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1.
Best Pract Res Clin Rheumatol ; : 101974, 2024 Jul 20.
Article in English | MEDLINE | ID: mdl-39034216

ABSTRACT

Rheumatoid arthritis (RA) is a systemic autoimmune inflammatory arthritis. Despite many treatment advances, achieving remission or low-disease activity in RA remains challenging, often requiring trial and error approaches with numerous medications. Precision medicine, particularly pharmacogenomics, explores how genetic factors influence drug response in individual patients, and incorporates such factors to develop personalized treatments for individual patients. Genetic variations in drug-metabolizing enzymes, transporters, and targets may contribute to inter-individual differences in drug efficacy and toxicity. Advancements in molecular sequencing have allowed rapid identification of such variants, including single nucleotide polymorphisms (SNPs). This review highlights recent major findings in the pharmacogenetics of therapies in RA, focusing on key genes and SNPs to provide insights into current trends and developments in this field.

2.
Molecules ; 29(2)2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38257359

ABSTRACT

The fabrication of chitosan (CH) biocomposite beads with variable copper (Cu2+) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-b-Cu) without CL; (2) cross-linking of the CH beads, followed by imbibition of Cu(II) ions (CH-b-CL-Cu); and (3) cross-linking of pristine CH, followed by bead formation with Cu(II) imbibing onto the beads (CH-CL-b-Cu). The biocomposites (CH-b-Cu, CH-b-CL-Cu, and CH-CL-b-Cu) were characterized via spectroscopy (FTIR, 13C solid NMR, XPS), SEM, TGA, equilibrium solvent swelling methods, and phosphate adsorption isotherms. The results reveal variable cross-linking and Cu(II) doping of the CH beads, in accordance with the step-wise design strategy. CH-CL-b-Cu exhibited the greatest pillaring of chitosan fibrils with greater cross-linking, along with low Cu(II) loading, reduced solvent swelling, and attenuated uptake of phosphate dianions. Equilibrium and kinetic uptake results at pH 8.5 and 295 K reveal that the non-CL Cu-imbibed beads (CH-b-Cu) display the highest affinity for phosphate (Qm = 133 ± 45 mg/g), in agreement with the highest loading of Cu(II) and enhanced water swelling. Regeneration studies demonstrated the sustainability and cost-effectiveness of Cu-imbibed chitosan beads for controlled phosphate removal, whilst maintaining over 80% regenerability across several adsorption-desorption cycles. This study offers a facile synthetic approach for controlled Cu2+ ion doping onto chitosan-based beads, enabling tailored phosphate oxyanion uptake from aqueous media by employing a sustainable polysaccharide biocomposite adsorbent for water remediation by mitigation of eutrophication.

3.
Int J Biol Macromol ; 260(Pt 2): 129275, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38242408

ABSTRACT

Adsorption-based treatment of sulfate contaminated water sources present challenges due to its favourable hydration characteristics. Herein, a copper-modified granular chitosan-based biocomposite (CHP-Cu) was prepared and characterized for its sulfate adsorption properties at neutral pH via batch equilibrium and fixed-bed column studies. The CHP-Cu adsorbent was characterized by complementary methods: spectroscopy (IR, Raman, X-ray photoelectron), thermal gravimetry analysis (TGA) and pH-based surface charge analysis. Sulfate adsorption at pH 7.2 with CHP-Cu follows the Sips isotherm model with a maximum adsorption capacity (407 mg/g) that exceeds most reported values of granular biosorbents at similar conditions. For the dynamic adsorption study, initial sulfate concentration, bed height, and flow rate were influential parameters governing sulfate adsorption. The Thomas and Yoon-Nelson models yield a sulfate adsorption capacity (146 mg/g) for the fixed bed system at optimized conditions. CHP-Cu was regenerated over 5 cycles (33 % to 31 %) with negligible Cu-leaching. The adsorbent also displays excellent sulfate uptake properties, regenerability, and sustainable adsorbent properties for effective point-of-use sulfate remediation in aqueous media near neutral pH (7.2). This sulfate remediation strategy is proposed for other oxyanion systems relevant to contaminated environmental surface and groundwater resources.


