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MINISTRY OF EDUCATION AND TRAINING VIETNAM ACADEMY OF SCIENCE AND TECHNOLOGY GRADUATE UNIVERSITY SCIENCE AND TECHNOLOGY PHAM THI LIEN RESEARCH ON THE SYNTHESIS, PROPERTIES OF GdPO4:Tb3+ AND Gd2O3:Eu3+ NANOMATERIALS ORIENTED FOR BIOMEDICAL APPLICATIONS Major: Code: Optical, optoelectronic and photonic materials 62 44 01 27 SUMMARY OF DOCTORAL THESIS IN MATERIAL SCIENCE Ha Noi - 2020 The thesis has been completed at: Graduate University of Science and Technology Vietnam Academy of Science and Technology Science supervisors: Dr Nguyen Thanh Huong Prof Dr Le Quoc Minh Reviewer 1: Reviewer 2: Reviewer 3: The thesis was defended at Evaluation Council held at Graduate University of Science and Technology - Vietnam Academy of Science and Technology on , 2020 Thesis can be further referred at: - The Library of Graduate University of Science and Technology - National Library of Vietnam INTRODUCTION 1 The necessity of the thesis Luminescent nano-materials containing Rare Earth (RE-NP) have received much attention in recent years Notably, the materials GdPO4: Tb3+ and Gd2O3:Eu3+ become the critical research tool for the wideranging biomedical applications in the diagnosis and treatment of human disease Magnetic resonance imaging (MRI) examination and especially live-cell fluorescence microscopy are widely utilized in hospitals and clinics In Vietnam, many research groups have focused on the synthesis of luminescent materials as photonic biomarkers, creating the analytical tool for assessing the quality of biologicals, foods and vaccines However, most of the biomedical applications are primarily based on a single functional tool, e.g either luminescent material as a biomarker or magnetic material as a hyperthermia agent for enhancing the contrast of image Therefore, it is urgent to develop a multifunctional tool, especially simultaneously possessing fluorescence and magnetic properties in a single system to improve the efficiency of diagnostic and treatment processes According to the latest reports in the field of rare-earth luminescent materials, we decide to chose Terbium (Tb3+) and Europium (Eu3+)-activated Gadolinium (Gd3+) compounds as research objects To our knowledge, these kinds of materials can meet the requirement of multifunctional tool because Gd3+ ions simultaneously exhibit fluorescence and magnetic properties, thus making them wellsuited to serve as nanoprobes in the diagnostic and treatment of human disease To meet the requirement for diverse applications, the aim of our thesis is to synthesize the luminescent nanomaterials with good repeatability, well-controlled morphology, high solubility in water and highly efficient luminescence My doctoral thesis is entitled: “Research on the synthesis, properties of GdPO4:Tb3+ and Gd2O3:Eu3+ nanomaterials oriented for biomedical applications” Research objectives of the thesis - Successful synthesis of GdPO4:Tb3+ nanorods and Gd2O3:Eu3+ nanospheres - Coating GdPO4:Tb3+ nanorods and Gd2O3:Eu3+ nanospheres with a silica shell, functionalizing with NH2 functional group, conjugating with anti-venom and anti-CEA antibodies for further biomedical applications - Initial experimental application of the nanocomplexs based GdPO4:Tb3+ nanorods and Gd2O3:Eu3+ nanospheres using immunofluorescence analysis method for labelling cells and detecting the antigen of cobra venom and CEA antigen