Fluorescent Graphitic Carbon Nitride (g-C3N4)-Embedded Hyaluronic Acid Microgel Composites for Bioimaging and Cancer-Cell Targetability as Viable Theragnostic.

Fluorescent graphitic carbon nitride (g-C3N4) doped with various heteroatoms, such as B, P, and S, named Bg-C3N4, Pg-C3N4, and Sg-C3N4, were synthesized with variable band-gap values as diagnostic materials. Furthermore, they were embedded within hyaluronic acid (HA) microgels as g-C3N4@HA microgel composites. The g-C3N4@HA microgels had a 0.5-20 µm size range that is suitable for intravenous administration. Bare g-C3N4 showed excellent fluorescence ability with 360 nm excitation wavelength and 410-460 emission wavelengths for possible cell imaging application of g-C3N4@HA microgel composites as diagnostic agents. The g-C3N4@HA-based microgels were non-hemolytic, and no clotting effects on blood cells or cell toxicity on fibroblasts were observed at 1000 µg/mL concentration. In addition, approximately 70% cell viability for SKMEL-30 melanoma cells was seen with Sg-C3N4 and its HA microgel composites. The prepared g-C3N4@HA and Sg-C3N4@HA microgels were used in cell imaging because of their excellent penetration capability for healthy fibroblasts. Furthermore, g-C3N4-based materials did not interact with malignant cells, but their HA microgel composites had significant penetration capability linked to the binding function of HA with the cancerous cells. Flow cytometry analysis revealed that g-C3N4 and g-C3N4@HA microgel composites did not interfere with the viability of healthy fibroblast cells and provided fluorescence imaging without any staining while significantly decreasing the viability of cancerous cells. Overall, heteroatom-doped g-C3N4@HA microgel composites, especially Sg-C3N4@HA microgels, can be safely used as multifunctional theragnostic agents for both diagnostic as well as target and treatment purposes in cancer therapy because of their fluorescent nature.

B, P, and S heteroatom doped, bio- and hemo-compatible 2D graphitic-carbon nitride (g-C3N4) with antioxidant, light-induced antibacterial, and bioimaging endeavors.

The synthesis of two-dimensional (2D) graphiticg-C3N4and heteroatom-doped graphitic H@g-C3N4(H: B, P, or S) particles were successfully done using melamine as source compounds and boric acid, phosphorous red, and sulfur as doping agents. The band gap values of 2Dg-C3N4, B50@g-C3N4, P50@g-C3N4, and S50@g-C3N4structures were determined as 2.90, 3.03, 2.89, and 2.93 eV, respectively. The fluorescent emission wavelengths of 2Dg-C3N4, B50@g-C3N4, P50@g-C3N4, and S50@g-C3N4structures were observed at 442, 430, 441, and 442 nm, respectively upon excitation atλEx= 325 nm. There is also one additional new emission wavelength was found at 345 nm for B50@g-C3N4structure. The blood compatibility test results ofg-C3N4, B50@g-C3N4, P50@g-C3N4, and S50@g-C3N4structures revealed that all materials are blood compatible with <2% hemolysis and >90% blood clotting indices at 100µg ml-1concentration. The cell toxicity of the prepared 2D graphitic structures were also tested on L929 fibroblast cells, and even the heteroatom doped hasg-C3N4structures induce no cytotoxicity was observed with >91% cell viability even at 250µg ml-1particle concentration with the exception of P50@g-C3N4which as >75 viability. Moreover, for 2Dg-C3N4, B50@g-C3N4, and S50@g-C3N4constructs, even at 500µg ml-1concentration, >90% cell viabilities was monitored. As a diagnostic material, B50@g-C3N4was found to have significantly high penetration and distribution abilities into L929 fibroblast cells granting a great potential in fluorescence imaging and bioimaging applications. Furthermore, the elemental doping with B, P, and S ofg-C3N4were found to significantly increase the photodynamic antibacterial activity e.g. more than half of bacterial elimination by heteroatom-doped forms ofg-C3N4under UVA treatment was achieved.

Super-Macroporous Pulluan Cryogels as Controlled Active Delivery Systems with Controlled Degradability.

