Chlorella filled poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blend bio-composites compatible with additive manufacturing processes: Fluorescent and anti-counterfeiting QR codes applications.

Anti-counterfeiting in 3D printing has gained significant attention, however, current approaches often fall short of fully capitalizing on the inherent advantages of personalized manufacturing with this technology. Herein, we propose an embedded anti-counterfeiting scheme for additive manufacturing, accompanied by a novel fluorescent encrypted quick response (QR) method. This approach involves the development of a 3D printing filament utilizing poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) bio-composites as the primary filament matrix, with varying quantities of Chlorella powder incorporated. The resulting filament has a good thermal stability near 200 °C and exhibits a distinctive red fluorescence under ultraviolet light, with the emission peak at 677 nm when excited by 415 nm blue light. Fluorescence imaging analysis confirms that the red fluorescence in 3D printed devices containing Chlorella is a result of the chlorophyll and its derivatives fluorescence effect. The fluorescent encrypted QR codes are inconspicuous in daylight but become easily discernible under ultraviolet light. In the cases of recognizable QR codes, the ∆Eab* values all exceed 35, and the LC/LB values deviate significantly from 1. This research delves into the fluorescence characteristics of Chlorella and highlights its applicability in 3D printing, specifically within the realm of product anti-counterfeiting, presenting a groundbreaking approach.

Application of 3D printing technology for green synthesis of Fe2O3 using ABS/TPU/chlorella skeletons for methyl orange removal.

Photocatalysis is widely acknowledged as an efficient and environmentally friendly method for treating dye-contaminated wastewater. However, the utilization of powdered photocatalysts presents significant challenges, including issues related to recyclability and the potential for secondary pollution. Herein, a novel technique based on 3D printing for the synthesizing of iron oxide (Fe2O3) involving chlorella was presented. Initially, chlorella powders were immobilized within acrylonitrile butadiene styrene (ABS) and thermoplastic polyurethane (TPU) substrate plastics using melt extrusion technology. Subsequently, these composite materials were transformed into ABS/TPU/chlorella skeletons (ATCh40), through fused deposition molding (FDM) technology. The integration of Fe2O3 onto the ATCh40 (ATCh40-Fe2O3) skeletons was accomplished by subjecting them to controlled heating in an oil bath. A comprehensive characterization of the synthesized materials confirms the successful growth of Fe2O3 on the surface of 3D skeletons. This strategy effectively addresses the immobilization challenges associated with powdered photocatalysts. In photocatalytic degradation experiments targeting methyl orange (MO), the ATCh40-Fe2O3 skeletons exhibited a remarkable MO removal rate of 91% within 240 min. Under conditions where the pH of MO solution was maintained at 3, and the ATCh40-Fe2O3 skeletons were subjected to a heat treatment in a 150 °C blast drying oven for 2 hours, the degradation rate of MO remained substantial, achieving 90% removal after 6 cycles. In contrast, when the same synthetic procedure was applied to ABS/TPU (AT) skeletons, the resulting product was identified as α-FeOOH. The MO removal rate by the AT-α-FeOOH skeletons was considerably lower, reaching only 49% after 240 min. This research provided a practical approach for the construction of photocatalytic devices through the use of 3D printing technology.

3D printed cylindrical capsules as a Chlorella pyrenoidosa immobilization device for removal of lead ions contamination.

Immobilization is considered as a promising strategy toward the practical applications of powdered adsorbent. Herein, three dimensional (3D) printing cylindrical capsules with cross-linked PVA hydrogels membrane in encapsulate Chlorella pyrenoidosa (Cp) were utilized for removal of lead ions. The chemical compositions, hydrogels performance and morphologies of the membranes were determined by Fourier transformed infrared spectroscopy (FTIR), cross-linking degree, swelling degree, membrane flux and scanning electron microscopy (SEM). It is found that PVA cross-linking structure is successfully synthesized on the surface of capsule body and cap due to the presence of PVA in the filament. The lead ions adsorption capacity related to initial concentration of 50 mg/L in 48 h is reached 75.61%, revealing a good removal ability. The self-floating 3D printed capsules device also shows an excellent recovering property. After 7 runs of adsorption experiment, the lead ions adsorption ratio remains 78.56%, which will bring a broad prospect in wastewater treatment, chemical slow release along with sample preparation and separation.

