Swelling characterization of novel ternary semi‐IPNs: acrylamide/1‐vinylimidazole/PEG hydrogels

New ternary semi interpenetrating polymer networks (semi‐IPNs) systems containing acrylamide (AAm), 1‐vinylimidazole (VI) and poly (ethylene glycol) (PEG) have been prepared. AAm/VI hydrogels and semi‐IPN's, poly (AAm/VI/PEG) with 0.25, 0.50, 0.75 and 1.00 g of PEG (per 1.00 g AAm) were prepared by free radical solution polymerization in aqueous solution of AAm with VI as comonomer and a multifunctional crosslinker such as 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of VI and PEG content in hydrogels were examined. AAm/VI and AAm/VI/PEG hydrogels showed large extents of swelling in aqueous media, the swelling being highly dependent on the chemical composition of the hydrogels. Percentage swelling ratio of AAm/VI hydrogels and AAm/VI/PEG hydrogels was shown as 650–4167%. The values of equilibrium water content (EWC) of the hydrogels are between 0.8990 and 0.9750. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non‐Fickian in character. Copyright © 2007 John Wiley & Sons, Ltd.     

Swelling equilibria and dye adsorption studies of chemically crosslinked superabsorbent acrylamide/maleic acid hydrogels

Superswelling acrylamide (AAm)/maleic acid (MA) hydrogels were prepared by free radical polymerization in aqueous solution of AAm with MA as comonomer with some multifunctional crosslinkers such as trimethylolpropane triacrylate and 1,4-butanediol dimethacrylate. AAm/MA hydrogels were used in experiments on swelling and adsorption of a water-soluble monovalent cationic dye such as Basic Blue 17 (Toluidin Blue). As a result of dynamic swelling tests, the influence of relative content of MA on the swelling properties of the hydrogel systems was examined. AAm/MA hydrogels were swollen in the range 1660-6050% in water, while AAm hydrogels swelled in the range 780-1360%. Equilibrium water content of AAm/MA hydrogels were calculated in the range 0.8873-0.9837. Water intake of hydrogels followed a non-Fickian type diffusion. The uptake of the cationic dye, BB-17 to AAm/MA hydrogels is studied by batch adsorption technique at 25 °C. In the experiments of the adsorption equilibrium, S-type adsorption in Giles's classification system was found. The binding ratio of hydrogel/dye systems was gradually increased with the increase of MA content in the AAm/MA hydrogels.     

Synthesis and Characterization of Sterculia Gum Based pH Responsive Drug Delivery System for Use in Colon Cancer

The present study deals with the modification of sterculia gum to develop the novel colon specific delivery system for use in colon cancer. The sterculia and acrylic acid based hydrogels were synthesized and characterized with FTIR, SEMs, TGA and swelling behavior. Swelling studies of the hydrogels were carried out as a function of reaction parameters such as monomer concentration, initiator concentration, amount of sterculia gum and crosslinker concentration and nature of swelling mediums. Swelling kinetics of the hydrogels and in vitro release dynamics of anticancer model drug methotrexate from the hydrogels were studied to evaluate the swelling mechanism and drug release mechanism from the drug-loaded hydrogels. The values of diffusion exponent for the release of drug were 0.883, 0.910 and 0.787 in distilled water, pH 2.2 buffer and pH 7.4 buffer, respectively. The release of drug from the polymer matrix occurred through a non -Fickian type diffusion mechanism.     

