Self-assembled luminescent CdSe-ZnS quantum dot bioconjugates prepared using engineered poly-histidine terminated proteins

We report a simple and versatile approach for the conjugation of luminescent CdSe-ZnS core-shell quantum dots (QDs) to proteins through coordination of engineered C-terminal oligohistidine sequences. Several histidine tail containing proteins were self-assembled onto the QD surface using this method. A recombinant antibody specific for the high explosive 2,4,6-trinitrotoluene (TNT) was conjugated to QDs through a carboxy terminal histidine tail and the bioconjugate used to detect TNT by competitive immunoassay. TNT was detected over the range of 10 μg/ml down to 41 ng/ml using the scFv conjugated to QDs. These results open up the possibility to conjugate luminescent QDs to a whole range of proteins to form QD bioconjugates that can be effectively used in bio-oriented applications, such as sensing, imaging, immunoassay and other diagnostics.     

Comparison of Py*+/dU*- charge transfer state dynamics in 5-(1-pyrenyl)-2'-deoxyuridine nucleoside conjugates with amido-, ethylenyl-, and ethynyl linkers

Femtosecond, picosecond, and nanosecond transient absorbance (TA) and picosecond emission kinetics results are presented for three 5-(1-pyrenyl)-2'-deoxyuridine nucleosides each with a different two-atom linker joining pyrenyl C-1 to uracil C-5. The linkers are respectively -NHCO-, -(CH(2))(2)-, and -C[triple bond]C- for PAdU, PEdU, and PYdU. For all three nucleoside conjugates, most conformers undergo intramolecular charge transfer (CT) from their pyrenyl (1)(pi,pi) excited states to form Py(*+)/dU(*-) CT products in ultrashort times: 相似文献   

Multiphoton ionization vibrational state selection of H2O, D2O and HDO

We present a study of single color (2 + 1) resonance-enhanced multiphoton ionization (REMPI) of H₂O, D₂O, and HDO via several Rydberg states lying in the energy range from 80 000 to 86 000 cm⁻¹. Photoelectron spectra (PES) show that the corresponding cations can be vibrationally state-selected for most vibrational states. The exception is the bend of H₂O⁺ and HDO⁺, where mixing in the REMPI intermediate level results in weak ion intensity and only 50% state purity.     

The first intermolecular Friedel-Crafts acylation with beta-lactams

The first intermolecular Friedel-Crafts acylation of a variety of aromatic substrates with azetidinones is described. The Friedel-Crafts acylations are performed under very mild conditions, using trifluoromethanesulfonic acid to produce beta-amino aromatic ketones in excellent yields.     

Relative Lewis basicities of six AI(ORF)4- superweak anions and the structures of LiA

The relative Lewis basicities of six Al(ORF)4- ions, Al[OC(CH3)(CF3)2]4-, Al(OC(CF3)3]4-, Al(OCPh(CF3)2]4-, Al[OC[4-C6H4(tBu)](CF3)2]4-, Al(OC(Cy)(CF3)2]4-, and Al(OCPh2(CF3)]4-, have been determined by measuring their relative coordinating abilities towards Li+ in dichloromethane. The relative Li- Lewis basicities of the Al(ORF)4- ions are linearly related to the aqueous pKa values of the corresponding parent HORF fluoroalcohols. The Lewis basicity of Al[OCH(CF3)2]4- could not be measured because two of these anions can coordinate to one Li+ cation. The structures of LiAl[OCH(CF3)2]4 and [1-Et-3-Me-1,3-C3H3N2][Li[Al[OCH(CF3)2)4]2] were determined.     

Determination of the fluoride distribution in rabbit bone using instrumental neutron activation analysis

An instrumental neutron activation analysis (INAA) technique, based on the¹⁹F(n,)²⁰F reaction, has been development for the determination of fluoride in bone. The purpose was to study fluoride distribution in different kinds of bone samples using a rabbit model. The rationale for the study stems from the posible correlation between fluoride in bone and osteoporosis. The sodium concentration in the bone was used to correct the²⁰F peak area for the²³F(n,)²⁰F contribution. Two secondary standards, teflon tape and teflon coated dacron line, were used to quantify fluoride concentration. They proved to be stable and consistent with respect to their fluoride concentration. Bone specimens from 10 sites and two tooth samples were analyzed for fluoride. Fluoride concentration ranged from 305 ppm in the tibia long bone to 585 ppm in the humerus trochanter end and the magnitude of fluoride concentration levels is age depdentent. The detection limit of the fluoride is approximately 5 ppm using a 100 mg bone sample.     

Catalytic synthesis of nitrogen-containing heterocycles (a review)

The process of the catalytic synthesis of a number of nitrogenous heterocyclic compounds based on the utilization of reactions involving the amination of oxygen-containing heterocycles, the dehydration cyclization of amino alcohols, the deamination of di- and polyamines, and the intermolecular dehydration cyclization of glycols with diamines have been considered.     

Hydrothermal synthesis of fluorated single crystals: BaMnF4 and BaF2·HF

Investigations to eliminate defects in the incommensurate phase BaMnF₄, led to a method of preparation at a temperature lower than the melting point of BaMnF₄. Qualitative studies of the systems BaF₂ -H₂O -HF and MnF₂ -H₂O -HF showed that very pure single crystals of BaMnF₄ could be grown at a temperature lower than 300°C. Several new phases could be isolated as single crystals, in particular: BaF_2^′HFSingle crystal X-ray analysis revealed the compound to be monoclinic (Space Group P2₁ and Z = 2) and confirmed the formula found by chemical analysis. However, because of the difficulty to distinguish between fluorine and oxygen atoms, some problems remain, which will be solved by neutron diffraction studies. Infrared analysis indicate the presence of HF^?₂ and suggest the following representation: (Ba²⁺)₂(HF^?₂)₂(F^?)₂.It is possible to extend this method of synthesis to the preparation of other fluorides and related compounds, in particular to those of europium and strontium.     

A highly stable short alpha-helix constrained by a main-chain hydrogen-bond surrogate

Herein we describe a strategy for the preparation of artificial alpha-helices involving replacement of one of the main-chain hydrogen bonds with a covalent linkage. To mimic the C=O...H-N hydrogen bond as closely as possible, we envisioned a covalent bond of the type C=X-Y-N, where X and Y are two carbon atoms connected through an olefin metathesis reaction. Our results demonstrate that the replacement of a hydrogen bond between the i and i + 4 residues at the N-terminus of a short peptide with a carbon-carbon bond results in a highly stable constrained alpha-helix at physiological conditions as indicated by CD and NMR spectroscopies. The advantage of this strategy is that it allows access to short alpha-helices with strict preservation of molecular recognition surfaces required for biomolecular interactions.     

Thermal conductivity of the urea-hexadecane inclusion compound

The thermal conductivity and the heat capacity per unit volumec _p have been measured for the urea-hexadecane inclusion compound using the transient hot-wire method. Measurements were made under isobaric conditions at a pressure of 0.1 GPa and in the temperature range of 100–300 K. There was evidence for a phase transition at a temperature of about 160 K, in reasonable agreement with previous work. For the high-temperature phase was independent of temperature within ±1%. The low-temperature phase showed a weak temperature dependence, with (d In/d InT) _p = –0.13. It was inferred that interaction between acoustic phonons and low-frequency vibrational excitations of the guest molecules made a major contribution to the thermal resistivity. For the quantityc _p a weak maximum was observed in the region of the phase transition temperature.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.