The data of the article "Manganese-doped Calcium Phosphate Nanoclusters with Hierarchical Structure: Construction and Performance"

The samples Mn:nCaP-7, Mn:nCaP-8, Mn:nCaP-9, Mn:nCaP-10, and Mn:nCaP-11 in the dataset were prepared by synthesizing Mn:nCaP under pH conditions of 7, 8, 9, 10, and 11, respectively; The Mn:nCaP@L7, Mn:nCaP@L8, Mn:nCaP@L9, Mn:nCaP@L10, and Mn:nCaP@L11 samples were prepared from Mn:nCaP@Lys under pH conditions of 7, 8, 9, 10, and 11, respectively.  DLS: The hydrodynamic diameter and zeta potential of the samples were measured using a dynamic light scattering (DLS) instrument (Malvern, UK). For this experiment, the samples were prepared as 1 mg/mL solutions, sonicated for 10 minutes in an ultrasonicator, and then placed in cuvettes to measure their hydrodynamic diameter and zeta potential values.FT-IR: A Fourier Transform Infrared Spectrometer (FT-IR, Nexus, USA) was used to analyze the functional groups of the samples. In this experiment, the samples were pressed into transparent thin films using potassium bromide, and the wavenumber range was set to 4000–400 cm⁻¹ for qualitative identification and structural analysis.XPS: Powder samples were placed on sample holders and analyzed using an X-ray photoelectron spectrometer (XPS, K-Alpha, Thermo Scientific, USA) to determine the valence state of manganese ions in the samples. In this experiment, the powder sample was secured on a sample holder and subjected to full-spectrum and high-resolution scans in an ultra-high vacuum analysis chamber to test and analyze the valence state of Mn ions in the sample. Peak fitting for Mn 2p was performed using the Advantage software to calculate the valence state and proportion of manganese in the sample.ICP: A full-spectrum direct-reading inductively coupled plasma (ICP) emission spectrometer (Prodigy 7, Teledyne Leeman, USA) was used to detect the three elements Ca, P, and Mn in the solution. Accurately weigh 1 mg of the sample to be tested and place it in a centrifuge tube. Add 10 mL of 5% nitric acid by volume and use ultrasonication to ensure complete dissolution. Quantify the elemental content based on the intensity of each element’s characteristic spectral lines, and thereby derive the material’s actual stoichiometric composition.Thermal Properties: Place 1 mL of the sample in a 24-well plate and irradiate it with an 808 nm near-infrared laser (NIL, Honglan Optoelectronics Technology, China) for 10 minutes, then cool for 10 minutes. Repeat this process three times and record the temperature rise using a thermal imager.Catalytic Oxidation Performance: To detect ·OH generated by Mn in a CDT-initiated Fenton-like reaction, a fluorescence method was employed to assess the material’s ability to catalyze the generation of ·OH from hydrogen peroxide (H₂O₂), and to investigate the regulatory role of glutathione (GSH) in the catalytic process. The experiment included a blank group, a control group, experimental group 1, and experimental group 2. PTA, PTA+H₂O₂, PTA+H₂O₂+material, and PTA+H₂O₂+material+GSH were added to the respective groups, respectively. After mixing thoroughly and allowing the solutions to stand in the dark for 4 h, fluorescence intensity was measured using a fluorescence spectrophotometer (FL, Tianmei, China) to measure the fluorescence intensity at an excitation wavelength λex = 320 nm and an emission wavelength λem = 423 nm. The cuvette contained 1 mL of PTA, 50 μL of H₂O₂, 50 μL of Mn:CaP, 83 μL of Mn:CaP@Lys, and 30 μL of GSH. The amounts of Mn:CaP and Mn:CaP@Lys added were calculated based on their manganese ion content during preparation to ensure that the total concentration of manganese ions in the system remained constant during the catalytic reaction.EPR: Electron Paramagnetic Resonance (EPR) spectrometers (EMXplus-6/1, Bruker, Germany) are a spectroscopic technique based on the interaction between the magnetic moment of unpaired electrons and microwaves. They are primarily used to detect and characterize paramagnetic centers in materials (such as free radicals, transition metal ions, and vacancy defects). The sample is injected into a