Carboxymethyl Cellulose Beads Research Articles

Phosphorylated g-C3N4/sulfur self-doped g-C3N4 homojunction carboxymethyl cellulose beads: An efficient photocatalyst for H2O2 production

The development of highly reusable, affordable, and durable photocatalysts for the production of hydrogen peroxide (H2O2) remained a challenge. In this study, a homojunction photocatalyst (SPGCN) is constructed between phosphorylated g-C3N4 (PCN) and sulfur self-doped g-C3N4 (SCN) using a simple wet impregnation method. Later, the obtained SPGCN homojunction is transformed into hydrogel beads using carboxymethyl cellulose via an effective cross-linking strategy (SPGCN/CMC). The photocatalytic beads displayed a phenomenal H2O2 production of 3.5 mM under visible light illumination for 60 min. The SPGCN/CMC hydrogel beads showed a maximum reusability of 10 cycles with a decline of 1.5 mM H2O2 production. The improved photocatalytic efficiency is indicated by strengthened utilization of visible light via tuning of the band gap, suppressed recombination of electron-hole pairs, and higher separation efficiency through the effective construction of Z-scheme between the phosphorylated carbon nitride and the sulfur-self-doped carbon nitride present in the SPGCN/CMC beads. The mechanistic studies affirmed the dominant role of superoxide radicals in H2O2 production. The photocatalytic H2O2 production followed a highly selective two-electron reduction reaction. Overall, this study highlights the efficient engineering of carbon nitride-based materials towards artificial photosynthesis.

An efficient wastewater treatment through reduction of organic dyes using Ag nanoparticles supported on cellulose gum beads

This work reports silver nanoparticles (AgNPs) supported on biopolymer carboxymethyl cellulose beads (Ag-CMC) serves as an efficient catalyst in the reduction process of p-nitrophenol (p-NP) and methyl orange (MO). For Ag-CMC synthesis, first CMC beads were prepared by crosslinking the CMC solution in aluminium nitrate solution and then the CMC beads were introduced into AgNO3 solution to adsorb Ag ions. Field emission scanning electron microscopy (FE-SEM) analysis suggests the uniform distribution of Ag nanoparticles on the CMC beads. The X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis revealed the metallic and fcc planes of AgNPs, respectively, in the Ag-CMC catalyst. The Ag-CMC catalyst exhibits remarkable reduction activity for the p-NP and MO dyes with the highest rate constant (kapp) of a chemical reaction is 0.519 and 0.697 min−1, respectively. Comparative reduction studies of Ag-CMC with CMC, Fe-CMC and Co-CMC disclosed that Ag-CMC containing AgNPs is an important factore in reducing the organic pollutants like p-NP and MO dyes. During the recyclability tests, the Ag-CMC also maintained high reduction activity, which suggests that CMC protects the AgNPs from leaching during dye reduction reactions.

Pd@HKUST-1@Cu(II)/CMC composite bead as an efficient synergistic bimetallic catalyst for Sonogashira cross-coupling reactions

We fabricated an efficient Pd@HKUST-1@Cu(II)/CMC composite bead catalyst through an innovative strategy based on the unique properties of metal-organic frameworks (MOFs) and carboxymethylcellulose (CMC). In this strategy, HKUST-1 MOFs were grown in-situ on the surface of micrometer-sized Cu-based CMC beads (Cu(II)/CMC), then Pd(II) ions were incorporated into the pores of the MOF and further be partially reduced to Pd(0) NPs, which is an active species for oxidative addition with aryl halides in Sonogashira reactions. The micron-sized Cu(II)/CMC beads were formed through inter/intramolecularly crosslinking facilitated by Cu(II) ions, which was achieved by the metathesis of Cu(II) with numerous carboxylic groups of CMC. Such Cu(II)/CMC bead offers many Cu(II) ions as interaction sites for in-situ nucleation and growth of HKUST-1 MOFs. The architecture and composition of the prepared Pd@HKUST-1@Cu(II)/CMC composite were fully verified by various techniques such as FTIR, XRD, TGA, BET, XPS, SEM, TEM, EDX, and elemental mapping analysis. This novel composite bead was applied as an efficient and reusable heterogeneous Pd/Cu bimetallic catalyst for Sonogashira reactions, decarbonylative Sonogashira reaction, and Sonogashira cyclization tandem reactions. The catalyst is readily isolated by simple filtration, and can be reused for five consecutive runs with retaining its activity and structural integrity.