Efficient Removal of Organic Contaminants from Aqueous Solution by Highly Compressible Reusable Three-Dimensional Printing Sponges.

Adsorption is considered to be one of the most effective and economically viable technologies for removing contaminants from the environment. However, the disadvantages of its high-cost complicated process and difficulty in efficient recycling limit its practical application. Herein, a thermoplastic elastomer-polyvinyl alcohol composite (LAY-FOMM 60) sponge three-dimensional structure (3D printing sponge) was fabricated by the fused filament fabrication combined with water erosion technique. The size and shape of the resultant sponge were tailored, and the batch of adsorption/desorption experiments of Rhodamine B (RhB) onto the sponge was performed. The results show that the adsorption of RhB on the 3D printing sponge was mainly via physical adsorption, and pseudo-second-order and Langmuir models exhibited good correlation with the adsorption kinetic and isotherm data, respectively. Thermodynamic parameters suggest that the adsorption is an endothermic and spontaneous process. It is worth to note that the adsorption/desorption efficiency can be raised by compression. This results in high efficiency and low cost for adsorption/desorption process and benefit for regeneration of the adsorbent. The adsorption capacity was maintained over 85% of the initial capacity after being used for five cycles. The approach provides a simple strategy for manufacturing customizable porous adsorbent materials that meet various water treatment requirements.

In Situ Growth of Ca2+-Based Metal-Organic Framework on CaSiO3/ABS/TPU 3D Skeleton for Methylene Blue Removal.

The work reports a novel strategy for combining polymers and metal-organic frameworks (MOFs) into composites for adsorption applications. Calcium silicate (CaSiO3) was introduced into acrylonitrile butadiene styrene/thermoplastic polyurethane (ABS/TPU) alloy, and the CaSiO3/ABS/TPU skeleton was fabricated by 3D printing technology. The Ca-MOF was directly loaded on the surface of acetone-etched 3D skeleton by in-situ growth method. The obtained 3D skeleton was characterized and the performance of methylene blue (MB) adsorption was determined. It is clear that Ca-MOF is successfully loaded on the surface of 3D skeleton due to the presence of CaSiO3. The MB adsorption ratios of the solutions with initial concentrations of 50, 100 and 200 mg/L at the equilibrium time (5 h) are 88%, 88% and 80%, respectively, revealing good MB adsorption performance of the 3D skeleton. The MB adsorption ratio remains 70% at six runs of adsorption-desorption experiment, indicating the excellent recovering property of the skeleton. The results show that the prepared CaSiO3/ABS/TPU 3D skeleton is a candidate adsorbent for printing and dyeing effluent treatment.

A ZnO@ABS/TPU/CaSiO3 3D skeleton and its adsorption/photocatalysis properties for dye contaminant removal.

Both adsorption and photocatalysis are considered to be effective methods for removing organic contaminants from dye wastewater. In this study, the construction of 3D skeletons based on the nanoparticles ZnO and ABS/TPU/calcium silicate (CaSiO3) (shortened as ATC) were fabricated via fused deposition molding (FDM) technology. Characterization by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) depicted that ZnO nanospheres had been successfully grown on the 3D skeleton surface with an enlarged specific surface area. As the results of the RhB adsorption and photocatalytic degradation experiments showed, the removal ratio of RhB onto the ZnO-ATC skeleton was as high as 97.94% and the synergistic effect of adsorption and photocatalysis greatly shortened the RhB degradation time under ultraviolet light irradiation. The nanocomposites synthesized in this study showed a significant removal ability for organic pollutants, and could effectively overcome the limitation of the secondary removal of photocatalysts.

An Sn doped 1T-2H MoS2 few-layer structure embedded in N/P co-doped bio-carbon for high performance sodium-ion batteries.