Subject(s)
Chitosan , Water Pollutants, Chemical , Water Purification , Chitosan/chemistry , Copper/chemistry , Sulfates , Water Pollutants, Chemical/chemistry , Water , Adsorption , Hydrogen-Ion Concentration , Kinetics
4.
J Cosmet Dermatol ; 21(10): 4545-4553, 2022 Oct.
Article in English | MEDLINE | ID: mdl-35037365

ABSTRACT

BACKGROUND: Striae distensae (SD) or stretch marks, a common condition causing significant cosmetic concern and distress, are linear dermal scars associated with epidermal atrophy that occur due to overstretching. Recently, micro-needling with dermapen is considered as one of the therapeutic modalities for SD. Also, plasma skin regeneration with plasma jet has been recommended as an effective method for the treatment of SD. AIM: The aim was to compare between the efficacy of both methods in the treatment of SD. METHODS: This study included 30 patients with striae distensae. Body was divided into two halves; one was treated with plasma jet for two sessions with 1 month interval and follow-up one month after the last session and the other half was treated with dermapen for four sessions with two weeks interval and follow-up one month after. RESULTS: There was no statistically significant difference (p- value >0.05) between dermapen and plasma jet procedures as regard to width, Total Atwal Score, Atwal score component, score of erythema, and skin texture after treatment. There was high statistically significant difference (p value <0.01) between dermapen and plasma jet as regards pain with higher values with plasma jet while there were statistical higher values concerning hyperpigmentation and erythema with dermapen. There was high statistically significant difference (p value <0.001) between width of striae before and after treatment with dermapen. CONCLUSIONS: Both lines of treatments are effective and promising therapeutic modalities for striae distensae with minimal side effects.


Subject(s)
Striae Distensae , Humans , Striae Distensae/therapy , Plasma Skin Regeneration , Patient Satisfaction , Needles , Erythema/etiology , Erythema/therapy , Treatment Outcome
5.
Biol Trace Elem Res ; 200(5): 2391-2405, 2022 May.
Article in English | MEDLINE | ID: mdl-34292461

ABSTRACT

The study aimed to determine the effects of wet salting, dry salting, and smoking processing methods on the heavy metal and mineral concentrations in the cultivated fish species which collected from private fish farms at Kafr El-Sheikh Governorate, Egypt, during winter, 2017. The impacts of fish processing on mineral contents of the raw and processed fish were significantly different (P ≤ 0.05). The maximum level of metals in the raw and processed fish samples (wet salted, dry salted, and smoked fish) were recorded for iron ion and the minimum level determined for cadmium ion. However, the highest sequences of the minerals in the raw and processed samples were obtained in this order Na > K > P > Ca. Regarding to processing methods, significant decreases occurred in the minerals of Ca, K, and P, but smaller decrease in the heavy metals of Cd, Cu, Fe, Mg, Ni, and Zn in the wet salted grass carp. In the dry salted mullet, the changes in the minerals and heavy metals are relatively small. However, the greatest changes are on smoked grass carp; most of the minerals, including Ca, K and P, except Na, significantly increased. In heavy metals, Cu, Fe, and Zn, except Mg and Ni, also significant increased.


Subject(s)
Carps , Metals, Heavy , Water Pollutants, Chemical , Animals , Egypt , Environmental Monitoring , Metals, Heavy/analysis , Minerals/analysis , Water Pollutants, Chemical/analysis
6.
Am J Transplant ; 21(7): 2583-2589, 2021 07.
Article in English | MEDLINE | ID: mdl-33794063

ABSTRACT

Extracellular vesicles, including exosomes, are regularly released by allogeneic cells after transplantation. Recipient antigen-presenting cells (APCs) capture these vesicles and subsequently display donor MHC molecules on their surface. Recent evidence suggests that activation of alloreactive T cells by the so-called cross-dressed APCs plays an important role in initiating the alloresponse associated with allograft rejection. On the other hand, whether allogeneic exosomes can bind to T cells on their own and activate them remains unclear. In this study, we showed that allogeneic exosomes can bind to T cells but do not stimulate them in vitro unless they are cultured with APCs. On the other hand, allogeneic exosomes activate T cells in vivo and sensitize mice to alloantigens but only when delivered in an inflammatory environment.


