Immunoassay for native enzyme quantification in biological samples

In order to detect low levels of enzyme activity, specifically glucose oxidase, in biological samples, an immunoenzymatic assay was developed since currently available methods could not be used because of either their lack of sensitivity or the conditions prevailing in our samples: turbidity of the medium, presence of redox systems other than glucose oxidase, and high concentration of proteins. The principle of the method is to coat a polystyrene surface with a fragment Fc-specific anti-IgG, then with an antibody directed against the looked-for enzyme, which is simultaneously the antigen and the enzyme activity required for immunoenzymatic detection. We applied this concept to biological samples after glucose oxidase administration to mice. This method achieves specificity and sensitivity (20 ng/mL or 1 ng) with samples of biological origin. No marker is needed since the antigen itself possesses an enzyme activity. This method, which requires a small sample volume (50 ΜL, 20 ΜL, if necessary), can be extended easily to the many enzymes currently used as markers. It could also be applied to the native enzymes of medical interest for which antibodies and a colorimetric reaction are available.     

How to reduce the experimental time in isotopic 2H NMR using the ERETIC method

Deuterium site-specific natural isotope abundance (Ai) is routinely measured by NMR spectroscopy and quantified using an internal reference peak. This study demonstrates that the substitution of the chemical compound used as internal reference by an electronically generated signal (the ERETIC method) allows a dramatic reduction of the experimental time. Measurements of Ai on eight samples of methylsalicylate have been performed using either an internal reference (TMU) or ERETIC. No significant difference in accuracy or precision had been found between the two methods. However, because the method is applicable in partially saturated conditions, the experiment time was divided by a factor of 4 and the drawbacks associated with an internal chemical reference were avoided when ERETIC was used.     

Two 2,6‐Dioxabicyclo[3.3.1]nonan‐3‐ones from Phragmanthera capitata (Spreng.) Balle (Loranthaceae)

Phytochemical investigation of the leaves of Phragmanthera capitata collected on Cassia spectabilis tree led to the isolation of two natural lactones, rel‐(1R,5S,7S)‐7‐[2‐(4‐hydroxyphenyl)ethyl]‐2,6‐dioxabicyclo[3.3.1]nonan‐3‐one ( 1 ) and 4‐{2‐[rel‐(1R,3R,5S)‐7‐oxo‐2,6‐dioxabicyclo[3.3.1]non‐3‐yl]ethyl}phenyl 3,4,5‐trihydroxybenzoate ( 2 ) together with the known compounds betulinic acid ( 3 ), dodoneine ( 4 ), quercetin 3‐O‐α‐L ‐rhamnopyranoside ( 5 ), quercetin 3‐O‐α‐L ‐arabinofuranoside ( 6 ), quercetin ( 7 ), betulin ( 8 ), lupeol ( 9 ), and sitosterol ( 10 ). Their structures were established by means of modern spectroscopic techniques, and the relative configuration of compound 1 was confirmed by X‐ray analysis. Compounds 1 and 2 were tested in vitro for their antiplasmodial activity against the Plasmodium falciparum chloroquine sensitive‐strains NF54 and 3D7. Compound 2 exhibited good antiplasmodial activity against both strains with IC₅₀ of 2.4 and 4.9 μM , respectively, while compound 1 was inactive.     

Synthesis and reactivity of pelletierine-derived building blocks and pelletierine analogs

Lycopodium alkaloids are unique (and often impressive in terms of structures) polycyclic alkaloids that attract great interest from a biological point of view and that also provide ideal targets for total synthesis. Propylpiperidine units closely related to pelletierine are involved in the biosynthesis of these alkaloids. Therefore, stable pelletierine-like compounds, especially a (R)-phenylglycinol-based oxazolopiperidine analog, were prepared and their reactivity investigated. The compounds described in this work expand the tool-box of small building blocks in the piperidine series and pelletierine analogs and could be suitable for the synthesis of Lycopodium alkaloids following biosynthetically inspired strategies.     

Particular behavior of ‘C6C2 units’ in the Chichibabin pyridine synthesis and biosynthetic implications

Several aspects of the unusual behavior of C₆C₂ aldehydes and amines during the formation of pyridiniums in analogy with the historical Chichibabin pyridine synthesis are clarified in this Letter. Interesting biosynthetic consequences are also discussed within two classes of polycyclic alkaloids of marine origin.     