of colorectal cancer cells Research contents of the thesis In the following chapter 1, we present a brief overview of rareearth doped luminescent material; GdPO4:Tb3+/Gd2O3:Eu3+ based luminescent materials and objects for biomedical application Next, we describe experimental methods and material characterizations used in the thesis We then present the material characterization results of GdPO4:Tb3+ nanorods and Gd2O3:Eu3+ nanospheres We also examine and determine the magnetic hyperthermia property of GdPO4 and GdPO4:Tb3+ nanorods These nanomaterials were then conjugated with anti-venom and anti-CEA antibodies for further biomedical applications Finally, we demonstrate the great potential of these multifunctional nanocomplexs for detecting cobra venom antigen and the CEA antigen of colorectal cancer cells We conclude in the last chapter In this thesis, the luminescent nanomaterials have been synthesized by using hydrothermal process and multistep synthesis approach Surface morphology and structural characteristics of assynthesized nanomaterials were examined with field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX) The optical properties of as-prepared samples were measured with the spectrometers (iHR550, Acton SP2300i and Fluorolof FL32-2, Horiba (USA)) The magnetic properties were investigated with magnetic field-dependent magnetization measurement using vibrating sample magnetometer (VSM) system The measurement of magnetic induction heating is performed with the commercial RDO-HFI (IMS) The biological experiments were performed at the Laboratory of Molecular Biology (Vietnam Military Medical Academy) Novel attribution of the thesis: - Successful synthesis of GdPO4:Tb3+ nanorods with a length of 300– 500 nm and width of 10–30 nm through hydrothermal process and Gd2O3:Eu3+ nanosphere with a diameter of 145–155 nm via multistep synthesis approach - Successfully coating GdPO4:Tb3+ nanorods and Gd2O3:Eu3+ nanospheres with a silica shell, functionalizing with NH2 functional group, conjugating with anti-venom antibodies and anti-CEA antibodies to detect the cobra venom antigen and CEA antigen of colorectal cancer cells - The magnetic inducting heater effect of GdPO4 and GdPO4:Tb3+ have been investigated, at 300 Oe, 390 kHz, the temperature reach to 44 - 49 oC in 1500 s The results indicating the synthesized materials are well-suited for application in magnetic hyperthermia therapy The thesis is divided into chapters: Chapter 1: Rare-earthe doped luminescent nanomaterials Chapter 2: Experimental methods Chapter 3: Synthesis of GdPO4:Tb3+ nanorods and the application of GdPO4:Tb3+ nanocomplexs for the detection of cobra venom antigen Chapter 4: Synthesis of Gd2O3:Eu3+ nanospheres and the application of Gd2O3:Eu3+ nanocomplexs for the detection of the CEA antigen of colorectal cancer cells The main results of the thesis were published in scientific papers CHAPTER 1: RARE EARTH ION-BASED LUMINESCENT NANO MATERIALS 1.1 Introduction of luminescent nano materials 1.2 Rare earth ion-based fluorescente materials 1.2.1 Luminescent properties of rare earth compounds 1.2.1.1 Characteristics of Gd3+ ion 1.2.1.2 Characteristics of Tb3+ ion 1.2.1.3 Characteristics of Eu2+ and Eu3+ ions 1.2.2 Allowed electronic transition in RE3+ ion 1.2.3 Energy transfer process (a) (b) Figure Energy level diagram and energy transfer mechanism of Gd3+ ion to Eu3+ ion (a), Gd3+ ion to Tb3+ ion (b) 1.3 Features and applications of Gadolini 1.3.1 Gadolini material 1.3.2 The luminescent host material of Gd2O3 1.3.3 The luminescent host nanomaterial of GdPO4 1.4 Characteristics of cobra venom and CEA antigens 1.4.1 Characteristics of Naja atra cobra venom 1.4.2 Characteristics of CEA colorectal cancer antigen CHAPTER EXPERIMENTAL METHOD 2.1 Chemical methods 2.1.1 Hydrothermal method 2.1.1.1 Introduction of hydrothermal method Characteristics of material can tune by adjusting the following parametrs: pH, temperature, speed of reaction, time of hydrolysis, and crystallographic influence on morphology, magnitude and properties of final products Synthesis process of GdPO4:Tb3+ Figure 2.4: Schematic representation for synthesis process of GdPO4:Tb3+ 2.1.2 Multi-step chemical synthesis method 2.1.2.1 Introduction of a multi-step chemical synthesis method 2.1.2.2 Synthesis process of Gd2O3:Eu3+ Figure 2.5 Experimental diagram for preparation of Gd2O3: Eu3+ 2.1.3 Synthetic method of biomedical nano compounds GdPO4:Tb3+; Gd2O3:Eu3+ 2.1.3.1 Surface treatment method 2.1.3.2 Methods of surface functionalization and conjugation between luminescent nanomaterials and biologically active elements 2.1.3.3 Coating GdPO4: Tb3+ nanorods by Silica 2.1.3.4 Functionalizing GdPO4:Tb3+@Silica nanorods by -NH2 Figure Experimental diagram for wrapping and surface functionalization of GdPO4:Tb3+ nanorods 2.1.3.5 Preparation of GdPO4:Tb3+@Silica-NH2 nano compound with the snake venom antibody (IgG) Figure Diagram of synthesizing nano compound by integrating GdPO4:Tb3+@silica-NH2 with the snake venom antibody (IgG) 2.1.3.6 Coating Gd2O3:Eu3+ by silica 2.1.3.7 Functionalization of Gd2O3:Eu3+ @Silica by -NH2 Figure 2.9 Diagram of wrapping Gd2O3:Eu3+ by Silica and integrating NH2 group 2.1.3.8 Synthesis of Gd2O3:Eu3+@Silica-NH2 nano compound with the CEA antibody Figure 2.10 Schematic illustration for the synthesis of nano compound by integrating Gd2O3:Eu3+@silica-NH2 with the CEA antibody (IgG) 2.2 Methods of material analysis CHAPTER 3: RESEARCHING RESULTS OF GdPO4:Tb3+ AND APPLICATION OF GdPO4:Tb3+ NANO COMPOUND TO DETECT THE VENOM ANTIGEN 3.1 Crystal structure, morphology, optical and magnetic properties of synthesized materials 3.1.1 FESEM analysis 3.1.1.1 FESEM images of GdPO4 3.1.1.2 FESEM images of GdPO4: Tb3+ Figure 3.2 exhibits as-prepared materials have nanorod morphology with the length of 300-500nm and the width of 10-30nm It can be seen the nanorods in the sample with [Tb3+]/[Gd3+] = 7% are rather uniform and not clustered in bundles compared to others 11 Figure PL spectra of GdPO4:Tb3+(1), GdPO4:Tb3+@silica (2), GdPO4:Tb3+@silica –NH2 (3), GdPO4:Tb3+@silica –NH2-IgG (4) 3.1.4 Infrared (IR) spectra Figure 3.9 IR spectra of GdPO4:Tb3+(a), GdPO4:Tb3+@silica (b) GdPO4:Tb3+@silica-NH2 (c) GdPO4:Tb3+@silica-NH2-IgG (d) The absorption bands of C-H (1400 cm-1), O-H of H2O (3500cm-1 and 1600 cm-1) and PO43- (1043, 622 and 545 cm-1) are observed in the IR spectrum of the samples, see figure 3.9 The presence of O-Si-O (1100-900 cm-1) and N-H (2200-2000 cm-1 and 3450 cm-1) bands proves the silica coating and surface functionalization by NH2 group were successful 12 3.1.5 Magnetism of GdPO4 and GdPO4:Tb3+ Figure 3.10 Magnetic curves of GdPO4:Tb3+ with the ratio [Tb3+]/[Gd3+] of 0, 1, 3, 5, 7, 9% Figure 3.11 The magnetic inducting heater effect of GdPO4:Tb3+ with [Tb3+]/[Gd3+]: 0, 1, 3, 5, 