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Most betting sites will offer a variety of these for deposits and withdrawals and they are by far the best way to do it. Skrill is like the MS Dhoni of e-wallets. Widely loved by all, this is one of the best ways to securely add funds to an online betting site. The PFO kinetic models were used to analyze the kinetic results, and estimates of q e and k 1 were obtained by plotting the Q e against time cf. Figure 3 b.

The single-point adsorption test for MB at variable pH cf. Figure 3 c shows a strong dependence on the surface charge of chitosan materials. Favorable binding between MB and the chitosan material surface occurs because of the existence of electrostatic interactions and hydration phenomena. Carboxyl groups are inferred as the active sites for MB adsorption on modified chitosan framework materials; therefore, an increase in the pH increases the negative charge of the surface and accounts for the favorable observed MB adsorption, which is in accordance with the results of zeta-potential measurements.

The uptake properties of all materials show a sudden drop-off, as evidenced by decreased sorption capacity at pH values above 8 because of precipitation of MB. The elution process using NaCl aq was utilized for the removal of adsorbed MB in several cycles and offered a low-cost and facile method for the regeneration. This process was repeated for four cycles in which the uptake capacity of MB dropped significantly for the first cycle and stayed constant for the rest of the cycles. It can be assumed that adsorption of MB onto these frameworks is primarily physical, so the application of a monovalent salt with an elevated level could saturate the binding sites and may result in desorption of the adsorbed dyes; however, the result of regeneration study on TMA1 infers that chemisorption may play a role in the process.

To further study the sorption kinetics and map the morphology of different chitosan materials, confocal microscopy was employed and rhodamine B RH was used as a dye probe because of its chemical structure similarity to MB cf. Figure S4. Figure 4 illustrates several representative confocal images for the Chi, CA1, and TMA1 in the presence of RH at certain exposure intervals 2, 10, and 30 min.

The variable fluorescence emission profile shows the extent of dye diffusion into the structure of various chitosan materials. The continual movement of RH over these intervals indicates that cross-linking not only prevents dye diffusion but also improves it by providing hydrophobic channels. These channels can be created during the cross-linking reaction because of pillaring effects.

Furthermore, comparison of brightness in the confocal images of RB dyes illustrates that the TMA1 cf. Two chitosan framework materials containing carboxyl functional groups were synthesized using CA and TMA cross-linkers. The presence of aromatic rings in the structure of TMA1 leads to the formation of channel structures, which form a water port for transferring the water molecules inside the chitosan polymeric network.

The channels of the network are occupied by water molecules via hydrogen bonding at low pressure. The chitosan framework materials exhibited variable adsorption affinity toward MB dye molecules from aqueous solutions because of the presence of variable polar functional groups. The observed differences for water vapor and dye uptake capacities of chitosan framework materials in this study come from differences in the surface chemistry and textural properties of each chitosan system.

Experimental Section. Figure 5 illustrates the material design of the synthesized chitosan framework materials using two types of cross-linkers. In brief, cross-linked chitosan frameworks were prepared by means of sonication in an ultrasonic bath. After drying, samples were grinded into a powder form for further studies. The BET SA and pore characteristics of materials were calculated from the adsorption isotherm of nitrogen gas. Approximately, a 1. An alumina standard Micromeritics was used for calibration of the instrumental parameters.

The sorption analyzer is an intelligent gravimetric analyzer, which uses the gravimetric technique to measure the magnitude of water vapor sorption of materials with the aid of the HIsorp software program accurately.

Each adsorption—desorption experiment took ca. The mass of samples used was ca. Samples were sealed in hermetic pans, the lid of which was punctured to avoid explosion. For imaging of water-swelled samples with high resolution and better signal-to-noise in a liquid environment, the magnetic AC mode MAC mode was used. Tapping mode cantilevers for imaging had a tip with a radius less than 10 nm. The height variation of the resulting topographic maps was illustrated by a color scale, where bright and dark colors represent higher and lower topographies, respectively.

