Sensitive targeted multiple protein quantification based on elemental detection of Quantum Dots

A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab₂). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab₂) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits.     

Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

New universality classes in “Percolative” dynamics

We study a site analogue of directed percolation. Random trajectories are generated and their critical behavior is studied. The critical behavior corresponds to that of simple percolation in some of the parameter space, but elsewhere the exponents reveal new universality classes. As a byproduct, we use the model to make an improved estimate of the percolation hull exponents and to calculate the site percolation probability for the square lattice.     

A solvent-free synthesis of coumarins using a Wells-Dawson heteropolyacid as catalyst

Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H₆P₂W₁₈O₆₂·24H₂O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples).     

Refraction holodiagrams and Snell's law

The refraction holodiagram RHD is analyzed here with respect to the law of refraction. Particularly, we study the surface that exactly conjugates by refraction a virtual point source with a real image or conversely. By using the total optical path as a parameter we build a diagram that consists in a family of Descartes ovals of the apple type that contains the Pascal's limaçon as a particular extreme case and the spherical surface with the Weierstrass points as another. These representations permit the straightforward application of Fermat's principle in the case of arbitrary refracting surfaces and show the shape of generalized Fresnel's zones in the intersections with any surface. Snell's law is applied to rays incident on the apple type surfaces to find out the conditions for exact conjugation. Sensitivity to optical path variations is also discussed. The RHD curves family can be represented in a Cartesian way where the ovals appear as equally spaced straight lines.     

Mineralogical analysis of auriferous ores from the El Diamante mine, Colombia

X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively.     

Equilibrium States in the Quadruple–Kerr Solution

The extended quadruple–Kerr metric is used to consider equilibrium states of four collinear Kerr particles. We explain our previous failure to solve numerically the full set of the balance equations, and we derive a self–consistent system of the axis conditions leading to the equilibrium of all four constituents which can be black holes or hyperextreme objects. The equilibrium configurations obtained in this paper exhibit similar features with those occurring in the systems of two Kerr particles, for instance, the balance of four Kerr black holes with positive masses does not seem possible. Equilibrium states of two identical compound Kerr objects are also discussed.     

Mapping Properties of a Projection Related to the Helmholtz Equation

We study the continuity properties of a projection derived from a recent characterization of Herglotz Wave Functions in the plane. Herglotz Wave Functions are the entire solutions of the Helmholtz equation which have L²-Far-Field-Pattern. The behavior of this projection is reminiscent of the Disc Multiplier Operator on both L^p and mixed L^p-normed spaces. In particular a Kakeya type set plays a central role in our analysis. As a consequence we answer a question posed by Alvarez, Folch-Gabayet and Pérez-Esteva.