7, 9% It can be seen from figure 3.10 that the magnetization of GdPO4 reaches the highest value of 1,7 emu/g which is twice larger than that of Zhang’s work and as much as that of Xu’s work The magnetization of Tb3+ doped samples decrease, nevertheless the lowest value of GdPO4:9%Tb3+ also achieves 0,8 emu/g equivalent to the value of Zhang’s group Therefore, GdPO4:Tb3+ can be used to increase the contrast level of the magnetic resonance image MRI The magnetic inducting heater effect of GdPO4 and GdPO4:Tb3+ have been investigated, at 300 Oe, 390 kHz (figure 3.11), the temperature reach to 44 - 49 oC in 1500 s The results indicating the synthesized materials are well-suited for application in magnetic hyperthermia therapy 3.2 Application of GdPO4:Tb3+ in the detection of Naja atra venom antigen The experiment of detecting the venom antigen of GdPO4:Tb @silica-NH2-IgG nano compound is shown in figure 3.12 3+ 13 Figure 12 Diagrammatic illustration for detection of the venom antigen by Gd2O3:Tb3+@silica-NH2-IgG fluorescent nano compund Attaching simultaneously the snake venom antigen and nano compound on the 6-disc wells Incubating the nano compound integrated the antivenom antibody with the venom antigen After washing, only the nano compound integrated the antibody and antigen of the venom The nano compound emits blue luminescence with excitation wavelength at 405nm 3.2.1 Evaluation of conjugating of nano material – IgG antigen based on FTIR spectra Figure 13 FTIR spectra of IgG antibody samples before and after conjugating luminescent material 14 The line (a) in figure 3.13 indicates the presence of the O-H (3459 cm ), N-H (2078 cm−1), C=O (1639 cm−1 to1442 cm−1) and the bond −1 of N-H in the first amine group of carbonyl (C-N) group The peak at 1389cm-1 in the line (b) is due to the formation of C - N bond by means of the aldehyd group (O = C - H) reaction of GDA bond with NH2 of IgG As a consequence, the combination of luminescent nanorods and anti-venom antibodies were formed 3.2.2 Evaluating the ability of GdPO4:Tb3+@silica-NH2-IgG nano compound in the detection Naja atra venom antigen (a) (b) (c) Figure 14 Image of Naja atra venom antigen under the visible light (a); Naja atra antigen combined with nano material under the visible light (b); Naja atra antigen combined with nano material under the visible light observed under fluorescence microscope of 405nm, the magnification of 40x and eyepiece of 10x (c) The results showed that the wells incubated with nanorods-antibodies provided a green image and nanoparticles distributed uniformly throughout the field green light under a 40x fluorescence microscope (Figure 3.14 (c)) This result shows that these wells have a specific association between the nanorods-antibodies and the Naja atra cobra antigen so that when it was washed, it does not wash away Meanwhile, other emissions were not green due to the absence of a combination of antibody-coated nanoparticles and Naja atra cobra venom antigens so they were washed away during washing Based on 15 these results, it could be concluded that this Naja atra venom detection procedure can shorten the time needed for early diagnosis and improve the efficacy of treatment and thus could facilitate early treatment of snake bite and save lives Thus, with respect to other green-emitting luminescent materials like Yb, Er-codoped NaYF4 or TbPO4·H2Obased nanomaterials, our synthesized