Here, super-macroporous cryogel from a natural polysaccharide, pullulan was synthesized using a cryo-crosslinking technique with divinyl sulfone (DVS) as a crosslinker. The hydrolytic degradation of the pullulan cryogel in various simulated body fluids (pH 1.0, 7.4, and 9.0 buffer solutions) was evaluated. It was observed that the pullulan cryogel degradation was much faster in the pH 9 buffer solution than the pH 1.0 and 7.4 buffer solutions in the same time period. The weight loss of the pullulan cryogel at pH 9.0 within 28 days was determined as 31% ± 2%. To demonstrate the controllable drug delivery potential of pullulan cryogels via degradation, an antibiotic, ciprofloxacin, was loaded into pullulan cryogels (pullulan-cipro), and the loading amount of drug was calculated as 105.40 ± 2.6 µg/mg. The release of ciprofloxacin from the pullulan-cipro cryogel was investigated in vitro at 37.5 °C in physiological conditions (pH 7.4). The amount of drug released within 24 h was determined as 39.26 ± 3.78 µg/mg, which is equal to 41.38% ± 3.58% of the loaded drug. Only 0.1 mg of pullulan-cipro cryogel was found to inhibit half of the growing Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) colonies for 10 min and totally eradicated within 2 h by the release of the loaded antibiotic. No significant toxicity was determined on L929 fibroblast cells for 0.1 mg drug-loaded pullulan cryogel. In contrast, even 1 mg of drug-loaded pullulan cryogel revealed slight toxicity (e.g., 66% ± 9% cell viability) because of the high concentration of released drug.

Physically and Chemically Crosslinked, Tannic Acid Embedded Linear PEI-Based Hydrogels and Cryogels with Natural Antibacterial and Antioxidant Properties.

Linear polyethyleneimine (L-PEI) was obtained from the acidic hydrolysis of poly(2-ethyl-2-oxazoline) and employed in the synthesis of physically crosslinked L-PEI hydrogel, PC-L-PEIH, chemically crosslinked L-PEI hydrogel, CC-L-PEIH, and cryogels, CC-L-PEIC. The preparation of L-PEI-based hydrogel networks was carried out in two ways: 1) by cooling the L-PEI solution from 90 °C to room temperature, and 2) by crosslinking L-PEI chains with a crosslinker, glycerol diglycidyl ether = 20 °C for CC-L-PEIC. Furthermore, a polyphenolic compound, tannic acid (TA), with superior antibacterial, antioxidant, and anti-inflammatory properties as an active biomedical functional agent, was encapsulated during the synthesis process within L-PEI-based hydrogels and cryogels, at 10% and 25% (w/w) based on the L-PEI amount. A linear and higher TA release was observed from physically crosslinked PEI-based hydrogels containing 10% and 25% TA-containing PC-L-PEI/TAH within 6 h, with 9.5 ± 05 mg/g and 60.2 ± 3.8 mg/g cumulative released amounts, respectively. A higher antioxidant activity was observed for 25% TA containing PC-L-PEI/TAH with 53.6 ± 5.3 µg/mL total phenol content and 0.48 ± 0.01 µmole Trolox equivalent/g. The minimum bactericidal concentration (MBC) of PC-L-PEIH and CC-L-PEIC networks against both E. coli (ATCC 8739) and Gram-positive B. subtilis (ATCC 6633) bacteria was determined at 5 mg/mL, whereas the MBC value of 10 mg/mL for CC-L-PEIH networks against the same bacteria was achieved.

Removal of Cd(II), Co(II), Cr(III), Ni(II), Pb(II) and Zn(II) ions from wastewater using polyethyleneimine (PEI) cryogels.