dedicated flat quartz cell or capillary tube, rapidly frozen in liquid nitrogen, and then placed in the resonant cavity. By scanning the applied magnetic field at a constant microwave frequency, absorption lines reflecting the characteristics of the paramagnetic centers are obtained.Hemolysis experiment: Collect 5% fresh red blood cells and prepare Mn:nCaP@Lys solutions with different mass concentrations (0, 50, 100, 200, 400, 800 μg/mL). Add 0.5 mL of saline and 0.5 mL of deionized water to 0.5 mL of 5% red blood cell suspension, respectively, to establish negative and positive control groups. Incubate at 37°C for 4 hours, then centrifuge and collect the supernatant. Measure the absorbance at 545 nm using a microplate reader (1510, Thermo Fisher) and calculate the hemolysis rate (%) according to Equation (1):                                                            (1)  Where ODtest, ODpositive, and ODnegative represent the absorbance at 545 nm for the experimental group, positive control group, and negative control group, respectively.  Cytotoxicity in 4T1 and L929 cells: Cytotoxicity was assessed using the CCK-8 assay. Seed L929 and 4T1 cells at a density of 5,000 cells per well in a 96-well plate and incubate in a 37°C, 5% CO₂ incubator (MCO175, SANYO) for 24 hours. Once the cells have fully adhered, remove the old medium and incubate them with different concentrations of Mn:nCaP and Mn:nCaP@ Lys for 48 hours. The old medium was then discarded, and CCK-8 reagent was added. After incubation in the incubator for 2 hours in the dark, the absorbance at 450 nm was measured using a microplate reader (1510, Thermo Fisher). Cell viability (%) was calculated using Equation (2):                                                             (2)Where ODtest, ODcontrol, and OD0 represent the absorbance at 450 nm for the experimental group, control group, and blank group, respectively.Seed 4T1 cells at a density of 5,000 cells per well into a 96-well plate (using the Countatar Mira BF-S fully automated cell counter, Shanghai Ruijue Biotechnology). After incubating in the incubator for 24 h, add different concentrations of Mn:nCaP@ Lys at different concentrations. After 2 hours of further incubation, the plates were irradiated with an 808 nm laser (1.5 W/cm²) for 10 minutes. Following an additional 46 hours of incubation in the incubator, the old medium was discarded, CCK-8 reagent was added, and the plates were incubated in the dark for 2 hours. Absorbance at 450 nm was measured using a microplate reader (1510, Thermo Fisher), and cell viability was calculated using Equation (2).Chemotherapy Sensitization Effect: CompuSyn is a commonly used software package for analyzing drug combination effects. Based on the classic Chou-Talalay method, CompuSyn calculates the combination index (CI) by analyzing the dose-response curves of the drugs. The calculation formula is as follows:                                                                                         (3)Where IC50A represents the half-maximal inhibitory concentration (IC50) of drug A alone, IC50B represents the IC50 of drug B alone, IC50(COA) represents the IC50 of drug A in the combination, and IC50(COB) represents the IC50 of drug B in the combination. The CI reflects the synergistic or antagonistic effects of drug combinations: CI < 1 indicates synergy, CI = 1 indicates an additive effect, and CI > 1 indicates antagonism. The software download link is included in the dataset appendix.    4T1 cells were seeded into a 96-well plate at a density of 5 × 10³ cells per well. After attachment, the cells were divided into a control group (culture medium only), a chemotherapy drug group (DOX, 0–40 μg/mL), a single material group (0–800 μg/mL), and a combination group (material + DOX). After culturing each group for 48 h, CCK-8 reagent was added to each well, incubated for 2 h, and the absorbance was measured to calculate cell viability. The synergistic effects of the chemotherapeutic drug and the material were quantitatively analyzed using CompuSyn software, and a relationship curve between the effect fraction (Fa) and CI was plotted.