immunoglobulin G-conjugated GdPO4·nH2O:Tb3+ nanorods are compatible for detection of antigenantibody reaction CHAPTER 4: RESEARCHING RESULTS OF Gd2O3:Eu3+ AND APPLICATION OF Gd2O3:Eu3+ NANO COMPOUND TO DETECT THE CEA ANTIGEN OF COLORECTAL CANCER CELLS 4.1 The analyses of structure, morphology, optical and magnetic properties of samples 4.1.1 FESEM images • FESEM images of Gd(OH)CO3.H2O:Eu3+ with the different ratio of [Urê]/ [Gd3++ Eu3+] Figure 4.1 FESEM images of Gd(OH)CO3.H2O:Eu3+ with the ratio [Urê]/[Gd3+ + Eu3+] of 20 (a), 25 (b), 30 (c), 35 (d), 40 (e) All samples obtained have nanospherical shape as seen in Figure 4.1 The diameter of such nanospheres increases with the increase of molar ratio [Urê]/ [Gd3+ + Eu3+] Typically, the average diameter of 16 nanospheres is 140, 190, 210, 240 and 270nm corresponding to the molar ratio [Urê]/[Gd3+ + Eu3+] of 20, 25, 30, 35 and 40, respectively With the ratio [Urê]/[Gd3+ + Eu3+] of 25, the nanospheres are generally the most uniform As a consequence, this ratio is used to synthesize Eu3+-doped Gd2O3 with the molar ratio Eu3+/ Gd3+ of 3,5; 5; 6; 7; 7,5 and 8% • FESEM images of Gd(OH)CO3.H2O: Eu3+ dried at 70oC Figure 4.3 FESEM images of Gd(OH)CO3.H2O:Eu3+ dried at 70oC with the ratio [Urê]/[Gd3++Eu3+] of (a); 3,5(b); 5(c); 6(d); 7(e); 7.5(f) and 8%(g) As shown in Figure 4.3, when Eu3+ is not doped, the nanospheres are quite uniform with the diameter of about 157-173nm (Figure 4.3a) When doping Eu3+ with different molar ratios Eu3+/Gd3 + of 3.5; 5; 6; 7; 7.5 and 8%, the nanospheres have the diameter in the range of 100230nm From FESEM images, for Eu3+-doped sample with the concentration of 6%, the nanospheres are rather uniform with the diameter of 185-195 nm compared to others As a result, this sample is selected for next experiments 4.1.2 Thermogravimetric analysis (TGA) From Figure 4.4, one can observe phases including: Phase (25200oC): the weight of sample decreases 5.79% due to the evaporation 17 of water molecules; Phase (200-380oC): the 8.13 wt % loss is observed because of the decomposition of OH group Phase 3: the decomposition of cacbonate group in the range of 380-550oC results in 15.21wt% loss Phase 4: a further 28.49 wt% loss between 550 and 1000oC is caused by the disintegration of cacbonate group In all phases, there are strong points of heat absorption at 170, 319, 427 and 609 oC These can be considered as the phase transition points, yielding to can be selected suitable processing temperature to obtain the material with a stable phase structure Therefore, we choose the sample processing temperature of 650 oC, at this temperature the product obtained will be Gd2O3:Eu3+ Figure 4 TG-DTG curves of the as-prepared Gd(OH)CO3.H2O:Eu3+ Figure 4.5 shows the diameter of Gd2O3 nanospheres (a) after annealing at 650oC with the diameter of about 104-130nm The diameter of nanospheres in the sample containing 3.5% Eu3+ (b), 5% Eu3+ (c), 6% Eu3+ (d), 7% Eu 3+ (e), 7.5% Eu3+ (f ) and 8% Eu 3+ (g) is about 105-143nm, 117-130nm, 145 -155nm, 136-150nm, 99-130nm and 176-200nm, respectively 18 Figure 4.5 FESEM vật liệu Gd2O3:Eu3+ ủ nhiệt độ 650oC với tỷ lệ [Eu3+]/[Gd3+] (a); 3,5(b); 5(c); 6(d); 7(e); 7.5(f);8%(g) 4.1.3 TEM images of Gd2O3: 6%Eu3+ Figure 4.6 TEM images of Gd2O3: 6%Eu3+ (a) and Gd2O3: 6%Eu3+@silica (b) Figure 4.6 exhibits that the nanospheres are uniformly synthesized with the diameter of about 145-155 nm which is