N-Rich Porous Polymer with Isolated Tb3+-Ions Displays Unique Temperature Dependent Behavior through the Absence of Thermal Quenching

The challenge of measuring fast moving or small scale samples is based on the absence of contact between sample and sensor. Grafting lanthanides onto hybrid materials arises as one of the most promising accurate techniques to obtain noninvasive thermometers. In this work, a novel bipyridine based porous organic polymer (bpyDAT POP) was investigated as temperature sensor after grafting with Eu(acac)₃ and Tb(acac)₃ complexes. The bpyDAT POP successfully showed temperature-dependent behavior in the 10–310 K range, proving the potential of amorphous, porous organic frameworks. We observed unique temperature dependent behavior. More intriguingly, instead of the standard observed change in emission as a result of a change in temperature for both Eu³⁺ and Tb³⁺, the emission spectrum of Tb³⁺ remained constant. This work provides framework- and energy-based explanations for the observed phenomenon. The conjugation in the bpyDAT POP framework is interrupted, creating energetically isolated Tb³⁺ environments. Energy transfer from Tb³⁺ to Eu³⁺ is therefore absent, nor energy back transfer from Tb³⁺ to bpyDAT POP ligand (i.e. no thermal quenching) is detected.     

d-xylose-based bolaamphiphiles: Synthesis and influence of the spacer nature on their interfacial and membrane properties

A two-step synthesis, with good yields, of d-xylose-based bolaamphiphiles is described. The monolayer properties, the adsorption behavior and membrane destabilization properties of two bolaamphiphiles differing by their spacers (presence or absence of one double bond) were studied. The presence of one unsaturation has no influence on the interfacial organization at low compression but impairs the stability of the monolayer at high compression. Saturated and unsaturated molecules are suggested to adopt a loop structure at the interface at low compression. The higher degree of freedom of the saturated hydrophobic spacer does not affect the initial diffusion step of the bolaform from the subphase to the interface but greatly slows the arrangement step at the interface. However, once at the interface, their surface-active properties are similar. The higher flexibility of the saturated analogue spacer also greatly increases its lipid vesicle destabilizing property. Its rearrangement within the lipid bilayer is in favour of the formation of inverted phases, facilitating membrane fusion.     

Detection range modeling of blue whale calls in Southwestern Indian Ocean

In the Southwestern Indian Ocean, one year of continuous acoustic data from calibrated hydrophones maintained by the International Monitoring System provided data on blue whale calls from two subspecies Antarctic and pygmy blue whales. Using an automatic detection method with a fixed threshold, both call types were detected and received levels were measured for each detected call. By using a parabolic equation loss model configured with the precise characteristics of the biological source, hydroacoustic station, and environment in the study area, distances at which calls could be detected were estimated. These methods were used to define the maximum detection range around each array of hydrophones and the influence of the seasonal variation of the ambient noise and sound velocity on the detection ranges. Results showed that detection ranges were critically dependent on the choice of the biological source’s input parameters, including frequency bandwidth and source level. Over the course of the year, detection distances were different for both subspecies; the pygmy blue whale seemed to be consistently closer to the station than the Antarctic blue whale. The distribution of the estimated distances confirmed the presence of both subspecies of blue whales near the Crozet Islands showing the importance of this sub-Antarctic area for these endangered species, especially during the austral summer feeding season.     

A Feynman-Kac type formula for a fixed delay CIR model

Stochastic delay differential equations (SDDE’s) have been used for financial modeling. In this article, we study a SDDE obtained by the equation of a CIR process, with an additional fixed delay term in drift; in particular, we prove that there exists a unique strong solution (positive and integrable) which we call fixed delay CIR process. Moreover, for the fixed delay CIR process, we derive a Feynman-Kac type formula, leading to a generalized exponential-affine formula, which is used to determine a bond pricing formula when the interest rate follows the delay’s equation. It turns out that, for each maturity time T, the instantaneous forward rate is an affine function (with time dependent coefficients) of the rate process and of an auxiliary process (also depending on T). The coefficients satisfy a system of deterministic differential equations.     

Overview of N-Rich Antennae Investigated in Lanthanide-Based Temperature Sensing

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields. To circumvent their low molar light absorption, the incorporation of a light-harvesting antenna is required. This Review provides an overview of the nitrogen-rich antennae in lanthanide-based temperature sensors, emitting in the visible light spectrum, and discusses their temperature sensor ability. The N-rich ligands are incorporated in many different platforms. The investigation of different antennae is required to develop temperature sensors with diverse optical properties and to create a diverse offer for the multiple application fields. Molecular probes, consisting of small molecules, are first discussed. Furthermore, the thermometer properties of ratiometric temperature sensors, based on di- and polynuclear complexes, metal–organic frameworks, periodic mesoporous organosilicas and porous organic polymers, are summarized. The antenna mainly determines the application potential of the ratiometric thermometer. It can be observed that molecular probes are operational in the broad physiological range, metal–organic frameworks are generally very useful in the cryogenic region, periodic mesoporous organosilica show temperature dependency in the physiological range, and porous organic polymers are operative in the cryogenic-to-medium temperature range.