Adsorption of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose beads: Characterization, toxicity tests, and adsorption experiments

Mercury (Hg) is widely used in many industrial processes and is released into the environment. Therefore, efficient removal of Hg from water is of vital importance worldwide. Here, we explored the adsorption characteristics of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose (PEI-CMC) beads and studied the toxicity of the beads toward Daphnia magna and Pseudokirchneriella subcapitata. The PEI-CMC beads had an average particle size of 2.04 ± 0.25 mm, a point of zero charge (pHpzc) of 5.8, and a swelling ratio of 2.45. Acute toxicity tests demonstrated that the PEI-CMC beads had no toxic effects on D. magna. The growth inhibition tests revealed that growth inhibition of P. subcapitata could be attributed to adsorption of trace elements in growth media on the PEI-CMC beads. The adsorption experiments exhibited that the Matthews and Weber model best described the kinetic data, whereas the Redlich–Peterson model was well fitted to the isotherm data. The theoretical maximum Hg(II) adsorption capacity of the PEI-CMC beads was 313.1 mg/g. The thermodynamic experiments showed endothermic nature of the Hg(II) adsorption on the PEI-CMC beads at 10–40 °C. The adsorption experiments exhibited that the Hg(II) adsorption capacity decreased gradually as pH increased from 2 to 12. The adsorption of Hg(II) on the PEI-CMC beads can occur through chelation and electrostatic attraction. The FTIR and XPS spectra before and after Hg(II) adsorption confirmed that chelation of neutral Hg(II) species (HgCl2, HgClOH, and Hg(OH)2) can occur with amino and oxygen-containing functional groups on the PEI-CMC beads. Considering species distribution of Hg(II) and the pHpzc of the PEI-CMC beads, electrostatic attraction between the positively-charged beads and anionic Hg(II) species (HgCl3− and HgCl42−) can take place in highly acidic solutions. The PEI-CMC beads were regenerated and reused for Hg(II) adsorption using 0.1 M HCl.

Removal of some hazardous ions using titanium oxide and Cunninghamella elegans immobilized in alginate–carboxymethyl cellulose beads

Removal of some hazardous ions using titanium oxide and Cunninghamella elegans immobilized in alginate–carboxymethyl cellulose beads

Hollow polyethyleneimine/carboxymethyl cellulose beads with abundant and accessible sorption sites for ultra-efficient chromium (VI) and phosphate removal

• Novel hollow beads with abundantly accessible sorption sites were prepared. • Demonstration of excellent removal capability of hexavalent chromium and phosphate. • Excellent adsorption and recycling performance for two anionic pollutants. • Easy-to-handle preparation and recovery. Novel millimeter-scale hollow polyethyleneimine/carboxymethylcellulose beads were facilely prepared by simply adjusting the usage of polyethyleneimine for surface modification of preformed solid carboxymethylcellulose beads, which were gradually transformed into hollow beads during the glutaraldehyde mediated cross-linking process. Taking advantage of the hollow structure and porous shells which possess abundant, accessible sorption sites, this newly designed bead-like sorbent exhibited very high adsorption capacity for Cr(VI) and phosphates, for which the exceptional value of 535.39 mg/g and 150.65 mg/g was achieved under fitting conditions, respectively, and both of them much superior to most reported studies. Most importantly, the adsorption capacity for Cr(VI) and phosphate over the typical sorbent remained at high levels even after 6 and 22 cycles, respectively, which is another feature of the hollow bead-like sorbent. Based on various characterization results like SEM-EDX, FT-IR, TGA, zeta potential, XPS, etc., it showed that the adsorption mechanism of Cr(VI) over as-fabricated hollow bead-like sorbents could be mainly correlated to the electrostatic attraction and reduction manner, while the adsorption process of phosphate was mainly due to the electrostatic interaction. By its millimeter-sized shape with surface accessible sorption sites, the column adsorption testing revealed that the Thomas model fitted well with the phosphate adsorption process. Given its controllable fabrication process, excellent adsorption performance, and exceptional mechanical properties, this newly designed millimeter-scale hollow bead-like sorbent has promising applications in the field of anionic pollutant removal.