The removal of the target analytes, Cd(II), Co(II), Cr(III), Ni(II), Pb(II), and Zn(II) from contaminated waters was achieved using super porous polyethyleneimine (PEI) cryogels as adsorbent. The optimum values of the sample pH and contact time were determined as 4.0 and 90 min, respectively, for the removal of the analytes. The adsorption capacities of the sorbent were between 19.88 and 24.39 mgg-1 from 10 mL of 50 mgL-1 target metal ion solutions. The sorption kinetics of metal ions were fitted with the pseudo-second-order model. The adsorption isotherms of the target analytes into PEI cryogel were well-fitted to the Langmuir isotherm model as expected from the material homogeneity. The selectivity of the PEI cryogel in the presence of Na+, Ca2+, Mg2+, NO3-, K+ and Cl- ions even at high concentrations was tested, and the tolerance limits were satisfactory enough, e.g., the adsorption of the target analytes was even not affected in the presence of 2000 mgL-1 Ca2+, K+, Na+, Cl- and 5000 mgL-1 NO3- ions. The PEI cryogels were successfully utilized in different industrial wastewater samples that were spiked with a known amount of analytes. The removal of the analytes from wastewater samples was in the following ranges 91.94-99.86% for Cd(II), 89.59-99.89% for Co(II), 80.35-99.76% for Cr(III), 92.02-99.84% for Ni(II), 83.28-99.86% for Pb(II), and 82.94-98.24% for Zn(II), respectively. The presented novel removal strategy offers a selective, efficient, and easy application for target metal ions from industrial wastewater samples.

Enhanced Bioactive Properties of Halloysite Nanotubes via Polydopamine Coating.

Halloysite nanotubes (HNT) were coated five times with dopamine (DOPA) in a tris buffer medium at pH 8.5 to acquire polydopamine-coated HNTs (PDOPA@HNT), e.g., PDOPA1@HNT, PDOPA3@HNT, and PDOPA5@HNT. Upon coating HNT with PDOPA, the surface area, pore volume, and pore size were decreased depending on the number of coatings. While the surface area of HNT was 57.9 m2/g, by increasing the number of coatings from 1 to 5, it was measured as 55.9, 53.4, 53.3, 47.4, and 46.4 m2/g, respectively. The isoelectric point (IEP) for HNTs was determined as 4.68, whereas these values are estimated as 2.31 for PDOPA1@HNTs, 3.49 for PDOPA3@HNT, and 3.55 for PDOPA5@HNT. Three different antioxidant studies were conducted for HNT and PDOPA@HNT, and the total phenol (TPC) value of HNT was found to be 150.5 ± 45.9 µmol gallic acid (GA) equivalent. The TPC values for PDOPA1@HNT, PDOPA3@HNT and PDOPA5@HNT coatings were found to be 405.5 ± 25.0, 750.0 ± 69.9, and 1348.3 ± 371.7 µmol GA equivalents, respectively. The Fe(II) chelation capacity of HNT was found to be 20.5% ± 1.2%, while the PDOPA1@HNT, PDOPA3@HNT and PDOPA5@HNT values were found to be 49.9 ± 6.5, 36.6 ± 12.7 and 25.4 ± 1.2%, respectively. HNT and PDOPA@HNTs inhibited the α-glucosidase (AG) enzyme to greater extents than acetylcholinesterase (AChE). As a result, the DOPA modification of HNTs was rendered to provide additional characteristics, e.g., antioxidant properties and higher AChE and AG enzymes inhibition capabilities. Therefore, PDOPA@HNTs have great potential as biomaterials.

Thiourea-Isocyanate-Based Covalent Organic Frameworks with Tunable Surface Charge and Surface Area for Methylene Blue and Methyl Orange Removal from Aqueous Media.

A thiourea hexamethylene diisocyanate covalent organic framework (TH COF) was synthesized by adjusting the surface charge and surface area. The surface charge value of TH COF, −3.8 ± 0.5 mV, can be changed to −29.1 ± 0.4 mV by treatment with NaOH (dp-TH) and 17.1 ± 1.0 mV by treatment with HCl (p-TH). Additionally, the surface area of TH COF was 39.3 m2/g, whereas the surface area of dp-TH COF and p-TH COF structures were measured as 41.4 m2/g and 42.5 m2/g, respectively. However, the COF structure had a better adsorption capability with acid and base treatments, e.g., dp-TH COF absorbed 5.5 ± 0.3 mg/g methylene blue (MB) dye, and p-TH COF absorbed 25.9 ± 1.4 mg/g methyl orange (MO) dye from 100 mL 25 ppm aqueous dye solutions, thereby increasing the MB and MO absorption amounts of the TH COF structure. Furthermore, by calculating the distribution, selectivity, and relative selectivity coefficients, the absorption capacity order was determined as dp-TH > TH > p-TH COFs for the MB dye, whereas it was p-TH > TH > dp-TH COFs for the MO dye. Finally, the reusability of dp-TH COF for MB absorption and p-TH COF for MO absorption were investigated. After five repeated uses, dp-TH COF retained 64.6 ± 3.7% of its absorption ability, whereas p-TH COF preserved 79.7 ± 3.2% of its absorption ability relative to the initial absorption amount.

