evidence of well‐known acid–epoxide and alcohol–anhydride reactions, respectively. In addition, numerous other species appeared because of the presence of alkoxysilane groups, such as alcohol–alkoxysilane exchange reactions, acyloxysilane formation, and hydrolysis–condensation reactions of alkoxysilane. All these reactions led to the formation of branched chains when transposed to PET melt modification. A size exclusion chromatography analysis and the rheological behavior confirmed the presence of branched structures embedded in shorter linear PET chains. The rheological behavior of this blend was drastically modified in comparison with that of neat PET; consequently, there was an important increase in the zero‐shear viscosity, with a maximum concentration of branched structures of about 17 vol % obtained with an ASSI/PET molar ratio of 4. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2207–2223, 2005