Subject(s)
Exosomes , Hematopoietic Stem Cell Transplantation , Animals , Antigen-Presenting Cells , Graft Rejection/prevention & control , Isoantigens , Mice , T-Lymphocytes
7.
Polymers (Basel) ; 12(7)2020 Jul 06.
Article in English | MEDLINE | ID: mdl-32640585

ABSTRACT

Binary (Chitosan-Cu(II), CCu) and Ternary (Chitosan-Alginate-Cu(II), CACu) composite materials were synthesized at variable composition: CCu (1:1), CACu1 (1:1:1), CACu2 (1:2:1) and CACu3 (2:1:1). Characterization was carried out via spectroscopic (FTIR, solids C-13 NMR, XPS and Raman), thermal (differential scanning calorimetry (DSC) and TGA), XRD, point of zero charge and solvent swelling techniques. The materials' characterization confirmed the successful preparation of the polymer-based composites, along with their variable physico-chemical and adsorption properties. Sulfate anion (sodium sulfate) adsorption from aqueous solution was demonstrated using C and CACu1 at pH 6.8 and 295 K, where the monolayer adsorption capacity (Qm) values were 288.1 and 371.4 mg/g, respectively, where the Sips isotherm model provided the "best-fit" for the adsorption data. Single-point sorption study on three types of groundwater samples (wells 1, 2 and 3) with variable sulfate concentration and matrix composition in the presence of composite materials reveal that CACu3 exhibited greater uptake of sulfate (Qe = 81.5 mg/g; 11.5% removal) from Well-1 and CACu2 showed the lowest sulfate uptake (Qe of 15.7 mg/g; 0.865% removal) from Well-3. Generally, for all groundwater samples, the binary composite material (CCu) exhibited attenuated sorption and removal efficiency relative to the ternary composite materials (CACu).

8.
J Chromatogr A ; 1543: 23-33, 2018 Mar 30.
Article in English | MEDLINE | ID: mdl-29478831

ABSTRACT

Sorbents were prepared by cross-linking ß-cyclodextrin (ß-CD) using two different types of cross-linker units at variable reactant mole ratios. The resulting polymers containing ß-CD were evaluated as sorbents in micro-solid phase extraction (µ-SPE) format for the extraction of the endogenous steroids testosterone (T), epitestosterone (E), androsterone (A), etiocholanolone (Etio), 5α-androstane-3α,17ß-diol (5αAdiol) and 5ß-androstane-3α,17ß-diol (5ßAdiol). The best sorbent (C1; cyclodextrin polymer) showed superior extraction characteristics compared with commercial sorbents (C18 and Bond Elut Plexa). Parameters influencing the extraction efficiency of the C1 sorbent such as extraction and desorption times, desorption solvent and volume of sample were investigated. The extracts were separated using a Hypersil Gold column (50 × 2.1 mm, 1.9 µm) under gradient elution coupled to a LC-MS/MS. The compounds were successfully separated within 8 min. The method offers good repeatability (RSD < 10%) and linearity (r2 > 0.995) were within the range of 1-200 ng mL-1 for T and E, 250-4000 ng mL-1 for A and Etio and 25-500 ng mL-1 for 5αAdiol and 5ßAdiol, respectively. The method was applied for the determination of steroid profile of urine from volunteers.


Subject(s)
Chromatography, Liquid , Solid Phase Microextraction , Steroids/isolation & purification , Tandem Mass Spectrometry , beta-Cyclodextrins/chemistry , Limit of Detection , Polymers/chemistry , Reproducibility of Results , Steroids/chemistry
9.
J Int Soc Prev Community Dent ; 8(6): 482-487, 2018.
Article in English | MEDLINE | ID: mdl-30596037

ABSTRACT

The knowledge of the skeletal maturation and the stage of the growth of the patients seeking orthodontic treatment are of great value in planning efficient orthodontic therapy. However, different craniofacial structures of patient show variation in growth potential. The routine use of hand-wrist radiograph for growth prediction exposes the patient to extra radiation. Cervical vertebrae in the lateral cephalograph have been recommended as an alternative method. The pubertal growth spurt is a vital period in the orthodontic treatment and should be kept in mind when planning orthodontic treatment in growing children. One of the main objectives of taking hand and wrist radiograph is to determine the amount of growth and get used of it in patients with skeletal discrepancy during adolescence. Further, this will help in the selection of the appliances required, the course of the treatment and the retention after active orthodontic therapy.

