The efficacy of radiation therapy (RT) is often limited by the poor response of hypoxia inside most solid tumors. The development of a theranostic nanoplatform for precision‐imaging‐guided sensitized RT for tumor hypoxia is still challenging. Herein, the creation of hypoxia‐targeted dendrimer‐entrapped gold nanoparticles complexed with gadolinium(III) (Gd‐Au DENPs‐Nit) for dual‐mode CT/MR imaging and sensitized RT of hypoxic tumors is reported. In this work, generation 5 poly(amidoamine) dendrimers are partially conjugated with Gd(III) chelator, entrapped with Au nanoparticles, and conjugated with hypoxia‐targeting agent nitroimidazole via a polyethylene glycol linker, and ending with chelation of Gd(III) and conversion of their leftover amine termini to acetamides. The designed dendrimer‐based nanohybrids with 3.2 nm Au cores exhibit an excellent X‐ray attenuation effect, acceptable r1 relaxivity (1.32 mM−1 s−1), and enhanced cellular uptake in hypoxic cancer cells, affording efficient dual‐mode CT/MR imaging of tumor hypoxia. Under X‐ray irradiation, the Gd‐Au DENPs‐Nit nanohybrids can produce reactive oxygen species, promote DNA damage, and prevent DNA repair, facilitating sensitized RT of hypoxic cancer cells in vitro and tumor hypoxia in vivo. The developed hypoxia‐targeted dendrimer‐based nanohybrids may be employed as both contrast agents and nanosensitizers for precision tumor hypoxia imaging and sensitized tumor RT.
The adsorption of glycine and l-cysteine on Si(111)-7 x 7 was investigated using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). The observation of the characteristic vibrational modes and electronic structures of NH3+ and COO- groups for physisorbed glycine (l-cysteine) demonstrates the formation of zwitterionic species in multilayers. For chemisorbed molecules, the appearance of nu(Si-H), nu(Si-O), and nu(C=Omicron) and the absence of nu(O-H) clearly indicate that glycine and l-cysteine dissociate to produce monodentate carboxylate adducts on Si(111)-7 x 7. XPS results further verified the coexistence of two chemisorption states for each amino acid, corresponding to a Si-NH-CH2-COO-Si [Si-NHCH(CH2SH)COO-Si] species with new sigma-linkages of Si-N and Si-O, and a NH2-CH2-COO-Si [NH2CH(CH2SH)COO-Si] product through the cleavage of the O-H bond, respectively. Glycine/Si(111)-7 x 7 and l-cysteine/Si(111)-7 x 7 can be viewed as model systems for further modification of Si surfaces with biological molecules.
Design and fabrication of noble metal nanocrystals have attracted much attention due to their wide applications in catalysis, optical detection and biomedicine. However, it still remains a challenge to scale-up the production in a high-quality, low-cost and eco-friendly way. Here we show that single crystalline silver nanobelts grow abundantly on the surface of biomass-derived monolithic activated carbon (MAC), using [Ag(NH3)2]NO3 aqueous solution only. By varying the [Ag(NH3)2]NO3 concentration, silver nanoplates or nanoflowers can also be selectively obtained. The silver growth was illustrated using a galvanic-cell mechanism. The lowering of cell potential via using [Ag(NH3)2]+ precursor, together with the AgCl crystalline seed initiation, and the releasing of OH− in the reaction process, create a stable environment for the self-compensatory growth of silver nanocrystals. Our work revealed the great versatility of a new type of template-directed galvanic-cell reaction for the controlled growth of noble metal nanocrystals.
The Covalent binding of p-benzoquinone (OC6H4O) and the formation of an aromatic ring (−OC6H4O−) on Si(111)-7×7 have been investigated by using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. For chemisorbed p-benzoquinone, the absence of v(CO) at 1659 cm−1, the retention of sp2-v(C−H) at 3050 cm−1, the appearance of v(Si−O) at 824 cm−1, and aromatic v(CC)/δip(C−H) at 1600/1505 cm−1 demonstrate that the molecule reacts with the surface in a [6+2]-like cycloaddition mode, which is further confirmed by XPS and density functional theory (DFT) vibrational calculations. DFT calculations indicate that the [6+2]-like cycloadduct (−OC6H4O−) bridging two nearest adatoms in neighboring half-unit cells is the most stable. This binding scheme may prove useful for chemical and electronic modification of the semiconductor surfaces.
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