Water uptake and dye sorption studies of chemically crosslinked highly swollen novel ternary acrylamide‐based hydrogels including citraconic acid and sodium acrylate

Highly swollen hydrogels made by the polymerization of acrylamide (AAm) with some anionic monomers such as citraconic acid (CITA) and sodium acrylate (SA) were investigated as a function of composition to find materials with swelling and dye sorption properties. Highly swollen AAm/CITA/SA or AAm/SA/CITA hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with CITA and SA as co‐monomers and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4‐butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. Chemically crosslinked AAm/CITA/SA or AAm/SA/CITA hydrogels were used in experiments on sorption of water‐soluble monovalent cationic dye such as “Nil blue” (Basic Blue 12; BB 12). Equilibrium percentage swelling values of AAm/CITA/SA or AAm/SA/CITA hydrogels were calculated in the range of 1797–22,098%. Some swelling kinetic parameters were found. Diffusion behavior of water was investigated. Water diffusion into the hydrogels was found to be non‐Fickian in character. For sorption of cationic dye, BB 12 into the hydrogels was studied by batch sorption technique at 25°C. AAm/CITA/SA or AAm/SA/CITA hydrogels in the dye solutions showed coloration, whereas AAm hydrogel did not show sorption of any dye from the solution. The sorption capacity of AAm/CITA/SA or AAm/SA/CITA hydrogels was investigated. At the end of the experiments, 21.70–78.91% BB 12 adsorptions were determined. Copyright © 2007 John Wiley & Sons, Ltd.     

Adsorption of Uranyl Ions into Poly(Acrylamide‐co‐Acrylic Acid) Hydrogels Prepared by Gamma Irradiation

Acrylamide (AAm)/Acrylic Acid (AAc) copolymers have been prepared by gamma irradiation of binary mixtures at three different compositions where the acrylamide/acrylic acid mole ratios varied around 15, 20, and 30%. Threshold dose for 100% conversion of monomers into hydrogels was found to be 8.0 kGy. Poly(Acrylamide‐co‐Acrylic Acid) (poly(AAm‐co‐AAc)) hydrogels have been considered for the removal of uranyl ions from aqueous solutions. Swelling behavior of these hydrogels was determined in distilled water at different pH values and in aqueous solutions of uranyl ions. The results of swelling tests at pH 8.0 indicated that poly(AAm‐co‐AAc) hydrogel, containing 15% acrylamide showed maximum % swelling. Diffusion of water and aqueous solutions of uranyl ion into hydrogels was found to be non‐Fickian in character and their diffusion coefficients were calculated. The effect of pH, composition of hydrogel, and concentration of uranyl ions on the adsorption process were studied at room temperature. It was found that one gram of dry poly(AAm‐co‐AAc) hydrogel adsorbed 70–320 mg and 70–400 mg uranyl ions from aqueous solutions of uranyl nitrate and uranyl acetate in the initial concentration range of 50–1500 mg UO₂ ²⁺L^?, depending on the amount of AAc in the hydrogels, respectively. Adsorption isotherms were constructed for poly(AAm‐co‐AAc)–uranyl ion system indicating an S type of adsorption in the Giles classification system. It is concluded that crosslinked poly(AAm‐co‐AAc) hydrogels can be successfully used for the removal of uranyl ions from their aqueous solutions.     

Synthesis of new hydrogels based on the macromolecular reaction of citraconic anhydride copolymers with γ‐aminopropyltriethoxysilane (APTS)

This work describes the synthesis and macromolecular reactions of citraconic anhydride (CA)–acrylamide (AAm) binary reactive copolymers with γ‐aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with given composition of poly(CA‐alt‐AAm) were synthesized by radical binary copolymerization with benzoyl peroxide (BPO) as an initiator in benzene at 70°C in nitrogen atmosphere with initial monomer ratio 1 : 1. It was shown that the network structure is formed in poly(CA‐alt‐AAm)/APTS in water by intermolecular reactions between the anhydride unit and the amine group, as well as between the ethoxysilyl fragment and free carboxyl groups of the CA unit and amide unit of AAm. Swelling parameters such as beginning time of the hydrogel‐formation, initial rate of the swelling, swelling rate constant, equilibrium swelling and equilibrium water content were determined for the copolymer/APTS/water system with certain (2.75 : 1) copolymer/crosslinker ratio. Formation of a hyperbranched network structure through the fragmentation of side‐chain reactive groups in studied systems was confirmed by Fourier transform infrared spectroscopy (FT‐IR) method. Copyright © 2004 John Wiley & Sons, Ltd.     