A facile method for fabricating Sn doped 1T-2H MoS2 embedded in N/P co-doped bio-carbon is developed using natural chlorella as an adsorbent and a nanoreactor. When used as an anode for sodium-ion batteries, it delivers an excellent rate performance (167 mA h g-1 at 15 A g-1), high capacity (533 mA h g-1 after 50 cycles at 0.1 A g-1), and superior long-term cycling stability (320 mA h g-1 after 500 cycles at 1 A g-1) which are attributed to the synergistic effects of few-layer 1T-2H MoS2 moderate Sn doping and the N/P co-doped bio-carbon.

A cyano-bridged Cu(i)-based organic framework coupled with the C-C bond cleavage of acetonitrile for selective and sensitive sensing of Fe3+ ions.

A cyano-bridged Cu(i) organic framework based on [Cu6(CN)6]n was synthesized, in which cyano anions were generated in situ from the C-C bond cleavage of acetonitrile. The as-synthesized compound displays orange-red luminescence and is further proven to be a promising Fe3+ luminescent sensor with high selectivity and sensitivity.

Apoptosis of breast cancer cells induced by hypocrellin B under light-emitting diode irradiation.

OBJECTIVES: Breast cancer is a common disease which threatens the life of women. To explore an alternative modality for combating breast cancer, a light-emitting diode (LED) that activates hypocrellin B was used in the present study to investigate apoptosis induction in breast cancer MDA-MB-231 cells. MATERIALS AND METHODS: Photocytotoxicity was investigated 24h after photodynamic treatment of hypocrellin B using MTT reduction assay and light microscopy. Apoptosis was observed 6h after photodynamic treatment using flow cytometry with Annexin V/PI staining as well as fluorescent microscopy with Hoechst33258 staining. The ultrastructure of the treated cells was observed using transmission electron microscopy (TEM). RESULTS: Hypocrellin B-induced photocytotoxicity in MDA-MB-231 cells exhibited a dose-dependent manner. The amount of MDA-MB-231 cells attached to the bottom of well decreased significantly after photodynamic treatment of hypocrellin B. Flow cytometry showed that the early and late apoptotic rate of MDA-MB-231 cells increased remarkably up to 17.46% and 32.80%, respectively, after treatment of LED-activated hypocrellin B. In addition, nuclear condensation, fragmentation and chromatin margination, and topical apoptotic body in the treated cells were observed by nuclear staining and TEM. CONCLUSION: Photodynamic action of hypocrellin B irradiated by light-emitting diodes could significantly kill breast cancer cells and induce apoptotic cell death, which suggests LED-activated hypocrellin B is a promising strategy for combating breast cancer.

Ultrasound-induced cell death of nasopharyngeal carcinoma cells in the presence of curcumin.

OBJECTIVES: Curcumin, a natural pigment from a traditional Chinese herb, has been attracting extensive attention. The present study aims to investigate cell death of nasopharyngeal carcinoma (NPC) cells induced by ultrasound sonication in the presence of curcumin in vitro. METHODS: The NPC cell line CNE2 was chosen as a tumor model, and curcumin concentration was kept constant at 10 µM while the cells were subjected to ultrasound exposure for 8 s at an intensity of 0.46 W/cm(2). Cell death was evaluated using flow cytometry with annexinV-FITC and propidium iodine staining, and nuclear staining with Hoechst 33258. Mitochondrial membrane potential and intracellular reactive oxygen species (ROS) were analyzed using flow cytometry with rhodamine 123 and dichlorodihydrofluorecein diacetate staining. RESULTS: Flow cytometry showed that the combination of ultrasound and curcumin significantly increased the necrotic or late apoptotic rate by up to 31.37% compared with the controls. Nuclear condensation was observed in the nuclear staining, and collapse of ΔΨm and ROS increase were found in the CNE2 cells after the treatment with curcumin and ultrasound. CONCLUSIONS: The findings demonstrate that the presence of curcumin significantly enhances the ultrasound-induced cell death and ROS level, and induces the collapse of ΔΨm, suggesting that ultrasound sonication can increase the cell death of NPC cells in the presence of curcumin and that the treatment using curcumin and ultrasound together is a potential therapeutic modality in the management of malignant tumors.

