Study of the brightness of trumpet tones

This study focuses on a particular attribute of trumpet tones, the brightness, and on the physical characteristics of the instrument thought to govern its magnitude. On the one hand, an objective study was carried out with input impedance measurements, and, on the other hand, a subjective study with hearing tests and a panel of subjects. To create a set of different trumpets a variable depth mouthpiece was developed whose depth can be easily and continuously adjusted from "deep" to "shallow." Using this mouthpiece and the same trumpet, several instruments were generated which may be played in three ways: (i) by a musician, (ii) by an artificial mouth, and (iii) using physical modeling simulations. The influence of the depth of the mouthpiece on the perception of the trumpet's tones was investigated, and the ability of a musician, the artificial mouth, or physical modeling simulations to demonstrate perceptively noticeable differences was assessed. Physical characteristics extracted from the impedance curves are finally proposed to explain the brightness of trumpet tones. As a result, the physical modeling simulations now seem to be mature enough to exhibit coherent and subtle perceptual differences between tones. This opens the door to virtual acoustics for instrument makers.     

Interpolation Formulas for Functions of Exponential Type

In the paper we present a derivative-free estimate of the remainder of an arbitrary interpolation rule on the class of entire functions which, moreover, belong to the space L² _(-,+). The theory is based on the use of the Paley-Wiener theorem. The essential advantage of this method is the fact that the estimate of the remainder is formed by a product of two terms. The first term depends on the rule only while the second depends on the interpolated function only. The obtained estimate of the remainder of Lagrange's rule shows the efficiency of the method of estimate. The first term of the estimate is a starting point for the construction of the optimal rule; only the optimal rule with prescribed nodes of the interpolatory rule is investigated. An example illustrates the developed theory.     

Diode-pumped Nd:YAG laser emitting at 899 nm and below

We present what is, to the best of our knowledge, the first diode-pumped Nd:YAG laser emitting at 899 nm and below, based on the (4)F(3/2) - (4)I(9/2) transition, generally used for a 946 nm emission. A power of 630 mW at 899 nm has been achieved in cw operation and 16 mW at 884 nm with a fiber-coupled laser diode emitting 9 W at 808 nm. Intracavity second-harmonic generation in cw mode has also been demonstrated with a power of 100 mW at 450 nm by using a LiB(3)O(5) nonlinear crystal.     

Tethered aminohydroxylation: dramatic improvements to the process

[reaction: see text] Changing the identity of the N leaving group on a hydroxylamine-based reoxidant gives a dramatic improvement to the tethered aminohydroxylation reaction. Using OCOC6F5 as a leaving group means that only 1 mol % of osmium is required and yields as high as 98% can be obtained. Acyclic homoallylic alcohols were substrates considered too unreactive for effective use in the tethered aminohydroxylation reaction; improved reaction conditions mean that they have now become viable substrates for oxidation.     

Dendri-RAFTs: a second generation of cyclopeptide-based glycoclusters

Synthetic glycoclusters and their related biological applications have stimulated increasing interest over the last decade. As a prerequisite to discovering active and selective therapeuticals, the development of multivalent glycoconjugates with diverse topologies is faced with inherent synthetic and structural characterisation difficulties. Here we describe a new series of molecularly-defined glycoclusters that were synthesized in a controlled manner using a robust and versatile divergent protocol. Starting from a Regioselectively Addressable Functionalized Template (RAFT) carrier, either a polylysine dendritic framework or a second RAFT, then 16 copies of βGal, αMan, βLac or cancer-related Thomsen-Freidenreich (αTF) antigen were successively conjugated within the same molecule using oxime chemistry. We thus obtained a new generation of dendri-RAFTs glycoclusters with high glycosidic density and variable spatial organizations. These compounds displaying 16 endgroups were unambiguously characterized by NMR spectroscopy and mass spectrometry. Further biological assays between a model lectin from Canavalia ensiformis (ConA) and mannosylated glycoclusters revealed a higher inhibition potency than the tetravalent counterpart, in particular for the hexadecavalent polylysine skeleton. Together with the efficiency of the synthetic and characterisation processes, this preliminary biological study provided clear evidence of promising properties that make the second generation of cyclopeptide-based glycoclusters attractive for biomedical applications.     