By considering the volume of solution V and mass of adsorbents m , the difference between initial C 0 and residual C e concentrations of MB was used for determination of the relative uptake capacity of the samples using eq 1 1. The equilibrium uptake of MB by the framework systems was analyzed by the Sips isotherm model, which can be defined by eq 2 31 2 where K s is the adsorption constant, n s is the heterogeneity parameter of the sorbent surface, C e represents the residual adsorbate concentration, and Q m represents the monolayer adsorption capacity of the sorbent surface.

This setup enabled time-dependent adsorption studies with continuous pipetting of aliquots 2 mL over a 60 min time interval. Confocal imaging was used to make an estimate the kinetics of adsorption by employing RH diffusion into the chitosan framework materials. Supporting Information. Author Information. Mohammad H. The pharmaceutical literature revealed several inconsistencies and uncertainties in values obtained for the sp.

With N and Ky adsorption following several methods of sample pretreatment, a value of 1. The very high values of sp. It appears that water sorbed to such polymers most likely exists in at least 3 states: tightly bound to an anhydroglucose unit, less tightly bound, and bulk water.

Colloid Interface Sci. The std. A comparison of the exptl. The identity of the sorption properties of the initial and dewatered porous celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphol. A comparative anal. The affinity of the std. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context. Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties.

Elsevier B. Effects of plasticizers glycerol, sorbitol, and mixt. The combined effects of relative humidity and plasticizer on mech. Water affinities of cassava starch films were affected by hydrophilicity of the plasticizer and its concn. Films plasticized with glycerol, under all RH conditions, adsorbed more moisture with higher initial adsorption rate, and films with higher plasticizers contents exhibited higher equil.

Elsevier Science B. Moisture equil. The application of the GAB model to the exptl. The net isosteric heat of sorption was estd. Isosteric heats of sorption were found to increase with increasing temp. The dynamics of the biodegrdn. The change in wood microstructure characteristics sp. Two-to-eight-nanometer-wide micropores, whose size and vol.

Adsorption Equilibria of Water Vapor on Cork. Food Chem. American Chemical Society. We report here for the first time a complete thermodn. Adsorption-desorption isotherms were accurately measured by thermogravimetry at , , and K in a large range of relative pressure.

Adsorption enthalpies were detd. Adsorption-desorption isotherms exhibit a hysteresis due to the swelling of the material. The influence of the presence of lenticels on the adsorption properties of cork is found to be negligible. A detailed anal. Asia Pac. Key Eng. The crosslinked films were characterized with respect to the mech. The crosslinked films were water-insol. The water vapor transmission rate of chitosan films linearly decreased with increasing concn.

An optimum crosslinking agent concn. Wet alginate films had lower puncture strength and higher elongation values when compared with dry films the mech. In acidic medium, the swelling of the alginate films was independent of the CaCl2 concn. The permeability to chlorpheniramine maleate and guaifenesin varied with pH and CaCl2 concn. Chitosan films showed swelling and permeability characteristics, which were dependent on pH and on the concn.

Diffusion of chlorpheniramine maleate through chitosan films increased with increasing concn. AgroLife Sci. Chitosan samples with different mol. The action of chitosans with mol. Mw from 1. The water-sol. Moreover, water-sol. In contrast, water-insol. The water-insol. The antimicrobial mechanism of dissolved water-insol. The results suggest that optimum chitosan as food preservative should be water-insol.

Cross-Linking Chitosan Nanofibers. In the present study, we have electrospun various grades of chitosan and crosslinked them using a novel method involving glutaraldehyde GA vapor, utilizing a Schiff base imine functionality. SEM images displayed evidence that unfiltered low-, medium-, and high-mol. The as-spun medium mol. As-spun mats were highly sol. After crosslinking, the medium-mol.

Though the extent to which GA penetrates into the chitosan fibers is currently unknown, the crosslinking resulted in increased brittleness, a color change, and the restriction of fiber sliding that resulted in the loss of a pseudo-yield point. Chitosan is a promising environment friendly active polymer packaging material due to its biodegradability, exceptional film forming capacity, great mech. Bifunctional reagent was used for producing water insol. Biopolymeric films crosslinked by Genipin Gp , which is a reagent of natural origin, should have high potential in food packaging.