Hypocrellin B-encapsulated nanoparticle-mediated rev-caspase-3 gene transfection and photodynamic therapy on tumor cells.

Gene therapy and photodynamic therapy are two kinds of important therapeutic strategies for treating malignant tumors. In order to explore the combined effects of gene therapy and PDT on tumor cells, rev-caspase-3 gene was transfected into the tumor model CNE2 cells using hypocrellin B-encapsulated nanoparticle (nano-HB) as a carrier. The transfected CNE2 cells were then irradiated by light from a LED source and the survival rate was investigated 18 h after PDT. Apoptosis was analyzed by a flow cytometer with propidium iodine (PI) staining and the active caspase-3 expression was measured using flow cytometry with phycoerythrin (PE)-conjugated anti-active caspase-3 antibody. The result from the flow cytometer showed that the level of the activated caspase-3 significantly increased up to 63.10% in the transfected CNE2 cells. The survival rate 18 h after gene transfection alone and nano-HB-mediated PDT was 96.6±2.07%, 72.6±4.15%, respectively. However, the survival rate of the transfected CNE2 cells 18 h after LED exposure significantly decreased to 50.6±5.98% under the light energy of 4 J/cm(2). Apoptotic rate 18 h after the combination of gene transfection and PDT increased up to 24.65%. Our findings demonstrated that nano-HB could significantly enhance the transfection efficiency of rev-caspase-3 gene in the CNE2 cells. LED irradiation could effectively kill the treated CNE2 cells and induce apoptosis, suggesting hypocrellin B-encapsulated nanoparticle as an efficient gene carrier and a novel photosensitizer. The combination of gene therapy and PDT using nanoparticle as a mediator can be developed for treating nasopharyngeal carcinoma.

Ultrasound induces cellular destruction of nasopharyngeal carcinoma cells in the presence of curcumin.

OBJECTIVES: Curcumin, a natural pigment from the traditional Chinese herb, has shown promise as an efficient enhancer of ultrasound. The present study aims to investigate ultrasound-induced cellular destruction of nasopharyngeal carcinoma cells in the presence of curcumin in vitro. METHODS: Nasopharyngeal carcinoma cell line CNE2 cells were incubated by 10µm curcumin and then were treated by ultrasound for 8s at the intensity of 0.46W/cm(2). Cytotoxicity was evaluated using MTT assay and light microscopy. Mitochondrial damage was analyzed using a confocal laser scanning microcopy with Rhodamine 123 and ultrastructural changes were observed using a transmission electron microscopy (TEM). RESULTS: MTT assay showed that cytotoxicity induced by ultrasound treatment alone and curcumin treatment alone was 18.16±2.37% and 24.93±8.30%, respectively. The cytotoxicity induced by the combined treatment of ultrasound and curcumin significantly increased up to 86.67±7.78%. TEM showed that microvillin disappearance, membrane blebbing, chromatin condensation, swollen mitochondria, and mitochondrial myelin-like body were observed in the cells treated by ultrasound and curcumin together. The significant collapse of mitochondrial membrane potential (MMP) was markedly observed in the CNE2 cells after the combined treatment of curcumin and ultrasound. CONCLUSIONS: Our findings demonstrated that ultrasound sonication in the presence of curcumin significantly killed the CNE2 cells and induced ultrastructural damage and the dysfunction of mitochondria, suggesting that ultrasound treatment remarkably induced cellular destruction of nasopharyngeal carcinoma cells in the presence of curcumin.

Apoptosis of ovarian cancer cells induced by methylene blue-mediated sonodynamic action.