similar to the FESEM results (Figure 4.6a) The diameter of such nanospheres increase significantly after coating silica, around 155-165nm The silica shell can be easily observed by naked eyes (Figure 4.6b) 4.1.4 Powder XRD patterns of as-synthesized samples The sample of Gd(OH)CO3.H2O:6%Eu3+ is almost amorphous annealed at 200oC However, X-ray diffraction peaks are observed at 2θ: 28,70; 33,10; 47,60; 56,40; and 59.10º, in agreement with the standard of JCPDS:110604, when annealing at 650oC This can be confirmed that the material obtained is cubic crystal 19 Figure The X-ray diffraction patterns of Gd(OH)CO3.H2O:6%Eu3+ heated at 200oC and 650oC 4.1.5 EDX spectrum analysis Through EDX spectrum analysis, it can be seen that the synthesized sample includes the chemical elements Gd, O, Eu Such sample hence can be considered to be pure The EDX spectrum of Gd2O3: Eu3+@silica indicates the presence of Si atom 4.1.6 FTIR spectra Figure 4.11 plots the infrared spectra of Gd2O3: 6% Eu 3+ calcined at 650oC with and without silica shell The specific absorption regions of Gd2O3 are represented at 415.49; 449.66 and 542.9 cm-1, see Figure 4.11a The oscillation of 543 cm-1 can be attributed to the strain oscillation of Gd-O, which confirms the formation of Gd2O3 Strong absorption regions at 3446 and 1634 cm-1 specify for the typical bonds of hydroxyl (OH) group and water hydration in structure Figure 4.11b is the infrared spectrum of Gd2O3:6%Eu3+@silica, the feature oscillations of OH and Si-O-Si bonds are observed at the regions of 1050 – 1250 cm-1 650 – 800 cm-1, respectively Combining the results of EDX and FTIR analysis can confirm that the silica is coated on the outer shell of the nanospheres 20 Figure 11 FTIR spectra of (a) Gd2O3:6%Eu3+ and (b) Gd2O3:6%Eu3+@Silica 4.1.7 Luminescent properties Figure 12 PLE spectrum of Gd2O3:6%Eu3+ Figure 4.12 shows the PLE spectrum of Gd2O3:6%Eu3+ observed at the emission wavelength of 611nm The strong absorption band at 266 nm is a charge-transfer band of Eu3+- O2, the weak absorption peaks of 272 and 275nm correspond to the shift of 8S – 6I, the absorption peaks at 305 and 310 nm correspond to the displacement of 8S – 6P All absorption peaks above are the characteristic of Gd3+ The excitation bands at 394, 467 and 534 nm are derived from the Eu3+ centers corresponding to the electron f-f transitions between the energy levels belonging to the configuration 4f6 of Eu3+ The PL spectra of Gd2O3:X%Eu (X=3,5; 5; 6; 7; 8%) excitated at 270nm wavelength are plotted in Figure 4.13 Strong emission peak at 611 nm corresponds to the shift of Eu3+ ion from 5Do →7F2 Other peaks at 590, 625, 650 and 705nm have lower intensity and they 21 correspond to the shift of 5D0 → 7F1; 5D0 → 7F2; 5D0 → 7F3 and 5D0 → 7F4 Figure 13 PL spectra of Gd2O3:X%Eu (X=3,5; 5; 6; 7; 8%) In Fig.4.14 it can be seen the photoluminescence spectra of Gd2O3:6%Eu3+coated with silica shell in different thickness First, the photoluminescence intensity of Gd2O3:6%Eu3+@silica nanospheres dried at 70ºC before being coated and annealed at 650ºC was stronger than that of pure core phosphor When the silica coating in the emission range from 611 to 621nm belonging to the 5D0 – 7F2 displacement occurs interaction on the orbit, the crystal field degenerates the energy level to make the line With the sample coated with one layer of silica, maximum separation occurs in the 5D0 – 7F2 emission range