Red Pepper and Turmeric-Flavored Virgin Olive Oil Oleogels Prepared with Whale Spermaceti Wax.

This study aimed to prepare and evaluate ground red pepper and turmeric added virgin olive oil (VOO) oleogels with whale spermaceti wax (WSW) as organogelator. The concentration of WSW was 8 wt%, and each spice was added at 1 overall wt%. Prepared oleogels were analyzed for main physico-chemical, structural, thermal, rheological properties. Further, aromatics volatile compositions, sensory descriptive analysis and consumer tests were completed. Results indicated that the new oleogels were quite spreadable preparates with acceptable quality indices. The oleogels included ß type polymorphs, and showed up to 38℃ of peak melting temperatures. Rheological measurements proved true gel structure stable within applicable frequencies and above 38°C surrounding temperatures. The oleogels were thermo-reversible, and their gel state was recoverable after high shear. Around 25 different aromatic volatile compounds were identified in the two oleogels, most shown to be originating from the VOO, and the spices added. The panel defined and scored the samples with 12 sensory descriptive (hardness, spreadability, liquefaction, sandiness, olive fruit, grassy, waxy, rancid, bitter, hay, cooling and mouth coating) terms. Sensory scores were mostly similar to each other and also within the ranges given in the literature for similar spreadable fat products. Consumer test identified the samples with liked scores (above 4 in 5-max point scale) for appearance, aroma, flavour and overall acceptability. In conclusion, ground spices enriched VOO oleogels with WSW were developed successively to offer consumers spreadable olive oil products to extent consumption patterns with special flavors and health benefits of the spices.

Improved Biomedical Properties of Polydopamine-Coated Carbon Nanotubes.

Carbon nanotubes (CNTs) due to their outstanding mechanical, thermal, chemical, and optical properties were utilized as a base material and were coated with polydopamine (PDA) (PDA@CNT) via the simple self-polymerization of dopamine (DA). Then, PDA@CNT coatings of up to five layers were examined for potential biomedical applications. The success of multiple coating of CNTs with PDA was confirmed via increased weight loss values with the increased number of PDA coatings of CNTs at 500 °C by thermogravimetric analysis. The surface area of bare CNTs was measured as 263.9 m2/g and decreased to 197.0 m2/g after a 5th coating with PDA. Furthermore, the antioxidant activities of CNT and PDA@CNTs were determined via total flavonoid content (TFC), total phenol content (TPC), and Fe(III)-reducing antioxidant power (FRAP) tests, revealing the increased antioxidant ability of PDA@CNTs with the increasing numbers of PDA coatings. Moreover, a higher inhibition percentage of the activity of the alpha-glucosidase enzyme with 95.1 ± 2.9% inhibition at 6 mg/mL PDA-1st@CNTs concentration was found. The CNT and PDA@CNTs exhibited blood compatibility, less than a 2.5% hemolysis ratio, and more than 85% blood clotting indexes. The minimum inhibition concentration (MIC) of PDA-5th@CNTs against E. coli and S. aureus bacteria was determined as 10 mg/mL.

Chondroitin Sulfate-Based Cryogels for Biomedical Applications.