OBJECTIVE: The present study aims to investigate apoptosis of ovarian cancer cells induced by methylene blue (MB)-mediated sonodynamic therapy (SDT). METHODS: The MB concentration was kept constant at 100µM and ovarian cancer HO-8910 cells were exposed to ultrasound therapy for 5s with an intensity of 0.46W/cm(2). The cytotoxicity was investigated 24h after MB-mediated sonodynamic action. Apoptosis was analyzed using a flow cytometer with Annexin V-FITC and propidium iodine (PI) staining as well as fluorescence microscopy with Hoechst 33258 staining. Intracellular reactive oxygen species (ROS) level was measured by flow cytometer with 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA) staining. RESULTS: The cytotoxicity of MB-mediated SDT on HO-8910 cells after MB-mediated SDT was significantly higher than those of other treatments including ultrasound alone, MB alone and sham treatment. Flow cytometric analysis showed a significant increase in the early and late apoptotic cell populations by MB-mediated SDT of HO-8910 cells. Nuclear condensation and increased ROS levels were also found in HO-8910 cells treated by MB-mediated SDT. CONCLUSIONS: Our findings demonstrated that MB-mediated sonodynamic action significantly induced apoptosis of HO-8910 cells and an increase in intracellular ROS level. This indicates that apoptosis is an important mechanism of cell death induced by MB-mediated SDT. Thus, MB-mediated SDT might be a potential therapeutic strategy for combating ovarian cancer.

Sonodynamic action of pyropheophorbide-a methyl ester induces mitochondrial damage in liver cancer cells.

Sonodynamic therapy with pyropheophorbide-a methyl ester (MPPa) presents a promising aspect in treating liver cancer. The present study aims to investigate the mitochondrial damage of liver cancer cells induced by MPPa-mediated sonodynamic action. Mouse hepatoma cell line H(22) cells were incubated with MPPa (2 µM) for 20 h and then exposed to ultrasound with an intensity of 0.97 W/cm(2) for 8 s. Cytotoxicity was investigated 24h after sonodynamic action using MTT assay and light microscopy. Mitochondrial membrane potential (ΔΨm) was analyzed using flow cytometry with rhodamine 123 staining and ultrastructural changes were observed using transmission electron microscopy (TEM). The cytotoxicity of MPPa-mediated SDT on H(22) cell line was 73.00±3.42%, greater than ultrasound treatment alone (28.12±5.19%) significantly while MPPa treatment alone had no significant effect on H(22) cells. Moreover, after MPPa-mediated SDT cancer cells showed swollen mitochondria under TEM and a significant collapse of mitochondrial membrane potential. Our findings demonstrated that MPPa-mediated SDT could remarkably induce cell death of H(22) cells, and highlighted that mitochondrial damage might be an important cause of cell death induced by MPPa-mediated SDT.

Sonodynamic action of pyropheophorbide-a methyl ester in liver cancer cells.

OBJECTIVE: This study aimed to investigate the sonodynamic action of pyropheophorbide-a methyl ester (MPPa) in liver cancer cells to explore a novel therapeutic modality. METHODS: H22 cells were chosen as model cells to investigate the sonodynamic action of MPPa on liver cancer. The MPPa concentration was kept constant at 2 micromol/L, and the cells were subjected to ultrasound exposure at an intensity of 0.97 W/cm(2). Cytotoxicity was investigated 24 hours after ultrasound exposure. Apoptosis was evaluated using flow cytometry with annexin V-fluorescein isothiocyanate and propidium iodine staining and nuclear staining with Hoechst 33258. Reactive oxygen species (ROS) were analyzed using flow cytometry with 2,7-dichlorodihydrofluorescein diacetate staining. RESULTS: No significant dark cytotoxicity of MPPa was shown in the H22 cells at the concentration of 2 micromol/L. The cell death rate induced by ultrasound treatment was significantly higher in the presence of MPPa than in the absence of it (P < .05). Flow cytometry showed that the sonodynamic action of MPPa significantly increased the early and late apoptotic rates of the H22 cells. Nuclear condensation and an ROS increase were found after sonodynamic treatment. CONCLUSIONS: Our findings showed that MPPa-mediated sonodynamic action significantly enhanced death of H22 cells and the ROS level, suggesting that MPPa is a novel sonosensitizer and the sonodynamic action of MPPa might be a potential therapeutic modality in the management of liver cancer.