10.
Mol Pharm ; 14(8): 2616-2623, 2017 08 07.
Article in English | MEDLINE | ID: mdl-28294623

ABSTRACT

Herein, we report on the systematic design and characterization of cross-linked polymer carriers containing ß-cyclodextrin (ß-CD) and divinyl sulfone (DVS). The polymer carriers were prepared at variable feed ratios (ß-CD-DVS; 1:1, 1:2, 1:3, and 1:6) and characterized using spectroscopy (IR, 1H solution NMR, and 13C CP-MAS solids NMR spectroscopy), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and a dye decolorization method using phenolphthalein. Uptake studies were carried out at pH 9.00 for the polymer carriers using single component bile acids (cholic acid, deoxycholic acid, glycodeoxycholic acid, and taurodeoxycholic acid). Equilibrium uptake results were evaluated by the Langmuir isotherm model where variable equilibrium parameters were related to the relative apolar character of the bile acid. The Langmuir model yields a carrier/bile acid binding affinity of ∼103 M-1 where the lipophilic inclusion sites of the polymer play a prominent role, while the DVS linker framework sites have a lower adsorption affinity, in accordance with the greater hydrophilic character of such sites.


Subject(s)
Polymers/chemistry , beta-Cyclodextrins/chemistry , Acetazolamide/chemistry , Acetazolamide/pharmacology , Cell Line, Tumor , Cell Survival/drug effects , Dacarbazine/analogs & derivatives , Dacarbazine/chemistry , Dacarbazine/pharmacology , Dendrimers/chemistry , Glioblastoma/metabolism , Humans , Micelles , Quercetin/chemistry , Quercetin/pharmacology , Spheroids, Cellular/drug effects , Temozolomide
11.
Sci Immunol ; 1(1)2016 Jul 14.
Article in English | MEDLINE | ID: mdl-27942611

ABSTRACT

Transplantation of allogeneic organs and tissues represents a lifesaving procedure for a variety of patients affected with end-stage diseases. Although current immunosuppressive therapy prevents early acute rejection, it is associated with nephrotoxicity and increased risks for infection and neoplasia. This stresses the need for selective immune-based therapies relying on manipulation of lymphocyte recognition of donor antigens. The passenger leukocyte theory states that allograft rejection is initiated by recipient T cells recognizing donor major histocompatibility complex (MHC) molecules displayed on graft leukocytes migrating to the host's lymphoid organs. We revisited this concept in mice transplanted with allogeneic skin, heart, or islet grafts using imaging flow cytometry. We observed no donor cells in the lymph nodes and spleen of skin-grafted mice, but we found high numbers of recipient cells displaying allogeneic MHC molecules (cross-dressed) acquired from donor microvesicles (exosomes). After heart or islet transplantation, we observed few donor leukocytes (100 per million) but large numbers of recipient cells cross-dressed with donor MHC (>90,000 per million). Last, we showed that purified allogeneic exosomes induced proinflammatory alloimmune responses by T cells in vitro and in vivo. Collectively, these results suggest that recipient antigen-presenting cells cross-dressed with donor MHC rather than passenger leukocytes trigger T cell responses after allotransplantation.

12.
Molecules ; 21(1): 93, 2016 Jan 14.
Article in English | MEDLINE | ID: mdl-26784153

ABSTRACT

This commentary reports on a recent scientific study reported in this journal (cf. Molecules 2015, 20(3), 3565-3581). Some key scientific issues that require further explanation and clarification in the former article are as follows: (i) the relationship between the inclusion site accessibility and the level of cross-linking employed are brought into question for the case of α-CD and ß-CD cross-linked adsorbent materials; (ii) the binding affinity of the CD/guest complexes were not related to the isotherm parameters for the CD-polymer/guest systems; (iii) the limited molecular level structural characterization of the cross-linked polymer materials; and (iv) the interpretation of the adsorption isotherm results by the authors.