Cryogels attained from natural materials offer exceptional properties in applications such as tissue engineering. Moreover, Halloysite Nanotubes (HNT) at 1:0.5 weight ratio were embedded into CS cryogels to render additional biomedical properties. The hemolysis index of CS cryogel and CS:HNT cryogels was calculated as 0.77 ± 0.41 and 0.81 ± 0.24 and defined as non-hemolytic materials. However, the blood coagulation indices of CS cryogel and CS:HNT cryogels were determined as 76 ± 2% and 68 ± 3%, suggesting a mild blood clotting capability. The maximum% swelling capacity of CS cryogel was measured as 3587 ± 186%, 4014 ± 184%, and 3984 ± 113%, at pH 1.0, pH 7.4 and pH 9.0, respectively, which were reduced to 1961 ± 288%, 2816 ± 192, 2405 ± 73%, respectively, for CS:HNT cryogel. It was found that CS cryogels can hydrolytically be degraded 41 ± 1% (by wt) in 16-day incubation, whereas the CS:HNT cryogels degraded by 30 ± 1 wt %. There is no chelation for HNT and 67.5 ± 1% Cu(II) chelation for linear CS was measured. On the other hand, the CS cryogel and CS:HNT cryogel revealed Cu(II) chelating capabilities of 60.1 ± 12.5%, and 43.2 ± 17.5%, respectively, from 0.1 mg/mL Cu(II) ion stock solution. Additionally, at 0.5 mg/mL CS, CS:HNT, and HNT, the Fe(II) chelation capacity of 99.7 ± 0.6, 86.2 ± 4.7% and only 11.9 ± 4.5% were measured, respectively, while no Fe(II) was chelated by linear CS chelated Fe(II). As the adjustable and controllable swelling properties of cryogels are important parameters in biomedical applications, the swelling properties of CS cryogels, at different solution pHs, e.g., at the solution pHs of 1.0, 7.4 and 9.0, were measured as 3587 ± 186%, 4014 ± 184%, and 3984 ± 113%, respectively, and the maximum selling% values of CS:HNT cryogels were determined as 1961 ± 288%, 2816 ± 192, 2405 ± 73%, respectively, at the same conditions. Alpha glucosidase enzyme interactions were investigated and found that CS-based cryogels can stimulate this enzyme at any CS formulation.

Preparation and Evaluation of Virgin Olive Oil Oleogels Including Thyme and Cumin Spices with Sunflower Wax.

This study aimed to prepare and evaluate virgin olive oil (VOO) oleogels enriched with thyme and cumin spices with sunflower wax (SW) organogelator. Common physico-chemical, structural, thermal, and rheological analyses were completed. Furthermore, aromatic volatiles composition, sensory descriptive analysis, and consumer tests were provided. Results indicated that spice addition does not interfere with gel formation, stability, and gelation time. The oleogels' color values were affected by the color of the VOO and the spices. The free fatty acidity and peroxide values were within the acceptable limits for virgin olive oils. There were ß' crystal polymorphs, and melting peak temperatures were around 62 °C. Rheological analyses proved that the oleogels were fairly stable under moderate frequencies, maintained their gelled state until around 52 °C, and recovered their shear induced structural loss after force cessation. There were 22 aromatic volatiles quantified in the samples, which originated from the VOO and spices used as ingredients. A trained panel defined the samples using 13 sensory descriptors. Consumer tests proved that the new oleogels were liked by consumers. Overall, this study provided information and the possibility of spice-enriched and spreadable VOO oleogels to enhance per capita consumption of olive oils with new consumption habits.

Poly(vinyl alcohol)-tannic Acid Cryogel Matrix as Antioxidant and Antibacterial Material.