5-Aminolaevulinic acid enhances ultrasound-induced mitochondrial damage in K562 cells.

BACKGROUND: Ultrasound therapy is a new modality in the control of malignant cancers. The aim of the present study was to investigate the effect of 5-aminolaevulinic acid on the ultrasonic killing action in the cancer cells. MATERIALS/METHODS: The K562 cells as a cancer cell model were subjected to investigate the effect of 5-aminolaevulinic acid (5-ALA) on the ultrasonic killing action, in which the 5-ALA concentration was 2mM and the ultrasound exposure was 15 s at the intensity of 0.46 W/cm(2) and the frequency of 1.7MHz. Cytotoxicity was investigated 24h after ultrasound exposure using the trypan blue exclusion test. Ultrastructural cell morphology and mitochondrial changes were observed using transmission electron microscopy (TEM). Mitochondrial membrane potential (DeltaPsim) was evaluated using Rhodamine 123 assay. RESULTS: The death rates of the K562 cells in the controls including sham radiation and 5-ALA treatment alone were 1.81+/-0.13%, 1.27+/-0.20%, respectively. Those in ultrasound radiation alone and 5-ALA-ultrasound treatment were 12.61+/-2.63%, 46.87+/-4.09%, respectively. There were significant differences between 5-ALA-ultrasound treatment, ultrasound radiation alone and the controls (P<0.05). TEM showed that the mitochondria expanding and some vacuoles were found in the ultrasound-treated cells. After the treatment of ultrasound and 5-ALA together some cells presented typical characteristics of apoptotic cells, such as nuclear condensation and crescent formation. Mitochondria of the cells were damaged more seriously than those treated by ultrasound alone, there were obvious swollen mitochondria and mitochondria in which cristae were almost perfectly disappeared, and more vacuolar mitochondria were founded. Mitochondrial membrane potential (DeltaPsim) was more significantly collapsed when the K562 cells were exposed to 2mM 5-ALA for 4h and then 0.46 W/cm(2) irradiation of ultrasound than ultrasound radiation alone. CONCLUSION: 5-ALA pretreatment significantly enhanced the cytotoxicity of ultrasound radiation in K562 cells. The damage of mitochondria structure and function might be an important cause of cell death in K562 cells induced by the treatment of ultrasound radiation and 5-ALA together.

Mitochondrial damage in nasopharyngeal carcinoma cells induced by ultrasound radiation in the presence of hypocrellin B.

OBJECTIVE: The mitochondrion is an important target of ultrasound-induced cell death. This study aimed to investigate the mitochondrial damage in nasopharyngeal carcinoma (NPC) cells induced by ultrasound radiation in the presence of hypocrellin B (HB). METHODS: The NPC cell line CNE2 was used to investigate the effect of HB on ultrasonic action with an HB concentration of 2.5 mumol/L and ultrasound exposure for 15 seconds at an intensity of 0.65 W/cm(2). Cytotoxicity was investigated 24 hours after ultrasound exposure. Mitochondrial structure changes were observed by transmission electron microscopy. The mitochondrial membrane potential was evaluated by confocal laser-scanning microscopy with rhodamine 123 staining. RESULTS: The mean death rates of the CNE2 cells +/- SD were 25.14% +/- 1.50% after ultrasound radiation alone and 76.72% +/- 1.13% after ultrasound radiation in the presence of HB. Transmission electron microscopy showed that slightly enlarging mitochondria were found in the ultrasound-treated cells. After treatment with ultrasound and HB together, some cells had seriously damaged mitochondria, namely, obvious swollen mitochondria and mitochondria in which cristae had almost completely disappeared. The mitochondrial membrane potential was more significantly collapsed when the CNE2 cells were exposed to HB for 5 hours and then ultrasound at 0.65 mW/cm(2) than with ultrasound radiation alone (P < .05). CONCLUSIONS: Hypocrellin B significantly enhanced the cytotoxicity of ultrasound radiation in the CNE2 cells. The damage to the mitochondrial structure and function might be an important cause of death in the CNE2 cells induced by treatment with ultrasound radiation and HB together.