1：Experimental Design and Method Selection:

The study involved assembling gold nanostars (AuNSs) on nanopipette tips using 3-aminopropyltrimethoxysilane (APTES) via electrostatic interaction to create a Raman probe for hypoxia sensing. Raman spectroscopy was employed to detect spectral changes in 4-nitrothiophenol (4NTP) under varying oxygen conditions.

2：Sample Selection and Data Sources:

Human cancer cell lines (A431, A549, MCF-10A, MCF-7, MDA-MB-231) were used. In vivo tests were conducted on mice with subcutaneous tumors.

3：List of Experimental Equipment and Materials:

Equipment included transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis spectrophotometer, dynamic light scattering (DLS) for zeta potential measurements, and Raman spectroscopy setup. Materials included gold nanostars, APTES, 4NTP, borosilicate nanopipettes, cell culture media, and inhibitors like oligomycin, antimycin A, and FCCP.

4：Experimental Procedures and Operational Workflow:

AuNSs were characterized using TEM and UV-Vis. Nanopipettes were functionalized with AuNSs and 4NTP. Cells were cultured under normoxic and hypoxic conditions (1%, 5%, 10%, 20% O2). RLs were inserted into cells or tumors, Raman spectra were collected, and the ratio of peak intensities (I1432/I1338) was measured. In vivo applications involved inserting RLs into tumors at different depths.

5：2). RLs were inserted into cells or tumors, Raman spectra were collected, and the ratio of peak intensities (I1432/I1338) was measured. In vivo applications involved inserting RLs into tumors at different depths. Data Analysis Methods:

5. Data Analysis Methods: Raman spectral data were analyzed by calculating intensity ratios. Statistical analysis used ANOVA and Tukey's post hoc test. FDTD simulations were performed for plasmonic predictions.