The influence of the ratio of functional groups in the chitosan-Gp system on film absorption in the visible and UV regions of the spectrum, sorption, phys. The degree of chitosan crosslinking in the films obtained from solns. Gp was estd. It is demonstrated that crosslinking with genipin improves swelling, water resistance, and mech. Food Biophys. Clay Sci. Many pores and pleats were visible on the surface of the composites and provided a good condition for dye adsorption.

Methyl orange MO was selected as a model anionic azo dye to examine the adsorption behavior of the composites. Therefore, the composites can be used as a low-cost alternative for anionic dyes removal from industrial wastewater. Kyzas, George Z. In this work, a grafted with carboxylic groups chitosan material was synthesized and the adsorption mechanism of a basic dye Remacryl Red TGL denoted as CR and a heavy metal Zn was investigated both in single-component and binary solns.

A common phenomenon in the wastewater treatment science is the simultaneous existence of different-type pollutants dyes, heavy metals etc. The adsorption behavior of the material prepd. The calcn. The reuse of this super-adsorbent was also proved with a series of 40 cycles of sequential adsorption and desorption modules.

Colloids Surf. Most importantly, the adsorbent can be easily and efficiently regenerated for reuse with hardly any compromise of the adsorption capacity. The adsorption kinetics, isotherms and thermodn. The thermodn. The inherent advantages of the nano-structured adsorbent, such as adsorption capacity, easy, handy operation, rapid extn. The adsorption of Remazol black 13 reactive dye onto chitosan in aq.

The equil. The max. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism.

Isotherms were also used to obtain the thermodn. The pos. Chitosan is suitable as adsorbent material for adsorption of reactive dye form aq. Process Saf. Elsevier Ltd. A review. Application of chitinous products in wastewater treatment has received considerable attention in recent years in the literature. In particular, the development of chitosan-based materials as useful adsorbent polymeric matrixes is an expanding field in the area of adsorption science.

This review highlights some of the notable examples in the use of chitosan and its grafted and crosslinked derivs. It summarizes the key advances and results that were obtained in their decolorizing application as biosorbents. The review provides a summary of recent information obtained using batch studies and deals with the various adsorption mechanisms involved. The effects of parameters such as the chitosan characteristics, the process variables, the chem.

The review also summarizes and attempts to compare the equil. Growth Des. The shape of grids varies from rhomboidal to squaric depending on the presence of a metal center. The channels of these MOFs are occupied by the one-dimensional water cages. They were also shown to be capable of dye methylene blue and crystal violet removal from aq. Water sorption of gluten and wheat starch films as a function of water activity was studied using gravimetric step-change sorption expts.

Films of different thicknesses were used with the aim to vary the characteristic diffusion time and to get insights in the contribution of the polymer-chain rearrangement in the sorption behavior. It is shown that both starch and gluten are in the glassy state for a water activity a w below 0. The results show that polymer-chain rearrangement and the stress built up in the matrix play an important role in the sorption dynamics of these films. Even when the material is in the glassy state matrix relaxation phenomena play a role in the sorption behavior of starch and gluten.

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ACS AuthorChoice. Article Views Altmetric -. Citations 1. Abstract High Resolution Image. Evaluation of physiochemical properties of newly synthesized materials is indispensably critical for the fate of their applications. Understanding the role of water molecule interactions with other materials is essential before using them because of their pertinent effects on the swelling and hydration properties of materials.

These interactions have been widely investigated in diverse types of materials such as cellulose, 1,2 starch, 3 fruit pills, 4 woods, 5 cork, 6 biomass, 7 and chitosan. Chitosan has high tendency to dissolve in water, which makes it an unsuitable candidate in many applications, particularly the aforementioned ones.

Therefore, there is a need to modify the structural and chemical properties of chitosan to overcome this obstacle. In another study, Acevedo-Fani et al. A few studies showed that the presence of organic vapor pollutants from the atmosphere can be involved in competitive sorption of water vapor because of the displacement of water molecules with adsorbed organic species.