due to its low crystal symmetry When coated with layers, layers at high crystal field symmetry leads to separate less When the crystal field is large, the average energy shifts towards the high energy, the emission peak of 621nm thus increases with increasing silica thickness 22 Figure 4.14 PL spectra of Gd2O3:6%Eu containing 1, and layers 4.2 Combining Gd2O3:Eu3+@Silica-NH2 luminescent material with IgG antbody to detect CEA 4.2.1 Evaluation of the ability to detect CEA antigen by nano compound Figure 4.16 Diagrammatic illustration for detection of CEA by Gd2O3:Eu3+@Silica-NH2-IgG nano fluorescent compound (a) (b) (c) (d) Figure 17 Fluorescent microscopy images of samples: Ref1 (a), disc (b), disc (c), disc (d) under the fluorescence microscope at 405nm wavelength, 40x magnification, 10x eyepiece Figure 4.17 is the images for detecting the CEA antigen by Gd2O3:Eu3+@silica-NH2-IgG nano compound under the fluorescence microscope with the magnification of 40x, the eyepiece of 10x As observed, reference disc (Figure 4.17a) is only the image of pure 23 CEA without glowing red Reference disc not recognize the image due to the nano compound being lost during washing For discs 3, and when the concentration of nano compounds increases from to 10 mg / ml (Figure 4.17b, c, d), it is easy to observe the increase of red luminescent points, the most obviously observation occurs for the nano compound with the concentration of 10 mg/ml This indicates that an immunofluorescent reaction has occurred between the nano compound and the CEA antigen 4.2.2 Evaluation of the ability to detect CEA antigen of the colorectal cancer cells HT-29 by nano compound After evaluating the results of detection of pure CEA antigen, we test on colorectal cancer HT-29 containing CEA antigen (a) (b) (c) (d) Figure 18 Fluorescence microscopy image of Ref1 (a), disk (b), disc (c), disc (d), under the fluorescence microscope at 405nm wavelength, 40x magnification, 10x eyepiece The results obtained show that reference dics (Figure 4.18a) with only the CEA antigens is not red luminescence Reference dics can not observe the image because the drifting elements were not conjugated during the washing process Discs 3, and (Figure 4.18 b, c, d) corresponding to the volumes of nano complex of 50µl (b), 75µl (c) and 100µl (d) record luminescent images The color becomes strong with increasing the volume of nano compound This proves that there is a conjugation between nano compound and cancer cell's CEA 24 antigen Therefore, this nano compound can be used to detect the CEA antigens of colorectal cancer cells CONCLUSION From the obtained research results, we briefly conclude the main conclusions as follow: Successful synthesis of GdPO4:7%Tb3+ nanorods with a length of 300–500 nm and width of 10–30 nm, single-phase crystallizing with the rhabdophane tetragonal structure type through hydrothermal process We investigated and determined the effect from the magnetic induction heating of GdPO4 and GdPO4:Tb3+ nanomaterials in aqueous solution The result exhibited that the temperature was increased to 44–49°C under an applied magnetic field of 300 Oe for 1500 seconds We also successfully synthesized Gd2O3:6%Eu3+ nanosphere with a diameter of 145–155 nm and high uniformity over 95% through multistep synthesis approach Successfully coating GdPO4:7%Tb3+ nanorods and Gd2O3:6%Eu3+ nanospheres with a silica shell, functionalizing with