Metal nanoparticles supported chitosan coated carboxymethyl cellulose beads as a catalyst for the selective removal of 4-nitrophenol

In the area of water pollution treatment, the coupling of biopolymers with metal/metal nanoparticles is getting a lot of interest these days. Herein, carboxymethyl cellulose (CMC) beads and chitosan (Cs) coated CMC beads were employed as a support for copper nanoparticles, (Cu/CMC) and (Cu/Cs@CMC), respectively. Following that, a reducing agent (NaBH4) was used to convert Cu/CMC and Cu/Cs@CMC beads to zero valent. The developed beads were employed for catalytic reductions of nitrophenol, dyes, and potassium hexacyanoferrate (III) in their mixed solution with NaBH4. Cu/Cs@CMC beads were more efficient compared to Cu/CMC beads toward selected pollutants. The reduction rate constants of 4-NP, MO, EY and K3[Fe(CN)6] by utilizing Cu/Cs@CMC were 3.8 × 10−1, 4.0 × 10−1, 1.4 × 10−1 and 4.48 × 10−1 min−1, respectively. Further, the catalytic activity of the Cu/Cs@CMC beads were optimized using 4-NP as a model compound for this study. Cu/Cs@CMC beads were able to use up to three cycles compared to Cu/CMC beads without losing catalytic activity in the reduction of 4-NP, according to the recyclability and reusability study of both beads. The chitosan coating beads Cu/Cs@CMC was simply prepared and have good catalytic activity, recyclable, and more efficient than Cu/CMC beads due to their high strength and stability.

Facile transformation of carboxymethyl cellulose beads into hollow composites for dye adsorption

Novel millimeter hollow microspheres were fabricated from carboxymethyl cellulose microspheres and polyethyleneimine using glutaraldehyde as a crosslinking agent. The hollow microspheres prepared with different polyethyleneimine usages and different polyethyleneimine treatment time were investigated deeply and characterized via SEM-EDX, FT-IR, and BET surface area analysis. It was shown that polyethyleneimine could break the coordination bonds between the carboxyl and Al (III) in carboxymethyl cellulose microspheres, leading to the formation of hollow structures. Most importantly, the usage and treatment time of polyethyleneimine can distinctly tailor the structure of the carboxymethyl cellulose microspheres, resulting in the formation of different hollow microspheres with varied shell thickness and size. Most importantly, we found that the prepared hollow microspheres have excellent adsorption performance toward targeted methyl blue under testing conditions. By virtue of the large accessible amount of -NH2 groups and its unique hollow structure, this type of millimeter hollow microspheres have broad application prospects in the treatment of emerging contaminants in wastewater.

Carboxymethyl cellulose-based cryogels for efficient heavy metal capture: Aluminum-mediated assembly process and sorption mechanism

Heavy metal ions pollution is a terrible issue that needs to be efficiently treated as a matter of priority to construct our sustainable society. However, the easy-to-handling of high-performance biomass-derived sorbents with fascinating features like high sorption capacity, favorable separation and recycling remain challenging. Herein, the development of a novel bead-like adsorbent with above features, that is, Al(III)-assembled carboxymethyl cellulose beads were used for the removal of Pb(II), Ni(II) and Co(II) from aqueous solution. Characterization methods like FT-IR, SEM, XPS and TGA were employed to confirm its physicochemical properties. Removal of the three heavy metal ions at different pH values, initial concentration and contact time were discussed at batch adsorption experiments. Meanwhile, regeneration was also discussed deeply. The results revealed that the adsorption capacity of the sorbents for three heavy metals increases with increasing pH and the initial concentration. The adsorption isotherm could be described well by the Freundlich model, and the maximum adsorption capacity for Pb(II), Ni(II) and Co(II) were 550, 620 and 760 mg/g, respectively. Kinetics study indicated that the Pseudo-second-order model described the best correlation with experimental data, this suggested that the complexation may participated in the adsorption process. More significantly, this type of bead-like adsorbents displayed excellent reusability after four sequential cycles.