A water vapor sorption study can therefore be used as a valuable technique for characterization using measurement of sorption isotherms. The dynamic vapor sorption DVS technique has been introduced more recently for studying the sorption properties of materials, which offers high data reproducibility and short measurement time.

Depending on the type of the modification process, chitosan materials may adopt variable surface chemistry e. Enhancement in adsorption properties of chitosan-based adsorbents take place because of alteration in physicochemical characteristics i. In a previous report, 24 chitosan framework materials were synthesized using two types of cross-linkers [citric acid CA and trimesic acid TMA ] using a one-pot method. Herein, this study reports systematic adsorption properties of chitosan framework materials toward water vapor and dye molecules.

This study hypothesized that the application of CA and TMA as tripodal cross-linkers would potentially enhance the adsorptive capacity of chitosan-based materials because of their unique structures. Employment of such tripodal cross-linkers enables the generation of a three-dimensional framework on the structure of chitosan.

It is also noteworthy to mention that TMA has a planar structure, whereas CA has a nonplanar one; therefore, generation of a three-dimensional network, specifically in the form of planar versus nonplanar could yield chitosan materials with tunable adsorptive properties.

To support the water vapor sorption study results and gain a better insight into the structure—property relationship of chitosan framework materials, several complementary techniques such as N 2 adsorption—desorption, differential scanning calorimetry DSC , contact angle measurement, confocal microscopy, and atomic force microscopy AFM were employed alongside a methylene blue MB adsorption study in aqueous solution. MB is a commonly used cationic dye in the diving industry because of its high water-solubility property.

MB is hazardous, especially if ingested. In many studies, adsorptive removal of MB with cross-linked chitosan is reported effective owing to its high adsorptive capacity, high surface area SA , and presence of variable functional groups e. To address the need for development of renewable biomaterial-based adsorbents with improved dye adsorption capacities, synthesized chitosan framework materials mentioned in this study could represent a versatile new class of adsorbents. The results of this study will contribute to development of chitosan framework materials with application as adsorbents, dehumidifiers, and packaging films owing to their tunable properties in terms of interaction with water molecules.

Results and Discussion. Because of the complexity of the chitosan structure and its modified forms and presence of various functionalities, evaluating the polarity and its effect on the adsorptive behavior can provide a useful means for understanding the adsorption process. Water contact angle measurement is a useful technique, which enables evaluation of polarity and HLB properties of the surface. A new technique based on the Young—Laplace equation was designed to measure the water contact angles.

Figure 1 represents the water contact angle measurements on chitosan materials. Although TMA1 has same functionalities on its structure, the presence of aromatic rings in the structure and their orientations makes it less hydrophilic. Interestingly, resistance of chitosan toward water diffusion after 15 s cf.

Figure 1 iii may be the result of the lack of channels, while existing channels inside the TMA1 and CA1 framework materials may serve as diffusion ports for transferring the water molecules. High Resolution Image. Noticeably, the SA of chitosan framework materials increased as the cross-linker ratio decreased cf. Cross-linking can alter textural properties of chitosan because of pillaring effects, which can change the accessibility of the functional groups in the modified forms of chitosan.

Figure S2. AFM images clearly show that TMA as a cross-linker can create stiffer and taller pillars, which can result in greater SA compared to the CA, probably because of the variation in the length of cross-linker units. The kinetics of water vapor uptake for chitosan and framework materials are shown in Figure 2 a. The successive sorption mass uptake curves become apparent in response to the steps in the external water content.

Kinetic curves approach an equilibrium point at each step and subsequently reach the saturation point. This trend indicates that rate of adsorption is faster for cross-linked samples. This observation agrees with the observed hysteresis for isotherm of these materials in Figure 2 b. The obtained isotherms from water vapor sorption using the DVS instrument for variable chitosan materials are given in Figure 2 b.

The differences in the isotherm shape at low pressure can be attributed to the presence of the functional groups e. The similarity of slopes in isotherms of all materials at low pressure indicates the same affinity toward water vapor because of abundant hydrophilic functionalities. Contrarily, observed disparity between obtained results from water vapor and N 2 sorption in the case of CA1 samples implies that the spatial arrangement of CA1 has changed throughout the water vapor sorption process.