RADIATION INDUCED ACRYLAMIDE/CITRIC ACID HYDROGELS AND THEIR SWELLING BEHAVIORS

Citric acid (CAc) moieties containing acrylamide (AAm) hydrogels were prepared by gamma irradiation of their aqueous solutions. A possible polymerization and crosslinking mechanism for acrylamide/citric acid (AAm/CAc) hydrogels is proposed. The effects of irradiation dose and citric acid content on swelling behavior were investigated. Swelling took place in water at 25°C and was followed gravimetrically. Incorporation of a relatively low amount of citric acid to acrylamide hydrogel increased its swelling up to 950% from 700%. The diffusion of water into AAm/CAc hydrogels was found to be a non-Fickian type. Diffusion coefficients of AAm/CAc hydrogels found as 5 × 10^?7? 10 × 10^?7 cm² sec^?1. It has also been found that the number average molar mass between crosslinks is increased with the CAc content and decreased with irradiation dose.     

pH and temperature responsive hydrogels of poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-methacrylic acid): Synthesis and swelling characteristics

Temperature and pH sensitive 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and methacrylic acid (MAA) homopolymer and copolymer hydrogels have been prepared using N,N′-methylenebisacrylamide (MBA) and ethylene glycol dimethacrylate (EGDMA) as crosslinkers. Swelling of these hydrogels has been studied in terms of monomer ratio, type and concentration of the crosslinkers and in various concentrations of mono, di and trivalent salt solutions. Though swelling of the EGDMA crosslinked poly(AMPS-co-MAA) hydrogels is found to be higher than those based on MBA crosslinker, strength of the latter system has been found to be better. Swelling behavior of these hydrogels in different salt solutions at different concentrations has shown a drop in swelling from monovalent to trivalent cations and also at higher salt concentrations. The results have indicated the possibilities of developing tailor made hydrogels combining optimum swelling with better strength characteristics that will suit different physiological and biological environments.     

Thermosensitive poly(N-isopropylacrylamide-co-acrylamide) hydrogels: Synthesis, swelling and interaction with ionic surfactants

Thermosensitive hydrogels were prepared by free-radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N-Methylenebis(acrylamide) (MBAAm) was used as a crosslinker. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(NIPA-co-AAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(NIPA-co-AAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In SDS and DTAB solutions, the equilibrium swelling ratio of the hydrogels increased, this is ascribed to the conversion of non-ionic P(NIPA-co-AAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(NIPA-co-AAm)—surfactant systems depended strongly on both the type and concentration of surfactant solutions.     

Poly(2‐oxazoline) hydrogels crosslinked with aliphatic bis(2‐oxazoline)s: Properties,cytotoxicity, and cell cultivation

A series of hydrogels from 2‐ethyl‐2‐oxazoline and three bis(2‐oxazoline) crosslinkers—1,4‐butylene‐2,2′‐bis(2‐oxazoline), 1,6‐hexamethylene‐2,2′‐bis(2‐oxazoline), and 1,8‐octamethylene‐2,2′‐bis(2‐oxazoline)—are prepared. The hydrogels differ by the length of aliphatic chain of crosslinker and by the percentage of crosslinker (2–10%). The influence of the type and the percentage of the crosslinker on swelling properties, mechanical properties, and state of water is studied. The equilibrium swelling degree in water ranges from 2 to 20. With a proper selection of the crosslinker, Young's modulus can be varied from 10 kPa to almost 100 kPa. To evaluate the potential for medical applications, the cytotoxicity of extracts and the contact toxicity toward murine fibroblasts are measured. The hydrogels with the crosslinker containing a shorter aliphatic exhibit low toxicity toward fibroblast cells. Moreover, the viability and the proliferation of pancreatic β‐cells incubated inside hydrogels for 12 days are analyzed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1548–1559     