In-situ formation and entrapment of Ag/AgCl photocatalyst inside cross-linked carboxymethyl cellulose beads: A novel photoactive hydrogel for visible-light-induced photocatalysis

In this work, a novel photoactive cellulose-based hydrogel was prepared by simultaneous AgCl formation and entrapment inside Al (III) and Fe (III) cross-linked carboxymethyl cellulose beads. Physio-chemical and optical properties of the synthesized composites were well characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, elemental mapping, Fourier transform infrared (FTIR) spectroscopy, photoluminescence (PL), and diffuse reflectance spectroscopy (DRS). The photocatalytic activity of hydrogels was evaluated by the degradation of rhodamine B (RhB), as a model environmental pollutant. A comparative study showed that different cross-linkers resulted in different AgCl content, optical properties, and photocatalytic performance of hydrogel beads. Ag/AgCl@Al-CMC and AgCl@Fe-CMC composites exhibited remarkable photocatalytic performance (98 % and 87 % removal efficiency within 60 min, respectively) under visible light irradiation, and the effect of operational factors contributing to the photocatalytic process, including catalyst dosage, dye concentration, and initial pH was investigated. Scavenging experiments indicated that photo-induced hole and hydroxyl radical made a significant contribution to the degradation of RhB, and a plausible reaction pathway for the generation of major active species was proposed, according to the calculated band edge potentials of the photocatalysts. Reusability experiments revealed that the decolorization performance of the photoactive beads decreased after five repetitive experiments. This decline was attributed to the partial photocatalyst leaching from CMC polymeric network into the aqueous environment, evidenced by the results of ICP-OES analysis. The present study opens a new avenue for the development of hydrogel-based photoactive materials.

PH-sensitive ZnO/carboxymethyl cellulose/chitosan bio-nanocomposite beads for colon-specific release of 5-fluorouracil

To develop relatively green and ecofriendly smart vehicles for colon-specific drug delivery, carboxymethyl cellulose (CMC) and chitosan (CS) pH-sensitive biopolymers were used in this study. To overcome the weaknesses of CMC carriers, such as poor mechanical performance and an explosive drug release, zinc oxide (ZnO) nanoparticles were incorporated into CMC beads and then coated with a CS layer via a self-assembly technique to form core-shell polyelectrolyte complexes. An anticancer drug, 5-fluorouracil (5-FU), used as a model drug, was loaded into ZnO/CMC/CS bio-nanocomposite beads. Fourier transform infrared spectroscopy, scanning and transmission electron microscopy, and thermogravimetric analysis were used to characterize the chemical structure, morphological changes, and thermal properties of the developed drug carrier, respectively. By studying their swelling and in vitro 5-FU release profiles under simulated gastrointestinal conditions, the pH sensitivity of the developed bio-nanocomposite hydrogel beads could be investigated. The obtained beads with reduced porosity could effectively encapsulate 5-FU and showed self-sustained release behavior depending on the concentrations of CMC, CS, and ZnO nanoparticles. The developed beads also demonstrated a capacity for biodegradation. The results indicated that the ZnO/CMC/CS bio-nanocomposite beads exhibited pH-sensitivity and could be applied efficiently as biodegradable carriers for colon-specific 5-FU delivery.

Removal of Pb(ii) and Cd(ii) from wastewater using arginine cross-linked chitosan-carboxymethyl cellulose beads as green adsorbent.

A one pot approach has been explored to synthesize crosslinked beads from chitosan (CS) and carboxymethyl cellulose (CM) using arginine (ag) as a crosslinker. The synthesized beads were characterized by FTIR, SEM, EDX, XRD, TGA and XPS analysis. The results showed that CS and CM were crosslinked successfully and the obtained material (beads) was analyzed for adsorption of Cd(ii) and Pb(ii) by using batch adsorption experiments; parameters such as temperature, contact time, pH and initial ion concentration were studied. Different kinetic and thermodynamic models were used to check the best fit of the adsorption data. The results revealed that the kinetics data of the adsorption of Pb(ii) and Cd(ii) ions shows the best fit with the pseudo second order model whereas the thermodynamics data shows the best fit with the Langmuir isotherm with maximum adsorption capacities of 182.5 mg g−1 and 168.5 mg g−1 for Pb(ii) ions Cd(ii) ions, respectively. For the recovery and the regeneration after the one use of the beads, several adsorption–desorption cycles were carried out to check the reusability and recovery of both the metal ion and the adsorbent without the loss of maximum adsorption efficiency.