Disappearance of mesopores from the structure of the CA1 framework material during water vapor sorption can be explained on the basis of its structure. Variable cross-linkers TMA vs CA have diverse effects on properties of the final cross-linked products. Where cross-linking the chitosan by the TM molecule with a planar shape results in layered and rigid structure, CA offers more flexibility to the chitosan structure because of its nonplanar structure. The observed hysteresis for water vapor sorption in TMA1 can be explained by the collapse of mesopores and structural deformation similar to the N2 adsorption isotherm.

In addition, another reason for occurrence of the hysteresis phenomenon is because of swelling properties that can take place during the hydration process. The adsorption process undergoes two stages; i in the first stage, water adsorbs on the surface, where it can form clusters around the hydrophilic functional groups e. The chitosan materials were tested using DSC right after the water swelling test to evaluate the hydration in adsorbents.

DSC results showed an endothermic peak ca. Lower observed intensities of this thermal event for chitosan and CA1 adsorbents compared to TMA1 is related to a reduced amount of water bound to the surface because of their smaller SA.

In turn, a wide temperature transition of the CA1 sample infers greater stabilization of water in the interior part of the polymer matrix versus surface bound environments. The presence of various active sites and channels in the framework materials proved by the water vapor sorption experiment motivated us to explore the sorption abilities of these chitosan frameworks toward a cationic dye, MB, in aqueous solution. Organic dyes are widely employed in many industries, which can cause serious environmental pollution because of their toxicity and carcinogenic effects in humans and animals.

Dye removal is therefore an essential step for treatment of the factory effluents. Chitosan materials as adsorbents are promising candidates for uptake of these pollutants. In Table S1 , the calculated monolayer adsorption capacity Q m from the Sips isotherm model Figure 3 a provides a measure for uptake of MB along with the best-fit results.

A comparison of the Q m values for the chitosan framework materials indicates that TMA1 displays the highest uptake, which implies its higher SA and polarity. MB sorption kinetic results indicated that saturation of the active adsorption sites of the chitosan materials with MB occurs within ca.

The PFO kinetic models were used to analyze the kinetic results, and estimates of q e and k 1 were obtained by plotting the Q e against time cf. Figure 3 b. The single-point adsorption test for MB at variable pH cf. Figure 3 c shows a strong dependence on the surface charge of chitosan materials. Favorable binding between MB and the chitosan material surface occurs because of the existence of electrostatic interactions and hydration phenomena.

Carboxyl groups are inferred as the active sites for MB adsorption on modified chitosan framework materials; therefore, an increase in the pH increases the negative charge of the surface and accounts for the favorable observed MB adsorption, which is in accordance with the results of zeta-potential measurements.

The uptake properties of all materials show a sudden drop-off, as evidenced by decreased sorption capacity at pH values above 8 because of precipitation of MB. The elution process using NaCl aq was utilized for the removal of adsorbed MB in several cycles and offered a low-cost and facile method for the regeneration.

This process was repeated for four cycles in which the uptake capacity of MB dropped significantly for the first cycle and stayed constant for the rest of the cycles. It can be assumed that adsorption of MB onto these frameworks is primarily physical, so the application of a monovalent salt with an elevated level could saturate the binding sites and may result in desorption of the adsorbed dyes; however, the result of regeneration study on TMA1 infers that chemisorption may play a role in the process.

To further study the sorption kinetics and map the morphology of different chitosan materials, confocal microscopy was employed and rhodamine B RH was used as a dye probe because of its chemical structure similarity to MB cf. Figure S4. Figure 4 illustrates several representative confocal images for the Chi, CA1, and TMA1 in the presence of RH at certain exposure intervals 2, 10, and 30 min. The variable fluorescence emission profile shows the extent of dye diffusion into the structure of various chitosan materials.

The continual movement of RH over these intervals indicates that cross-linking not only prevents dye diffusion but also improves it by providing hydrophobic channels. These channels can be created during the cross-linking reaction because of pillaring effects.