Silica nanoparticles containing a rhodamine dye and multiple gold nanorods

Silica shells are grown around colloidally synthesized gold nanorods (AuNRs) to form core–shell particles (AuNR@SiO₂) of variable occupancy, defined as the number of AuNRs per silica particle. Multiple AuNR occupancy within the silica shell, confirmed with high-resolution electron microscopy, is reflected in a redshift of the longitudinal plasmon mode of the nanorods due to multipolar coupling between AuNRs of a favored end–end orientation. In addition to the plasmon resonance that dominates their absorbance spectra, FL-AuNR@SiO₂, core–shell particles incorporating a lipid probe (rhodamine-DOPE), can be monitored by their fluorescence and Raman signals. Optical and scanning electron microscopy (SEM) images are compared directly, enabling the correlation of spectroscopic characteristics with particle morphology. Raman and SEM images show that the most intense Raman signals come from aggregates of AuNRs trapped within the silica matrix. Biexponential fits to fluorescence decays indicate that competing mechanisms of quenching and fluorescence enhancement contribute to a reduced fluorescence lifetime of rhodamine-DOPE located near the AuNRs.     

Synthesis of 3-aryl-2-arylamidobenzofurans based on the Curtius rearrangement

The synthesis of novel 3-aryl-2-arylamidobenzofurans has been accomplished via a Curtius rearrangement strategy in four steps from benzofuran-2-carboxylic acids. The requisite Suzuki-Miyaura cross-coupling, with benzyl 3-bromobenzofuran-2-ylcarbamate or 2-arylamido-3-bromobenzofurans, revealed an unusual reductive debromination process due to the presence of the free NH group. This dehalogenation can be suppressed by N-alkylation. DMAP is an efficient reagent for the one-pot conversion of benzyl benzofuran-2-ylcarbamates into the corresponding benzofuran-2-arylamides through aroylation, thus acting both as an acyl transfer reagent and a deprotecting agent of the Cbz group. A mechanism is postulated.     

Gram-scale synthesis of iejimalide B

Iejimalide B ( 2 ) is the most promising member of a small family of marine polyene macrolides endowed with remarkably selective activity against human cancer cell lines. As this product, however, is hardly available from the natural sources, a detailed evaluation requires the development of an efficient and practical synthetic approach. This challenge has now been met by adapting the first total synthesis of 2 previously reported by our group to the needs of high material throughput. Redesigning the access routes to the five required building blocks in combination with a careful optimization of the fragment coupling processes provided gram amounts of this valuable compound in a sequence of no more than 16 linear steps with an overall yield of about 7 %. Key elements of the successful strategy include: i) three hydrostannylation processes of elaborate terminal alkynes with “lower order” stannyl cuprates, ii) a Brown allylation, a Noyori transfer hydrogenation, and a Marshall propargylation to set the chiral centers at C9, C17, C22 and C23, and iii) a modified Takai–Utimoto olefination for the preparation of the very labile skipped 1,4‐diene flanking the ester group. The assembly process benefited from a particularly mild protocol for the Stille cross‐coupling previously developed in this laboratory, which clearly outperformed the alternative Suzuki reaction in terms of yield and scalability. The 24‐membered macrocyclic frame was forged by a remarkably selective ring‐closing metathesis reaction (RCM), in which two out of the ten double bonds present in the cyclization precursor were selectively activated with the aid of a second‐generation Grubbs catalyst.     

The binding of CNA35 contrast agents to collagen fibrils

CryoTEM demonstrates that a CNA35-bearing liposomal MRI contrast agent selectively binds to poorly assembled collagen type I as opposed to well-assembled collagen fibrils, whereas monomeric CNA35 binds to all forms of collagen. It is shown that upon conjugation to liposomes and micelles CNA35 loses its ability to dissociate ordered collagen fibrils and thereby to create its own binding sites.     

Improved DFT-Based Interpretation of ESI-MS of Aqueous Metal Cations

We present results showing that our recently developed density functional theory (DFT)-based speciation model of the aqueous Al³⁺ system has the potential to improve the interpretations of ESI-MS studies of aqueous metal cation hydrolytic speciation. The main advantages of our method are that (1) it allows for the calculation of the relative abundance of a given species which may be directly assigned to the signal intensity in a mass spectrum; (2) in cases where species with identical m?z ratios may coexist, the assignment can be unambiguously assigned based on their theoretical relative abundances. As a demonstration of its application, we study four pairs of monomer and dimer aqueous Al³⁺ species, each with identical m/z ratio. For some of these pairs our method predicts that the dominant species changes from the monomer to the dimer species under varying pH conditions.