The biocompatible, viscoelastic properties of poly(vinyl alcohol) (PVA) in combination with the antimicrobial and antioxidant natural polyphenolic, tannic acid (TA), and the natural flavonoid and antioxidant curcumin (Cur), were used in the preparation of PVA:TA and PVA:TA:Cur cryogel composites using cryotropic gelation to combine the individually beneficial properties. The effect of TA content on the antioxidant and antimicrobial activities of PVA:TA cryogel composites and the antioxidant activities of PVA:TA:Cur cryogel composites was determined using Trolox equivalent antioxidant capacity (TEAC) and total phenol content (TPC) assays, and were compared. The PVA:TA:Cur cryogel composite showed the highest antioxidant activity, with a TEAC value of 2.10 ± 0.24 and a TPC value of 293 ± 12.00. The antibacterial capacity of the PVA:TA and PVA:TA:Cur 1:1:0.1 cryogel composites was examined against two different species of bacteria, E. coli and S. aureus. It was found that the minimum inhibition concentration (MIC) value of the PVA:TA:Cur 1:1:0.1 cryogel composites varied between 5 and 10 mg/mL based on the type of microorganism, and the minimum bactericidal concentration (MBC) value was 20 mg/mL irrespective of the type of microorganism. Furthermore, the hemocompatibility of the PVA:TA cryogel composites was evaluated by examining their hemolytic and coagulation behaviors. PVA:TA 1:1 cryogels with a value of 95.7% revealed the highest blood clotting index value amongst all of the synthesized cryogels, signifying the potential for blood contacting applications. The release of TA and Cur from the cryogel composites was quantified at different pH conditions, i.e., 1.0, 7.4, and 9.0, and additionally in ethanol (EtOH) and an ethanol-water (EtOH:Wat) mixture. The solution released from the PVA:TA cryogels in PBS was tested for inhibition capability against α-glucosidase (E.C. 3.2.1.20). Concentration-dependent enzyme inhibition was observed, and 70 µL of 83 µg/mL PVA:TA (1:1) cryogel in PBS inhibited α-glucosidase enzyme solution of 0.03 unit/mL in 70 µL by 81.75 ± 0.96%.

Enhanced enzymatic activity and stability by in situ entrapment of α-Glucosidase within super porous p(HEMA) cryogels during synthesis.

Here, poly(2-hydroxyethyl methacrylate) (p(HEMA)) cryogel were prepared in the presence 0.48, 0.96, and 1.92 mL of α-Glucosidase enzyme (0.06 Units/mL) solutions to obtain enzyme entrapped superporous p(HEMA) cryogels, donated as α-Glucosidase@p(HEMA)-1, α-Glucosidase@p(HEMA)-2, and α-Glucosidase@p(HEMA)-3, respectively. The enzyme entrapped p(HEMA) cryogels revealed no interruption for hemolysis and coagulation of blood rendering viable biomedical application in blood contacting applications. The α-Glucosidase@p(HEMA)-1 was found to preserve its' activity% 92.3 ±â€¯1.4 % and higher activity% against free α-Glucosidase enzymes in 15-60℃ temperature, and 4-9 pH range. The Km and Vmax values of α-Glucosidase@p(HEMA)-1 cryogel was calculated as 3.22 mM, and 0.0048 mM/min, respectively versus 1.97 mM, and 0.0032 mM/min, for free enzymes. The α-Glucosidase@p(HEMA)-1 cryogel was found to maintained enzymatic activity more than 50 % after 10 consecutive uses, and also preserved their activity more than 50 % after 10 days of storage at 25 ℃, whereas free α-Glucosidase enzyme maintained only 1.9 ±â€¯0.9 % activity under the same conditions.

Graphene Aerogels for In Situ Synthesis of Conductive Poly(para-phenylenediamine) Polymers, and Their Sensor Application.

In this study, macroporous graphene aerogels (GAs) were synthesized by chemical reduction of graphene oxide sheets and were used as a support material for in situ synthesis of conductive poly(para-phenylenediamine) (p(p-PDA)). The in situ synthesis of p(p-PDA) in GA was carried out by using a simple oxidation polymerization technique. Moreover, the prepared conductive p(p-PDA) polymers in the networks of GAs were doped with various types of acids such as hydrochloric acid (HCl), nitric acid (HNO3), sulfuric acid (H2SO4), phosphoric acid (H3PO4), respectively. The prepared GA and different acid-doped forms as GA/p(p-PDA) composites were characterized by FT-IR, TGA, and conductivity measurements. The observed FT-IR peaks at 1574 cm-1, and 1491 cm-1, for stretching deformations of quinone and benzene, respectively, confirmed the in situ synthesis of P(p-PDA) polymers within GAs. The conductivity of GAs with 2.17 × 10-4 ± 3.15 × 10-5 S·cm-1 has experienced an approximately 250-fold increase to 5.16 × 10-2 ± 2.72 × 10-3 S·cm-1 after in situ synthesis of p(p-PDA) polymers and with HCl doping. Conductivity values for different types of acid-doped GA/p(p-PDA) composites were compared with the bare p(p-PDA) and their undoped forms. Moreover, the changes in the conductivity of GA and GA/p(p-PDA) composites upon CO2 gas exposure were compared and their sensory potential in terms of response and sensitivity, along with reusability in CO2 detection, were evaluated.