Subject(s)
Cross-Linking Reagents/pharmacology , Cyclodextrins/chemistry , Polymers/chemistry , Starch/chemistry , Sulfones/chemistry
13.
Chemosphere ; 136: 252-8, 2015 Oct.
Article in English | MEDLINE | ID: mdl-26042363

ABSTRACT

Various sorbent materials were evaluated for the fractionation of naphthenic acid fraction components (NAFCs) from oil sand process-affected water (OSPW). The solid phase materials include activated carbon (AC), cellulose, iron oxides (magnetite and goethite), polyaniline (PANI) and three types of biochar derived from biomass (BC-1; rice husks, BC-2; acacia low temperature and BC-3; acacia high temperature). NAFCs were semi-quantified using electrospray ionization high resolution Orbitrap mass spectrometry (ESI-MS) and the metals were assessed by inductively coupled plasma optical emission spectrometry (ICP-OES). The average removal efficacy of NAFCs by AC was 95%. The removal efficacy decreased in the following order: AC, BC-1>BC-2, BC-3, goethite>PANI>cellulose, magnetite. The removal of metals did not follow a clear trend; however, there was notable leaching of potassium by AC and biochar samples. The bound NAFCs by AC were desorbed efficiently with methanol. Methanol regeneration and recycling of AC revealed 88% removal on the fourth cycle; a 4.4% decrease from the first cycle. This fractionation method represents a rapid, cost-effective, efficient, and green strategy for NAFCs from OSPW, as compared with conventional solvent extraction.


Subject(s)
Carboxylic Acids/analysis , Environmental Monitoring/methods , Oil and Gas Fields , Water Pollutants, Chemical/analysis , Chemical Fractionation , Metals/analysis , Spectrometry, Mass, Electrospray Ionization/methods
14.
Nanomaterials (Basel) ; 5(2): 969-980, 2015 Jun 04.
Article in English | MEDLINE | ID: mdl-28347046

ABSTRACT

Challenges exist for the study of time dependent sorption processes for heterogeneous systems, especially in the case of dispersed nanomaterials in solvents or solutions because they are not well suited to conventional batch kinetic experiments. In this study, a comparison of batch versus a one-pot setup in two variable configurations was evaluated for the study of uptake kinetics in heterogeneous (solid/solution) systems: (i) conventional batch method; (ii) one-pot system with dispersed adsorbent in solution with a semi-permeable barrier (filter paper or dialysis tubing) for in situ sampling; and (iii) one-pot system with an adsorbent confined in a semi-permeable barrier (dialysis tubing or filter paper barrier) with ex situ sampling. The sorbent systems evaluated herein include several cyclodextrin-based polyurethane materials with two types of phenolic dyes: p-nitrophenol and phenolphthalein. The one-pot kinetics method with in situ (Method ii) or ex situ (Method iii) sampling described herein offers significant advantages for the study of heterogeneous sorption kinetics of highly dispersed sorbent materials with particles sizes across a range of dimensions from the micron to nanometer scale. The method described herein will contribute positively to the development of advanced studies for heterogeneous sorption processes where an assessment of the relative uptake properties is required at different experimental conditions. The results of this study will be advantageous for the study of nanomaterials with significant benefits over batch kinetic studies for a wide range of heterogeneous sorption processes.

15.
Rev Environ Health ; 29(1-2): 5-8, 2014.
Article in English | MEDLINE | ID: mdl-24552956

ABSTRACT

The incorporation of ß-cyclodextrin (ß-CD) within the framework structure of copolymer sorbent materials, represents a novel modular design approach with significant potential for controlled tuning of the textural mesoporosity of such sorbent frameworks. ß-CD copolymers represent an innovative design strategy for the development of "smart" or "functional" porous materials with improved solid phase extraction (SPE) and molecular recognition properties because of the porogen characteristics and their unique host-guest properties. Carbohydrate-based copolymers containing cyclodextrins (CDs) are of interest, in part, because of their ability to form stable inclusion complexes in aqueous solution. The inclusion properties of ß-CD copolymers are determined by the surface area, pore structure, and site accessibility of inclusion sites within the copolymer framework. A mini-review of recent research in our group concerning the use of copolymers containing ß-CD as sorbent materials for naphthenic acids is presented herein.


