Metabolic tumor profiling with pH, oxygen, and glucose chemosensors on a quantum dot scaffold.

Acidity, hypoxia, and glucose levels characterize the tumor microenvironment rendering pH, pO2, and pGlucose, respectively, important indicators of tumor health. To this end, understanding how these parameters change can be a powerful tool for the development of novel and effective therapeutics. We have designed optical chemosensors that feature a quantum dot and an analyte-responsive dye. These noninvasive chemosensors permit pH, oxygen, and glucose to be monitored dynamically within the tumor microenvironment by using multiphoton imaging.

Energy Transfer of CdSe/ZnS Nanocrystals Encapsulated with Rhodamine-Dye Functionalized Poly(acrylic acid).

Energy transfer between a CdSe/ZnS nanocrystal (NC) donor and a rhodamine isothiocyanate (RITC) acceptor has been achieved via a functionalized poly(acrylic acid) (PAA) encapsulating layer over the surface of the NC. The modification of PAA with both N-octylamine (OA) and 5-amino-1-pentanol (AP), [PAA-OA-AP], allows for the simultaneous water-solubilization and functionalization of the NCs, underscoring the ease of synthesizing NC-acceptor conjugates with this strategy. Photophysical studies of the NC-RITC constructs showed that energy transfer is efficient, with kFRET approaching 108 s-1. The ease of the covalent conjugation of molecules to NCs with PAA-OA-AP coating, together with efficient energy transfer, makes the NCs encapsulated with PAA-OA-AP attractive candidates for sensing applications.

A Nanocrystal-based Ratiometric pH Sensor for Natural pH Ranges.

A ratiometric fluorescent pH sensor based on CdSe/CdZnS nanocrystal quantum dots (NCs) has been designed for biological pH ranges. The construct is formed from the conjugation of a pH dye (SNARF) to NCs coated with a poly(amido amine) (PAMAM) dendrimer. The sensor exhibits a well-resolved ratio response at pH values between 6 and 8 under linear or two-photon excitation, and in the presence of a 4% bovine serum albumin (BSA) solution.

CdSe nanocrystal based chem-/bio- sensors.

Semiconductor nanocrystals (NCs) have found application in biology mostly as optical imaging agents where the photophysical properties of the NCs are insensitive to species in their environment. This tutorial review examines the application of CdSe NCs as optical sensing agents where the NC's photophysical properties are sensitive to species in their environment. For this case, the NC is modified at the surface with a conjugate, which interacts with an external agent by physical (i.e. recognition) or chemical means. Signal transduction in these chem-bio (CB) sensitive NCs is derived primarily from energy transfer between the NC and the external agent, which functions as the energy transfer acceptor or donor. Signaling may be obtained by directly detecting luminescence from the NC and/or the conjugate. New developments for the use of NCs as gain materials in micro-lasing cavities (distributed feedback gratings and spherical resonators) opens the way to designing CB-sensitive NCs for high-gain sensing applications.

A ratiometric CdSe/ZnS nanocrystal pH sensor.

The development of a reversible chemical sensor based on a CdSe/ZnS nanocrystal (NC) is described. Signal transduction is accomplished by fluorescence resonance energy transfer (FRET) between the NC and a fluorescent pH-sensitive squaraine dye attached to the surface of the NC. The efficiency of FRET, and consequently the relative intensity of NC and dye emissions, is modulated with the pH-dependent absorption cross section of the squaraine dye. The design of a NC sensor based on FRET results in a ratiometric sensor since the emission intensities of dye and NC may be referenced to the isosbestic point between NC and dye emissions. The ratiometric approach allows sensing to be performed, regardless of issues surrounding collection efficiency (scattering environment, light fluctuations, etc.) and dye:NC loadings.

Syntheses, structure, and selected physical properties of CsLnMnSe3 (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ3 (A = Rb, Cs; Q = S, Se, Te).

CsLnMnSe(3) (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ(3) (A = Rb, Cs; Q = S, Se, Te) have been synthesized from solid-state reactions at temperatures in excess 1173 K. These isostructural materials crystallize in the layered KZrCuS(3) structure type in the orthorhombic space group Cmcm. The structure is composed of LnQ(6) octahedra and MQ(4) tetrahedra that share edges to form [LnMQ(3)] layers. These layers stack perpendicular to [010] and are separated by layers of face- and edge-sharing AQ(8) bicapped trigonal prisms. There are no Q-Q bonds in the structure of the ALnMQ(3) compounds so the formal oxidation states of A/Ln/M/Q are 1+/3+/2+/2-. The CsLnMnSe(3) materials, with the exception of CsYbMnSe(3), are Curie-Weiss paramagnets between 5 and 300 K. The magnetic susceptibility data for CsYbZnS(3), RbYbZnSe(3), and CsYbMSe(3) (M = Mn, Zn) show a weak cusp at approximately 10 K and pronounced differences between field-cooled and zero-field-cooled data. However, CsYbZnSe(3) is not an antiferromagnet because a neutron diffraction study indicates that CsYbZnSe(3) shows neither long-range magnetic ordering nor a phase change between 4 and 295 K. Nor is the compound a spin glass because the transition at 10 K does not depend on ac frequency. The optical band gaps of the (010) and (001) crystal faces for CsYbMnSe(3) are 1.60 and 1.59 eV, respectively; the optical band of the (010) crystal faces for CsYbZnS(3) and RbYbZnSe(3) are 2.61 and 2.07 eV, respectively.

The CsLnMSe3 semiconductors (Ln = rare-earth element, Y; M = Zn, Cd, Hg).

CsLnCdSe(3) (Ln = Ce, Pr, Sm, Gd, Tb, Dy, Y) and CsLnHgSe(3) (Ln = La, Ce, Pr, Nd, Sm, Gd, Y) have been synthesized at 1123 K. These isostructural materials crystallize in the layered KZrCuS(3) structure type in the orthorhombic space group Cmcm and are group X extensions of the previously characterized Zn compounds. The structure is composed of two-dimensional [LnMSe(3)] layers that stack perpendicular to [010] and are separated by layers of face- and edge-sharing CsSe(8) bicapped trigonal prisms. Because there are no Se-Se bonds in the structure of CsLnMSe(3) (M = Zn, Cd, Hg), the formal oxidation states of Cs/Ln/M/Se are 1+/3+/2+/2-. CsSmHgSe(3) does not adhere to the Curie-Weiss law, whereas CsCeHgSe(3) and CsGdHgSe(3) are Curie-Weiss paramagnets with micro (eff) values of 2.77 and 7.90 micro (B), corresponding well with the theoretical values of 2.54 and 7.94 micro (B) for Ce(3+) and Gd(3+), respectively. Single-crystal optical absorption measurements were performed with polarized light perpendicular to the (010) and (001) crystal faces of these materials. The band gaps of the (010) crystal faces range from 1.94 eV (CsCeHgSe(3)) to 2.58 eV (CsYCdSe(3)) whereas those of the (001) crystal faces span the range 2.37 eV (CsSmHgSe(3)) to 2.54 eV (CsYCdSe(3) and CsYHgSe(3)). The largest band gap variation between crystal faces is 0.06 eV for CsYCdSe(3). Theoretical calculations for CsYMSe(3) indicate that these materials are direct band gap semiconductors whose colors and optical band gaps are dependent upon the orbitals of Y, M, and Se.