Natural Celluloses as Catalysts in Dehydrogenation of NaBH4 in Methanol for H2 Production.

Cellulose, the most abundant renewable biopolymer, exists in many forms, such as microgranular cellulose (MGCell), sigmacell cellulose (SCell), cellulose fibers (FCell), and α-cellulose (AlfaCell). Several of these cellulose forms were protonated with an amine-containing agent polyethyleneimine (PEI), and the modified celluloses (XCell-PEI+) were studied as catalysts in methanolysis of NaBH4 for hydrogen (H2) generation. It was found that the SCell-PEI+-catalyzed reaction is the fastest one among the modified celluloses with a hydrogen generation rate of 5520 ± 119 mL H2/(g of catalyst × min). The activation energies of MGCell-PEI+, SCell-PEI+, FCell-PEI+, and AlfaCell-PEI+ were determined as +21.7, +23.4, +24.8, and + 21.8 kJ/mol, respectively. Reusability of catalysts was investigated, and regeneration of cellulose based catalysts after the fifth cycle could be readily achieved by HCl treatment to completely recover its activity. Therefore, PEI-modified-protonated cellulose forms constitute sustainable, re-generable, and renewable catalysts for production of H2, an environmentally benign green energy carrier.

Cryogel composites based on hyaluronic acid and halloysite nanotubes as scaffold for tissue engineering.

We present here preparation of mechanically strong and biocompatible cryogel composites based on hyaluronic acid (HA) and halloysite nanotubes (HNTs) of various compositions, and their applications as scaffold for different cell growing media. Uniaxial compression tests reveal that the incorporation of HNTs into HA cryogels leads to a ~2.5-fold increase in their Young moduli, e.g., from 38 ±â€¯1 to 99 ±â€¯4 kPa at a HA:HNTs weight ratio of 1:2. Although HA:HNTs based cryogels were found to be blood compatible with 1.37 ±â€¯0.11% hemolysis ratio at a HA:HNTs weight ratio of 1:2, they trigger thrombogenic activity with a blood clotting index of 17.3 ±â€¯4.8. Remarkably, HA:HNTs cryogel composites were found to be excellent scaffold materials in the proliferation of rat mesenchymal stem cells (MSC), human cervical carcinoma cells (HeLa), and human colon cancer cells (HCT116). The cell studies revealed that an increased amount of HNT embedding into HA cryogels leads to an increase of MSC proliferation.

Can PEI microgels become biocompatible upon betainization?

Polyethylene imine (PEI) microgels prepared via micro emulsion polymerization technique were treated with 1,3-propane sultone to obtained betainized PEI (b-PEI) microgels. The betainization reaction generated zwitterions on PEI microgel that are positive charges from quarternized amine groups of PEI, and the newly formed negative charges from SO3- groups from the modifying agent, 1,3-propane sultone offered interesting properties. The smaller size of b-PEI microgels that are obtained by simple filtration were increased with betainization from 512±14 to 1114±86nm. Also, the betainization of PEI microgel provided negative zeta potential values at high pH values as 9, 10, 11, and 12. Moreover, the b-PEI microgels render more effective dye absorption capabilities for anionic or cationic organic dyes such as Methyl Orange (MO) and Methylene Blue (MB) separately with the significant increase dye adsorption capacity of 354±31 and 274±19mg/g respectively. Moreover, antibacterial properties of b-PEI microgels tested on the E. coli ATCC 8739 and S. aureus ATCC 6538 were diminished whereas bare PEI has low MIC and MBC values (strong antibacterial properties). Interestingly, the PEI microgels known for their strong antibacterial and toxic nature found to be biocompatible upon betainization reaction. The biocompatibility test were carried with WST-1 tests and double staining methods. The cytotoxicity, apoptotic and necrotic cell tests were shown that PEI microgels induce no cytotoxicity up to 400µg/mL whereas PEI microgels possessed 50% toxicity at this concentration, suggesting that b-PEI microgels become biocompatible upon betainization with, 3-propane sultone.