Furthermore, comparison of brightness in the confocal images of RB dyes illustrates that the TMA1 cf. Two chitosan framework materials containing carboxyl functional groups were synthesized using CA and TMA cross-linkers.

The presence of aromatic rings in the structure of TMA1 leads to the formation of channel structures, which form a water port for transferring the water molecules inside the chitosan polymeric network. The channels of the network are occupied by water molecules via hydrogen bonding at low pressure. The chitosan framework materials exhibited variable adsorption affinity toward MB dye molecules from aqueous solutions because of the presence of variable polar functional groups.

The observed differences for water vapor and dye uptake capacities of chitosan framework materials in this study come from differences in the surface chemistry and textural properties of each chitosan system. Experimental Section.

Figure 5 illustrates the material design of the synthesized chitosan framework materials using two types of cross-linkers. In brief, cross-linked chitosan frameworks were prepared by means of sonication in an ultrasonic bath.

After drying, samples were grinded into a powder form for further studies. The BET SA and pore characteristics of materials were calculated from the adsorption isotherm of nitrogen gas. Approximately, a 1. An alumina standard Micromeritics was used for calibration of the instrumental parameters.

The sorption analyzer is an intelligent gravimetric analyzer, which uses the gravimetric technique to measure the magnitude of water vapor sorption of materials with the aid of the HIsorp software program accurately. Each adsorption—desorption experiment took ca. The mass of samples used was ca. Samples were sealed in hermetic pans, the lid of which was punctured to avoid explosion.

For imaging of water-swelled samples with high resolution and better signal-to-noise in a liquid environment, the magnetic AC mode MAC mode was used. Tapping mode cantilevers for imaging had a tip with a radius less than 10 nm.

The height variation of the resulting topographic maps was illustrated by a color scale, where bright and dark colors represent higher and lower topographies, respectively. By considering the volume of solution V and mass of adsorbents m , the difference between initial C 0 and residual C e concentrations of MB was used for determination of the relative uptake capacity of the samples using eq 1 1.

The equilibrium uptake of MB by the framework systems was analyzed by the Sips isotherm model, which can be defined by eq 2 31 2 where K s is the adsorption constant, n s is the heterogeneity parameter of the sorbent surface, C e represents the residual adsorbate concentration, and Q m represents the monolayer adsorption capacity of the sorbent surface. This setup enabled time-dependent adsorption studies with continuous pipetting of aliquots 2 mL over a 60 min time interval.

Confocal imaging was used to make an estimate the kinetics of adsorption by employing RH diffusion into the chitosan framework materials. Supporting Information. Author Information. Mohammad H. The pharmaceutical literature revealed several inconsistencies and uncertainties in values obtained for the sp. With N and Ky adsorption following several methods of sample pretreatment, a value of 1. The very high values of sp. It appears that water sorbed to such polymers most likely exists in at least 3 states: tightly bound to an anhydroglucose unit, less tightly bound, and bulk water.

Colloid Interface Sci. The std. A comparison of the exptl. The identity of the sorption properties of the initial and dewatered porous celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphol. A comparative anal. The affinity of the std. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context.

Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties. Elsevier B. Effects of plasticizers glycerol, sorbitol, and mixt. The combined effects of relative humidity and plasticizer on mech. Water affinities of cassava starch films were affected by hydrophilicity of the plasticizer and its concn. Films plasticized with glycerol, under all RH conditions, adsorbed more moisture with higher initial adsorption rate, and films with higher plasticizers contents exhibited higher equil.

Elsevier Science B. Moisture equil. The application of the GAB model to the exptl. The net isosteric heat of sorption was estd. Isosteric heats of sorption were found to increase with increasing temp. The dynamics of the biodegrdn.

The change in wood microstructure characteristics sp. Two-to-eight-nanometer-wide micropores, whose size and vol. Adsorption Equilibria of Water Vapor on Cork. Food Chem. American Chemical Society. We report here for the first time a complete thermodn. Adsorption-desorption isotherms were accurately measured by thermogravimetry at , , and K in a large range of relative pressure. Adsorption enthalpies were detd. Adsorption-desorption isotherms exhibit a hysteresis due to the swelling of the material.

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