Phase Transition of Acrylamide‐Based Polyampholyte Gels in Water

The swelling behavior of acrylamide (AAm)–based polyampholyte hydrogels in water and in aqueous salt (NaCl) solutions was investigated. [(Methacrylamido)propyl]trimethyl‐ammonium chloride (MAPTAC) and acrylic acid (AAc) were used as the ionic comonomer in the hydrogel preparation. Three sets of hydrogels containing 70 mol% AAm and 30 mol% ionic comonomers of varying mole ratios were prepared. The variations of the hydrogel volume in response to changes in pH, and salt concentration were measured. As pH increases from 1, the hydrogel volume V _eq in water first increases and reaches a maximum value at a certain pH. Then, it decreases again with a further increase in pH and attains a minimum value around the isoelectric point (IEP). After passing the collapsed plateau region, the gel reswells again up to pH=7.1. The reswelling of the collapsed gels containing 10 and 4% MAPTAC occurs as a first‐order phase transition at pH=5.85 and 4.35, respectively, while the hydrogel with 1% MAPTAC reswells continuously beyond its IEP. Depending on pH of the solution, the hydrogels immersed in salt solutions exhibit typical polyelectrolyte or antipolyelectrolye behavior. The experimental swelling data were compared with the predictions of the Flory‐Rehner theory of swelling equilibrium including the ideal Donnan equilibria. It was shown that the equilibrium swelling theory qualitatively predicts the experimental behavior of polyampholyte hydrogels.     

Synthesis and characterization of thermoresponsive isopropylacrylamide-acrylamide hydrogels

In this study, hydrogels of poly(N-isopropylacrylamide-co-acrylamide) having a thermoresponsive character were prepared by a redox polymerization method. NIPAM-co-AAm hydrogels with different thermoresponsive properties were obtained by changing the initial NIPAM/AAm mole ratio and crosslinker concentration.Equilibrium-swelling ratio, dynamic swelling ratio and dynamic deswelling ratio were evaluated for all hydrogel systems. The fast shrinking was observed with all gels. The time required for equilibrium shrinking increased with the increase of acrylamide content in the gel.     

含甲基丙烯酸-N,N-二甲氨基乙酯水凝胶的紫外辐射合成及其性质研究

紫外光辐照 ,H2 O2 为光引发剂 ,N ,N′ 亚甲基双丙烯酰胺为交联剂合成了含甲基丙烯酸 N ,N 二甲氨基乙酯的水凝胶 .研究了水溶液中单体、光敏引发剂、交联剂浓度及光照时间对生成的水凝胶的凝胶含量和溶胀性能的影响 ,给出了最佳合成条件 .用该聚合法合成的聚甲基丙烯酸 N ,N 二甲氨基乙酯水凝胶不仅具有较好的透明性和适当的弹性 ,而且在 40℃和 pH =3时有明显的温度及 pH敏感性 .但离子强度对凝胶溶胀性能没有明显影响     

Copper and Nickel Removal from Aqueous Solutions Using New Chelating Poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid] Hydrogels

New poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid], poly [AAm/NVP/HECA], chelating hydrogels with different composition of HECA monomer have been prepared via free radical solution polymerization using N,N‐methylene bisacrylamide as a crosslinker. The hydrogels obtained were loaded with metal ions and characterized by FT‐IR spectroscopy, Scanning Electron Microscope (SEM) and Thermogravimatric analysis (TGA). The removal of Cu²⁺ and Ni²⁺ from aqueous solutions by the hydrogel was examined by a batch equilibrium method. The influence of treatment time, pH, initial concentration of the metal ions and HECA content in the feed compositions on the amount of adsorbed metal ions was studied. Swelling of the hydrogel was also carried out in distilled water and metal ion solutions. The removal of the metal ions followed the following order: Ni²⁺>Cu²⁺. The amount of metal ions removed increased with increasing HECA content in the feed composition, treatment time, pH of the medium and initial concentration of metal ions. The desorption of metal ions were carried out using 1 N HCl and 0.5 N H₂SO₄. The poly[AAm/NVP/HECA] hydrogels could be used many times without significantly decreasing their adsorption capacity.     