Introduction of double amidoxime group by double post surface modification on poly(vinylbenzyl chloride) beads for higher amounts of organic dyes, As (V) and Cr (VI) removal.

In this study, the synthesis of micron-sized poly(vinylbenzyl chloride) (p(VBC)) beads and subsequent conversion of the reactive chloromethyl groups to double amidoxime group containing moieties by post modification is reported. The prepared beads were characterized by SEM and FT-IR spectroscopy. The amidoximated p(VBC) beads were used as adsorbent for the removal of organic dyes, such as eosin y (EY) and methyl orange (MO), and heavy metals containing complex ions such as dichromate (Cr2O7(2-)) and arsenate (HAsO4(2)(-)) from aqueous media. The effect of the adsorbent dose on the percent removal, the effect of initial concentration of adsorbates on the adsorption rate and their amounts were also investigated. The Langmuir, Freundlich and Temkin adsorption isotherms were applied to the adsorption processes. The results indicated that the adsorption of both dichromate and arsenate ions obeyed the Langmuir adsorption model. Interestingly, it was found that the prepared beads were capable of removing significant amounts of arsenate and dichromate ions from tap and river (Saricay, Canakkale-Turkey) water.

Fast removal of high quantities of toxic arsenate via cationic p(APTMACl) microgels.

Hydrogels are resourceful materials and can be prepared in different morphology, size, surface charge and porosity adopting different polymerization techniques and reaction conditions. The cationic poly(3-acrylamidopropyl)trimethylammonium chloride (p(APTMACl)) microgels were synthesized by photo-initiated inverse suspension polymerization technique. These microgels were utilized as absorbents for the removal of toxic arsenate (As) from different aqueous environments. The experimental parameters affecting absorption efficiency were investigated, and it was demonstrated that these types of microgels are highly efficient in removing arsenate anions from different aqueous environments compared to the previously reported bulk hydrogel, and cryogel of the same material. A removal efficiency of approximately 97.25% was obtained by immersing 0.5 g microgel in 250 ppm 100 mL solution of arsenate anions for 60 min. Both Langmuir and Freundlich adsorption isotherms were applied to adsorption of arsenate anions by p(APTMACl) microgels, and the Langmuir isotherm was a better representation of the adsorption of arsenate with a high value of R(2) (0.9982). Furthermore, mag-p(APTMACl) microgels were synthesized for the adsorption of arsenate anions to provide easy removal of the microgel composite by using an externally applied magnetic field. Furthermore, re-usability of the p(APTMACl) microgels was also investigated for the adsorption of arsenate anions.

Removal of As(V), Cr(III) and Cr(VI) from aqueous environments by poly(acrylonitril-co-acrylamidopropyl-trimethyl ammonium chloride)-based hydrogels.

Cationic poly(Acrylonitril-co-Acrylamidopropyl-trimethyl Ammonium Chloride) (p(AN-co-APTMACl)) hydrogels in bulk were synthesized by using acrylonitrile (AN) and 3-acrylamidopropyl-trimethyl ammonium chloride (APTMACl) as monomers. The prepared hydrogels were exposed to amidoximation reaction to replace hydrophobic nitrile groups with hydrophilic amidoxime groups that have metal ion binding ability. Those replacements were increased the hydrogels absorption capacity for As(V) and Cr(VI). Langmuir and Freundlich isotherms equations were utilized to obtain the best-fitted isotherm model for the absorption of the ions at different metal ion concentrations. The absorption data of As(V) ion were fitted well to Freundlich isotherm while those of Cr(VI) and Cr(III) ions were fitted well to Langmuir isotherm. The maximum absorption of poly(3-acrylamidopropyl-trimethyl ammonium chloride (p(APTMACl)) and amid-p(AN-co-APTMACl) macro gels were 22.39 mg and 21.83 mg for As(V), and 30.65 mg and 18.16 mg for Cr(VI) ion per unit gram dried gel, respectively. Kinetically, the absorption behaviors of Cr(III) and Cr(VI) ions were fitted well to a pseudo 2nd-order kinetic model and those of As(V) ions were fitted well to a pseudo 1st order kinetic model.