Subject(s)
Environmental Restoration and Remediation/methods , Oil and Gas Fields , Polymers/chemistry , Solid Phase Extraction/methods , beta-Cyclodextrins/chemistry , Nanoparticles , Porosity
16.
J Phys Chem B ; 117(13): 3659-66, 2013 Apr 04.
Article in English | MEDLINE | ID: mdl-23470092

ABSTRACT

The sorption properties are reported for several examples of single-component carboxylic acids representing naphthenic acids (NAs) with ß-cyclodextrin (ß-CD) based polyurethane sorbents. Seven single-component examples of NAs were chosen with variable z values, carbon number, and chemical structure as follows: 2-hexyldecanoic acid (z = 0 and C = 16; S1), n-caprylic acid (z = 0 and C = 8; S2), trans-4-pentylcyclohexanecarboxylic acid (z = -2 and C = 12; S3), 4-methylcyclohexanecarboxylic acid (z = -2 and C = 8; S4), dicyclohexylacetic acid (z = -4; C = 14; S5), 4-pentylbicyclo[2.2.2]octane-1-carboxylic acid (z = -4; C = 14; S6), and lithocholic acid (z = -6; C = 24; S7). The copolymer sorbents were synthesized at three relative ß-CD:diisocyanate mole ratios (i.e., 1:1, 1:2, and 1:3) using 4,4'-dicyclohexylmethane diisocyanate (CDI) and 4,4'-diphenylmethane diisocyanate (MDI). The sorption properties of the copolymer sorbents were characterized using equilibrium sorption isotherms in aqueous solution at pH 9.00 with electrospray ionization mass spectrometry. The equilibrium fraction of the unbound carboxylate anions was monitored in the aqueous phase. The sorption properties of the copolymer sorbents (i.e., Qm) were obtained from the Sips isotherm model. The Qm values generally decrease as the number of accessible ß-CD inclusion sites in the copolymer framework decreases. The chemical structure of the adsorbates played an important role in their relative uptake, as evidenced by the adsorbate lipophilic surface area (LSA) and the involvement of hydrophobic effects. The copolymers exhibit molecular selective sorption of the single-component carboxylates in mixtures which suggests their application as sorbents for fractionation of mixtures of NAs. By comparison, granular activated carbon (GAC) and chitosan sorbents did not exhibit any significant molecular selective sorption relative to the copolymer materials; however, evidence of variable sorption capacity was observed among the sorbents investigated.


Subject(s)
Carboxylic Acids/chemistry , Polyurethanes/chemistry , Adsorption , Models, Molecular , Molecular Structure , Surface Properties , beta-Cyclodextrins/chemistry
17.
J Colloid Interface Sci ; 395: 104-10, 2013 Apr 01.
Article in English | MEDLINE | ID: mdl-23374435

ABSTRACT

Tensiometry was used to provide estimates of the critical micelle concentration (cmc) values for three sources of naphthenic acids (NAs) and three examples of single component NAs (S1-S3) in aqueous solution at pH 10.5 and 295 K. Two commercially available mixtures of NAs and an industrially derived mixture of NAs obtained from Alberta oil sands process water (OSPW) were investigated. The three examples of single component NAs (C(n)H(2n+z)O2) were chosen with variable z-series to represent chemical structures with 0-2 rings, as follows: 2-hexyldecanoic acid (z=0; S1), trans-4-pentylcyclohexanecarboxylic acid (z=-2; S2) and dicyclohexylacetic acid (z=-4; S3). The estimated cmc values for S1 (35.6 µM), S2 (0.545 mM), and S3 (4.71 mM) vary over a wide range according to their relative lipophile characteristics of each carboxylate anion. The cmc values for the three complex mixtures of NAs were evaluated. Two disctinct cmc values were observed (second listed in brackets) as follows: Commercial sample 1; 50.9 µM (109 µM), Commercial sample 2; 22.3 µM (52.2 µM), and Alberta derived OSPW; 154 µM (417 µM). These results provide strong support favouring two general classes of NAs in the mixtures investigated with distinct cmc values. We propose that the two groups may be linked to a recalcitrant fraction with a relatively large range of cmc values (52.2-417 µM) and a readily biodegradable fraction with a relatively low range of cmc values (22.3-154 µM) depending on the source of NAs in a given mixture.