Modified chitosan 4. Superabsorbent hydrogels from poly(acrylic acid-co-acrylamide) grafted chitosan with salt- and pH-responsiveness properties

Graft copolymerization of mixtures of acrylic acid (AA) and acrylamide (AAm) onto chitosan was carried out by using potassium persulfate (KPS) as a free radical initiator in the presence of methylenebisacrylamide (MBA) as a crosslinker. The effect of reaction variables, such as MBA concentration and AA/AAm ratio on the water absorbency capacity have been investigated. The polymer structures were confirmed by FTIR spectroscopy. Water absorbencies were compared for the hydrogels before and after alkaline hydrolysis. In the non-hydrolyzed hydrogel, enhanced water absorbency was obtained with increasing AA in monomer feed. However, after saponification, the sample with high AAm ratio exhibited more water absorbency. These behaviors were discussed according to structural parameters. The swelling kinetics of the superabsorbing hydrogels was studied as well. The hydrogels exhibited ampholytic and reversible pH-responsiveness characteristics. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The hydrogels exhibited salt-sensitivity and cation exchange properties. The pH-reversibility and on-off switching properties of the hydrogels make the intelligent polymers as good candidates for considering as potential carriers for bioactive agents, e.g. drugs.     

Modeling of Swelling Behaviors of Acrylamide-Based Polymeric Hydrogels by Intelligent System

Hydrogels based on acrylamide (AAm) were synthesized by free radical polymerization in an aqueous solution using N,N’-methylenebisacrylamide (MBAAm) as crosslinker. To obtain anionic hydrogels, 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS) and acrylic acid (AAc) were used as comonomers. The swelling behaviors of all hydrogel systems were modeled using an artificial neural network (ANN) and compared with a multivariable least squares regression (MLSR) model and phenomenal model. The predictions from the ANN model, which associated input parameters, including the amounts of crosslinker (MBA) and comonomer, and swelling values with time, produce results that show excellent correlation with experimental data. The parameters of swelling kinetics and water diffusion mechanisms of the hydrogels were calculated using the obtained experimental data. Model analysis indicated that the ANN models could accurately describe complex swelling behaviors of highly swellable hydrogels.     

Temperature Sensitive Superabsorbent Hydrogels from Poly(N-t-butyl acrylamide-co-acrylamide) Grafted on Sodium Alginate

Temperature-sensitive hydrogels based on N-t-butylacrylamide (TBA), acrylamide (AAm), and sodium alginate were prepared by free radical polymerization method. Methylenebisacrylamide (MBA) and amonium persulfate (APS) were applied as water soluble crosslinker and initiator, respectively. The chemical structure of the hydrogels was confirmed by FT-IR spectroscopy and thermogravimetric analysis (TGA) methods. Morphology of the samples was examined by scanning electron microscopy (SEM). By changing the initial TBA/AAm mole ratios, hydrogels with different swelling properties were obtained. The rate parameters were found to be 2.0, 2.4, and 3.5 min for the superabsorbents with AAm/TBA weight ratio of 1.0, 1.3 and 2.0 respectively. The swelling behavior in distilled water and different pH solutions was investigated. A preliminary swelling kinetics and the absorbency under load (AUL) were also studied. At the applied pressure (2.07 kPa), maximum swelling was found to be 17, 19, and 21 (g/g) for the superabsorbent hydrogels with AAm/TBA weight ratios of 1.0, 1.5 and 2.0, respectively.     

