As the major redox couple and nonprotein thiol source in human tissues, the level of glutathione (GSH) has been a concern for its relation with many diseases. However, the similar physical and chemical properties of interference molecules such as cysteine (Cys) and homocysteine (Hcy) make discriminative detection of GSH in complex biological fluids challenging. Here we report a novel surface-enhanced Raman scattering (SERS) platform, based on silver-nanoparticleembedded porous silicon disks (PSDs/Ag) substrates for highly sensitive and selective detection of GSH in biofluids. Silver nanoparticles (AgNPs) were reductively synthesized and aggregated directly into pores of PSDs, achieving a SERS enhancement factor (EF) up to 2.59 × 10 7 . Ellman's reagent 5,5′-ditho-bis (2-nitrobenzoic acid) (DTNB) was selected as the Raman reactive reporting agent, and the GSH quantification was determined using enzymatic recycling method, and allowed the detection limit of GSH to be down to 74.9 nM using a portable Raman spectrometer. Moreover, the significantly overwhelmed enhancement ratio of GSH over other substances enables the discrimination of GSH detection in complex biofluids.
Single-crystalline FeTe 2 in marcasite phase with orthorhombic structure was prepared via chemical vapor transport. Cooling FeTe 2 single crystals from room temperature down to 2 K, multiple magnetic phase transitions were observed. Paramagnetic (PM) to antiferromagnetic (AFM) and then to ferromagnetic (FM) occurred at 79 K and 35 K for in-plane, 73 K and 29 K for out-of-plane, respectively. A strong uniaxial magnetic anisotropy was found due to FeTe 6 octahedron distortion and structural modulation in FM region. The novel negative volume expansion (NVE) initiated in the vicinity of AFM to FM transition. An abrupt frequency shift of the most intense mode at 118 cm −1 and evolution of the Te-Te stretching mode near 40 K, corresponding to the phase transition from AFM to FM were observed. The temperature-dependent resistance revealed an anomaly (semiconductor to metallic transition) around AFM-FM transition, which can easily be suppressed and move to high temperature by the applied magnetic field. The results from XRD, Raman and resistivity indicated that the structural parameters, vibration frequency and transport are sensitive to the phase transition from AFM to FM. The nature of direct band gap with 0.67 eV was identified through UV-Vis-NIR spectrum of FeTe 2 single crystals at room temperature.
Porous silicon nanodisks (PSD) were fabricated by the combination of photolithography and electrochemical etching of silicon. By using PSD as a reducing agent, gold nanorods (AuNR) were in situ synthesized in the nanopores of PSD, forming PSD-supported-AuNR (PSD/AuNR) hybrid particles. The formation mechanism of AuNR in porous silicon (pSi) was revealed by exploring the role of pSi reducibility and each chemical in the reaction. With the PSD support, AuNR exhibited a stable morphology without toxic surface ligands (CTAB). The PSD/AuNR hybrid particles showed enhanced plasmonic property compared to free AuNR. Because high-density "hot spots" can be generated by controlling the distribution of AuNR supported in PSD, surface-enhanced raman scattering (SERS) using PSD/AuNR as particle substrates was demonstrated. A multifunctional vector, PSD/AuNR/DOX, composed of doxorubicin (DOX)-loaded PSD/AuNR capped with agarose (agar), was developed for highly efficient, combinatorial cancer treatment. Their therapeutic efficacy was examined using two pancreatic cancer cell lines, PANC-1 and MIA PaCa-2. PSD/AuNR/DOX (20 μg Au and 1.25 μg DOX/mL) effectively destroyed these cells under near-IR laser irradiation (810 nm, 15 J·cm(-2) power, 90 s). Overall, we envision that PSD/AuNR may be a promising injectable, multifunctional nanovector for biomedical application.
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