18.
Nanomaterials (Basel) ; 2(2): 163-186, 2012 Jun 06.
Article in English | MEDLINE | ID: mdl-28348302

ABSTRACT

In this review, the preparation of porous copolymer resin (PCR) materials via suspension polymerization with variable properties are described by tuning the polymerization reaction, using solvents which act as porogens, to yield microporous, mesoporous, and macroporous materials. The porogenic properties of solvents are related to traditional solubility parameters which yield significant changes in the surface area, porosity, pore volume, and morphology of the polymeric materials. The mutual solubility characteristics of the solvents, monomer units, and the polymeric resins contribute to the formation of porous materials with tunable pore structures and surface areas. The importance of the initiator solubility, surface effects, the temporal variation of solvent composition during polymerization, and temperature effects contribute to the variable physicochemical properties of the PCR materials. An improved understanding of the factors governing the mechanism of formation for PCR materials will contribute to the development and design of versatile materials with tunable properties for a wide range of technical applications.

19.
J Colloid Interface Sci ; 357(1): 215-22, 2011 May 01.
Article in English | MEDLINE | ID: mdl-21349528

ABSTRACT

The surface area and pore structure characteristics were investigated for a series of aliphatic- and aromatic-based polyurethane (PU) copolymers containing a macromolecular porogen (ß-cyclodextrin). The bi-functional diisocyanates used as crosslinker units were: 1,6-hexamethylene, 4,4'-dicyclohexylmethane, 4,4'-diphenylmethane, 1,4-phenylene, and 1,5-naphthalene diisocyanate, respectively. The macromolecular porogen content was controlled by fixing the composition of ß-CD and varying the co-monomer mole ratio from unity to larger integer values. Nitrogen adsorption results reveal that copolymer materials with variable mole ratios (ß-CD: crosslinker) from 1:1 to 1:3 displayed relatively low BET surface areas (SA∼10(1) m(2)/g) and mesopore diameters (∼16-29 nm). In contrast, a dye adsorption method in aqueous solution with p-nitrophenol (PNP) at pH=4.60 and 295 K provided estimates of the surface area (1.5-6.2×10(2) m(2)/g) for the corresponding copolymer materials. Variation of the copolymer SA was attributed to the type of diisocyanate crosslinker and its relative mole ratio. The differences in the estimated SA values from porosimetry and the UV-Vis dye adsorption method for these nanoporous copolymers were attributed to the role of solvent as evidenced by swelling of the copolymer framework in aqueous solution and the respective temperature conditions.

20.
J Colloid Interface Sci ; 356(1): 217-26, 2011 Apr 01.
Article in English | MEDLINE | ID: mdl-21255790

ABSTRACT

The sorption of p-nitrophenol (PNP), phenolphthalein (phth) and naphthenates (NAs) with ß-cyclodextrin (ß-CD) based polyurethane sorbents from aqueous solutions are reported. The copolymer sorbents were synthesized at various ß-CD/diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and hydrogen deficiency. The copolymer sorbents were characterized in the solid state using (13)C CP-MAS NMR spectroscopy, IR spectroscopy and elemental (C,H,N) analysis. The equilibrium sorption properties of the copolymer sorbents in aqueous solution were characterized using isotherm models at pH 4.6 and 9.0 for PNP, pH 9.0 for naphthenates and pH 10.5 for phth. UV-Vis spectroscopy was used to monitor the unbound fraction of the phenolic dyes in the aqueous phase, whereas, electrospray ionization mass spectrometry was used to monitor the unbound fraction of naphthenates. The sorption results of the copolymer sorbents were compared with a commercially available carbonaceous standard; granular activated carbon (GAC). The sorption properties and capacities of the copolymer sorbents (Q(m)) were estimated using the Sips isotherm. The sorption capacity for GAC was 2.15 mmol PNP/g, 0.0698 mmol phth/g, and 142 mg NAs/g, respectively, whereas the polymeric materials ranged from 0.471 to 1.60 mmol/g (PNP), 0.114 to 0.937 mmol/g (phth), and 0 to 75.5 mg/g (naphthenates), respectively, for the experimental conditions investigated. The observed differences in the sorption properties were attributed to the accessible surface areas and pore structure characteristics of the copolymer sorbents. The binding constant, K(eq), for copolymer materials for each sorbate is of similar magnitude to the binding affinity observed for native ß-CD. PNP showed significant binding onto the copolymer framework containing diisocyanate domains, whereas, negligible sorption to the sites was observed for phth and naphthenates. The ß-CD inclusion sites in the copolymer framework are concluded to be the main sorption site for phth and naphthenates through the formation of well-defined inclusion complexes.

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