NH2 functional group, conjugating with anti-venom and anti-CEA antibodies Testing GdPO4:7%Tb3+@Silica-NH2-IgG nanocomplexs in the detection of cobra venom antigen and Gd2O3:6%Eu3+@Silica-NH2IgG nanocomplexs in the detection of the CEA antigen of colorectal cancer cells The obtained results show that the nanosystems based on GdPO4:7%Tb3+ nanorods and Gd2O3:6%Eu3+ nanospheres are feasible for many applications in photonics, display, security, magnetic hyperthermia in biomedicine, which contributes to early diagnosis and improves disease treatment efficiency LIST OF PUBLICATIONS Pham Thi Lien, Vu Duc Tu, Lai Ngoc Diep, Nguyen Thanh Huong, Hoang Thi Khuyen, Nguyen Thi Ngoc Anh, Vu Xuan Nghia, Tran Kim Anh, Robert Tomala and Le Quoc Minh, Characterization of Gd2O3: Eu3+ nanocomplexes conjugate with IgG for the indentification of CEA tumor cell, Materials Transactions, 2020, Vol.61, No.8 Issue, 1575-1579 Pham Thi Lien, Nguyen Thanh Huong , Tran Thu Huong, Hoang Thi Khuyen,Nguyen Thi Ngoc Anh, Nguyen Duc Van, Nguyen Ngoc Tuan, Vu Xuan Nghia, and Le Quoc Minh, Optimization of Tb3+/Gd3+ Molar Ratio for Rapid Detection of Naja Atra Cobra Venom by Immunoglobulin G-Conjugated GdPO4.nH2O:Tb3+ Nanorods, Hindawi, Journal of Nanomaterial, Volume 2019, Article ID 3858439, pages Tran Kim Anh, Nguyen Thanh Huong, Pham Thi Lien, Do Khanh Tung, Vu Duc Tu, Nguyen Duc Van, Wieslaw Strek, Le Quoc Minh Great enhancement of monodispersity and luminescent properties of Gd2O3:Eu and Gd2O3:Eu@Silica nanospheres, Materials Science & Engineering B 241 (2019) 1–8 Nguyen Thanh Huong, Nguyen Manh Hung, Pham Thi Lien, Nguyen Duc Van, Pham Hong Nam, Nguyen Thanh Binh and Le Quoc Minh, Fabrication and Characterization of Luminescent Magnetic Bifunctional Nanocomposite Based on TbPO4⋅H2O Nanowires and Fe3O4 Nanoparticles, Journal of Electrotric Materials, Vol 45(7), 2016, 36463650 Nguyen Thanh Huong, Pham Thi Lien, Nguyen Manh Hung, Nguyen Duc Van, Tran Thi Thuy, Nguyen Thanh Binh and Le Quoc Minh, Conjugation of TbPO4.H2O-based nanawises with immunoglobulin G for bioimaging, Journal of Electrotric Materials, Vol 45(5), 2016, 2463-2467 Phạm Thị Liên, Nguyễn Thanh Hường, Hoàng Thị Khuyên, Trần Thu Hương, Lê Quốc Minh, Chế tạo khảo sát tính chất quang vật liệu phốt phát chứa đất (Tb3+) dạng tổng hợp phương pháp thủy nhiệt sử dụng khn mềm diethylene glycol, Tạp chí Hóa học, 57(4e12), 2019, 172-175 Phạm Thị Liên, Lê Thị Thùy Linh, Bùi Kỳ Anh, Dương Thu Hà, Nguyễn Thanh Hường, Vũ Xuân Nghĩa, Trần Kim Anh, Lê Quốc Minh, Nghiên cứu chế tạo vật liệu nano phát quang Gd2O3:Eu3+ liên hợp với kháng thể IgG nhằm ứng dụng phát sớm carcinoembryonic antigen (CEA) phương pháp xét nghiệm in vitro, Tạp chí Hóa học, 55(3e12), 2018, 317320 ... Research objectives of the thesis - Successful synthesis of GdPO4: Tb3+ nanorods and Gd2O3: Eu3+ nanospheres - Coating GdPO4: Tb3+ nanorods and Gd2O3: Eu3+ nanospheres with a silica shell, functionalizing... characterization results of GdPO4: Tb3+ nanorods and Gd2O3: Eu3+ nanospheres We also examine and determine the magnetic hyperthermia property of GdPO4 and GdPO4: Tb3+ nanorods These nanomaterials were then... of GdPO4: Tb3+( 1), GdPO4: Tb3+@ silica (2), GdPO4: Tb3+@ silica –NH2 (3), GdPO4: Tb3+@ silica –NH2-IgG (4) 3.1.4 Infrared (IR) spectra Figure 3.9 IR spectra of GdPO4: Tb3+( a), GdPO4: Tb3+@ silica (b) GdPO4: Tb3+@ silica-NH2
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