Protein‐loaded sodium alginate and carboxymethyl cellulose beads for controlled release under simulated gastrointestinal conditions

AbstractNetwork characteristics of sodium alginate and carboxymethyl cellulose, in relation to the controlled release of bovine serum albumin under simulated gastrointestinal conditions, have been examined. Small‐deformation dynamic oscillation in‐shear, compression testing and optical microscopy were employed to monitor the structural characteristics of polysaccharide beads as excipients for protein entrapment. Work focused on gastrointestinal functionality and controlled release utilising variable acidity and counterion addition in preparations. Beads were found to shrink in gastric and swell in intestinal conditions, thus emphasising the disparate effect of experimental conditions. Changes in mechanical properties reflected alterations in gel microstructure, with beads becoming relatively strong in the gastric environment. In contrast, networks were weakened in the intestinal environment resulting in bead disintegration towards the end of digestion time. This type of structural behaviour allows the controlled delivery of the protein, as a model bioactive, in a particular part of the gastrointestinal tract.

Removal of Disperse Red 60 dye from aqueous solution using free and composite fungal biomass of Lentinus concinnus.

Lentinus concinnus biomass was immobilized to carboxyl derivative of cellulose, carboxymethyl cellulose (CMC), in the presence of FeCl3 (0.1 mol L−1) via ionic cross-linking. The beads containing immobilized fungal biomass were incubated at 30 °C for three days to permit growth of the fungus. The free and immobilized fungal biomass were tested for adsorption of Disperse Red 60 (DR-60) from aqueous solution using bare CMC beads as a control system. The maximum adsorption of DR-60 on the free and immobilized fungal biomass was observed at pH 6.0. The adsorption of DR-60 by the free, and immobilized fungal biomass increased as the initial concentration of DR-60 in the medium increased up to 100 mg/L. The maximum adsorption capacity of the CMC beads, the free and immobilized fungal biomass (i.e. composite beads) were found to be 43.4, 65.7, and 92.6 mg g−1 dry sorbents, respectively. The equilibrium of the adsorption system was well described by Langmuir and Temkin isotherm models. Adsorption equilibrium was established in about 1.0 h. The adsorption of DR-60 on the fungal preparations followed pseudo-second-order kinetic model. It was observed that the immobilized fungal biomass has a high potential for the removal of DR-60 as a model dye from aqueous solution.

Immobilized Kluyveromyces marxianus cells in carboxymethyl cellulose for production of ethanol from cheese whey: experimental and kinetic studies.

Cheese whey fermentation to ethanol using immobilized Kluyveromyces marxianus cells was investigated in batch and continuous operation. In batch fermentation, the yeast cells were immobilized in carboxymethyl cellulose (CMC) polymer and also synthesized graft copolymer of CMC with N-vinyl-2-pyrrolidone, denoted as CMC-g-PVP, and the efficiency of the two developed cell entrapped beads for lactose fermentation to ethanol was examined. The yeast cells immobilized in CMC-g-PVP performed slightly better than CMC with ethanol production yields of 0.52 and 0.49g ethanol/g lactose, respectively. The effect of supplementation of cheese whey with lactose (42, 70, 100 and 150g/l) on fermentative performance of K. marxianus immobilized in CMC beads was considered and the results were used for kinetic studies. The first order reaction model was suitable to describe the kinetics of substrate utilization and modified Gompertz model was quite successful to predict the ethanol production. For continuous ethanol fermentation, a packed-bed immobilized cell reactor (ICR) was operated at several hydraulic retention times; HRTs of 11, 15 and 30h. At the HRT of 30h, the ethanol production yield using CMC beads was 0.49g/g which implies that 91.07% of the theoretical yield was achieved.

Polyaniline coated magnetic carboxymethylcellulose beads for selective removal of uranium ions from aqueous solution

Magnetic carboxymethylcellulose (CMC) beads were prepared via ionic cross-linking. Then CMC beads were coated with polyaniline (PANI). The results of FTIR, SEM, DTA and N2 adsorption–desorption demonstrated that aniline was successfully grafted onto the surface of mCMC beads. The potential use of the prepared adsorbent was used for removal of U(VI) ions. The determined maximum adsorption capacities of the mCMC and mCMC-g-PANI beads for U(VI) ions were 129.4 and 386.5 mg/g dry weight at pH 4.5, respectively. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) were evaluated. The adsorbent systems were regenerated using 0.1 M HCl.