An evaluation on S-type adsorption isotherm in the model of crosslinked polyhydroxamates/oxazine dyes/water interactions

The effects of crosslinker and dye type on swelling and S-type adsorption properties of crosslinked polyhydroxamates (CHP) were investigated. CHPs containing N,N?-methylenebisacrylamide (N), or ethylene glycol dimethacrylate (E) were used in the swelling, diffusion, and adsorption experiments in solutions of oxazine dyes such as Brilliant Cresyl Blue, Nile Blue, and Cresyl Violet. Swelling and diffusion parameters of CHPs in dye solutions (such as equilibrium swelling, half time of swelling, swelling value at half time, network parameter, diffusion exponent, and diffusion constant) were calculated. It is understood from the time of swelling to reach equilibrium that CHPs swell very fast. CHP-E in all dyes solutions swelled considerably more than CHP-N. Dye solution diffusion into CHPs was determined to be of non-Fickian character. It has been observed that the swelling properties of hydrogels are highly influenced by the crosslinker type. The adsorption of oxazine dyes onto CHPs is similar to the S-type adsorption in the Giles classification system. When it was seen that the experimental data fit the Sigmoidal 4 parameter equation with a high correlation (r²?>?0.995), the use of this equation determined the adsorption parameters such as the highest bonding rate or monolayer coverage, the transition point of the isotherm, the magnitude of the absorbent's absorbability and the slope parameter. Site-size, maximum fractional occupancy, the binding ratio at the transition point, binding constant, the initial binding constant, partition coefficient, and adsorption free energy values were also calculated by using the found adsorption values. Dye adsorption from all dyes solutions to CHP-E is considerably higher than CHP-N. An increasing linear relationship was found between swelling and adsorption. In conclusion, the sigmoidal equation approach can be a useful tool for chemists, chemical, agricultural and environmental engineers, polymer scientists to find the adsorption parameters of polymer adsorbents, and at the same time, it can be said that CHP can be used as a good sorbent in the removal of some chemical agents (such as dye molecules, organic molecules, biologically active molecules).

     

Uptake of Basic Blue 17 from aqueous solutions by using chemically crosslinked polyelectrolyte AAm/AASS hydrogels

In this study, the removal of a cationic thiazin dye such as Basic Blue 17 (Toluidin Blue, BB 17) by chemically crosslinked acrylamide (AAm)/acrylic acid sodium salt (AASS) hydrogels was investigated. Super water retainer AAm/AASS hydrogels with various compositions were prepared from ternary mixtures of AAm, AASS and water by free radical polymerization in aqueous solution using multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA), N,N′ methylenebisacrylamide (NMBA), 1,4 butanediol dimethacrylate (BDMA) and trimethylolpropane triacrylate (TMPTA). Adsorption of Basic Blue 17 from aqueous solutions was studied by batch sorption technique at 25^°C. The effect of Basic Blue 17 concentration and mass of adsorbent on the dye adsorption were examined. In the experiments of the sorption, C type and L type sorption in the Giles classification system was found. Some binding parameters such as initial binding constant (K _i ), equilibrium constant (K), monolayer coverage (n), site-size (u), and maximum fractional occupancy (Ô) for AAm/AASS hydrogel-dye binding system were calculated by using Klotz linearization method. Finally, the amount of sorbed Basic Blue 17 per gram of dry hydrogel (q) was calculated to be 1.96–21.35 μ mol dye per gram for AAm/AASS hydrogels. Adsorption of Basic Blue 17 was changed range 39.17–96.63%. AAm/AASS hydrogels crosslinked by TMPTA, EGDMA, BDMA or NMBA can be used a sorbent in biotechnology, environment, sorption, separation, purification, immobilization and enrichment of some species.     

Synthesis and swelling characterizations of a poly(gamma-glutamic acid) hydrogel

Natural, biosynthesized poly(gamma-glutamic acid) (γ-PGA) was crosslinked using dihalogenoalkanes yielding hydrogels with various features. Crosslinking reactions of the polymer and swelling of the hydrogels were studied. Various reaction parameters, like temperature and catalyst content, were adjusted to give highest yields in the network production. Swelling of the hydrogels showed dramatic changes when varying experimental conditions such as the molecular weight of γ-PGA, the nature and concentration of the crosslinker, and the solution used for the swelling (ionic strength, pH). © 1996 John Wiley & Sons, Inc.