Adsorption of Hexavalent Chromium Ion from Aqueous Solution by Sodium Alginate and Carboxymethyl Cellulose Beads: Kinetics and Isotherm Studies

Adsorption of Hexavalent Chromium Ion from Aqueous Solution by Sodium Alginate and Carboxymethyl Cellulose Beads: Kinetics and Isotherm Studies

Biosorption of uranium(VI) by free and entrapped Chlamydomonas reinhardtii: kinetic, equilibrium and thermodynamic studies

Biosorption of uranium from aqueous solution onto the free and entrapped algae, “Chlamydomonas reinhardtii” in carboxymethyl cellulose (CMC) beads was investigated in a batch system using bare CMC beads as a control system. CMC can be a potential natural biosorbent for radionuclide removal as it contains carboxyl groups. However, limited information is available with the biosorption of uranium by CMC, when adsorption isotherm, kinetics and thermodynamics parameters are concerned. The biosorbent preparations were characterized by swelling tests, FTIR, and surface area studies. The effects of pH, temperature, ionic strength, biosorbent dosage, and initial uranium concentrations on uranium biosorption were investigated. Freely suspended algae exhibited the highest uranium uptake capacity with an initial uranium ion concentration of 1,000 mg/L at pH of 4.5 and at 25 °C. The removal of U(VI) ion from the aqueous solution with all the tested biosorbents increased as the initial concentration of U(VI) ion increased in the medium. Maximum biosorption capacities for free algal cells, entrapped algal cells, and bare CMC beads were found to be 337.2, 196.8, and 153.4 mg U(VI)/g, respectively. The kinetic studies indicated that the biosorption of U(VI) ion was well described by the pseudo-second order kinetic model. The variations in enthalpy and entropy for the tested biosorbent were calculated from the experimental data. The algal cells entrapped beads were regenerated using 10 mM HNO3, with up to 94 % recovery. Algal cells entrapped CMC beads is a low cost and a potential composite biosorbent with high biosorption capacity for the removal of U(VI) from waters.

Preparation and characterization of crosslinked alginate–CMC beads for controlled release of nitrate salt

Carboxymethyl cellulose (CMC)/sodium alginate (SA) hydrogel beads were successfully prepared by Ca2+ ions crosslinking followed by gamma irradiation. The factors affecting beads formation are the composition of SA in the blend and concentration of calcium chloride as a crosslinking agent. The results indicated that the addition of CMC to SA increases the swelling (%) upto (1:3) (CMC:SA) ratio. The effect of different irradiation doses (2.5, 5, and 10 kGy) on swelling (%) was studied. At low doses, swelling (%) decreases upto 5 kGy then starts to increase at 10 kGy. The degree of the swelling (%) and release (%) of ammonium nitrate salt from beads were investigated under different pH (1.2, 5 and 7). The beads were characterized by FTIR, SEM and TGA to investigate molecular structure, morphology and thermal stability of beads.

Ionically crosslinked alginate–carboxymethyl cellulose beads for the delivery of protein therapeutics

We developed Fe3+-crosslinked alginate–carboxymethyl cellulose (AC) beads in various volume ratios by dropping an AC solution into a ferric chloride solution to form protein therapeutic carrier beads. Scanning electron microscopy revealed that the roughness and pore size of the crosslinked beads increased with the volume ratio of the carboxymethyl cellulose. Fourier transform-infrared analysis revealed the formation of a three-dimensional bonding structure between the anionic polymeric chains of AC and the Fe3+ ions. The degree of swelling and the release profile of albumin from the beads were investigated under simulated gastrointestinal conditions (pH 1.2, 4.5, and 7.4). The Fe3+-crosslinked AC beads displayed different degrees of swelling and albumin release for the various AC volume ratios and under various pH conditions. An in vitro release test was used to monitor the controlled release of albumin from the AC beads under simulated gastrointestinal conditions over 24h. The Fe3+-crosslinked AC beads protected and controlled the release of protein, demonstrating that such beads present a promising protein therapeutic carrier for the oral delivery.