Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

We report the syntheses and characterizations of the first polyoxothiometalate complexes isolated from the reaction of the oxothiocationic [Mo(V)(2)O(2)S(2)](2+) precursor and bisphosphonate ligands H(2)O(3)PCR(OH)PO(3)H(2) (R = C(4)H(5)N(2), zoledronic acid; R = C(3)H(6)NH(2), alendronic acid). [(Mo(2)O(2)S(2)(H(2)O))(4)(O(3)PC(O)(C(4)H(6)N(2))PO(3))(4)](8-) (Mo(8)S(8)(Zol)(4)) and [(Mo(2)O(2)S(2)(H(2)O))(4)(O(3)PC(O)(C(3)H(6)NH(3))PO(3))(4)](8-) (Mo(8)S(8)(Ale)(4)) contain four Mo(V) dimers connected via bisphosphonate ligands. These compounds offer a unique opportunity to compare the structures and properties of cyclic compounds obtained with [Mo(2)O(2)S(2)](2+) and with [Mo(2)O(4)](2+). The oxothio compounds appear less stable in solution than the oxo analogue, confirming the higher lability and versatility of [Mo(2)O(2)S(2)]-based compounds compared to [Mo(2)O(4)]-based POMs. Multinuclear and multidimensional solid-state NMR studies were carried out to complement X-ray diffraction analysis. Information on short-range interactions, dynamic behaviors, and local disorder within the crystalline materials are therefore reported. Furthermore, the electrocatalytic properties of Mo(8)S(8)(Ale)(4) and of the analogous [(Mo(2)O(4)(H(2)O))(4)(O(3)PC(O)(C(3)H(6)NH(3))PO(3))(4)](8-) (Mo(8)O(8)(Ale)(4)) immobilized onto the surface of a glassy carbon electrode were studied, thus evidencing the ability of [Mo(2)O(2)S(2)]-based cycles to promote the reduction of protons into hydrogen, whereas the oxo analogue appeared inactive.     

Ultrasensitive electrochemical detection of prostate-specific antigen (PSA) using gold-coated magnetic nanoparticles as 'dispersible electrodes'

Herein, we demonstrate the use of modified gold-coated magnetic nanoparticles as 'dispersible electrodes' which act as selective capture vehicles for electrochemical detection of prostate-specific antigen (PSA). A key advantage of this system is the ability to quantify non-electrochemical active analytes such as proteins with unprecedented detection limits and fast response times.     

The biochemiresistor: an ultrasensitive biosensor for small organic molecules

New sensation: A resistance-based biosensor uses gold-coated magnetic nanoparticles (Au@MNPs) functionalized with the antibiotic enrofloxin (see picture; purple), which bind to anti-enrofloxin as analyte (blue). The Au@MNPs can be magnetically assembled between electrodes, and the measured resistance R is a function of analyte concentration.     

X-ray transient absorption and picosecond IR spectroscopy of fulvalene(tetracarbonyl)diruthenium on photoexcitation

Caught in the light: The fulvalene diruthenium complex shown on the left side of the picture captures sun light, causing initial Ru-Ru bond rupture to furnish a long-lived triplet biradical of syn?configuration. This species requires thermal activation to reach a crossing point (middle) into the singlet manifold on route to its thermal storage isomer on the right through the anti?biradical.     

Critical point coupling and proximity effects in ^{4}he at the superfluid transition

We report measurements of the superfluid fraction ρ_{s}/ρ and specific heat c_{p} near the superfluid transition of ^{4}He when confined in an array of (2 μm)^{3} boxes at a separation of S=2 μm and coupled through a 32.5?nm film. We find that c_{p} is strongly enhanced when compared with data where coupling is not present. An analysis of this excess signal shows that it is proportional to the finite-size correlation length in the boxes ξ(t,L), and it is measurable as far as S/ξ～30-50. We obtain ξ(0,L) and the scaling function (within a constant) for ξ(t,L) in an L^{3} box geometry. Furthermore, we find that ρ_{s}/ρ of the film persists a full decade closer to the bulk transition temperature T_{λ} than a film uninfluenced by proximity effects. This excess in ρ_{s}/ρ is measurable even when S/ξ>100, which cannot be understood on the basis of mean field theory.     

All-Optical Modulation of Localized Surface Plasmon Coupling in a Hybrid System Composed of Photo-Switchable Gratings and Au Nanodisk Arrays

We conduct a real-time study of all-optical modulation of localized surface plasmon resonance (LSPR) coupling in a hybrid system that integrates a photo-switchable optical grating with a gold nanodisk array. This hybrid system enables us to investigate two important interactions: 1) LSPR-enhanced grating diffraction, and 2) diffraction-mediated LSPR in the Au nanodisk array. The physical mechanism underlying these interactions was analyzed and experimentally confirmed. With its advantages in cost-effective fabrication, easy integration, and all-optical control, the hybrid system described in this work could be valuable in many nanophotonic applications.     

Observations on braided thin wire nucleate boiling in microgravity

A microgravity experiment was conducted on the Space Shuttle Endeavor (STS-108) to observe sustained nucleate boiling of water. Subcooled water was boiled with a single strand and a braid of three 0.16 mm diameter and 80 mm long Nichrome resistive wires. A CCD video camera recorded the experiment while six thermistors recorded the temperature of the fluid at various distances from the heating element. This paper reports experimental results in observations, measurements, and data analysis. Bubble explosions were found to take place shortly after the onset of boiling for both the single and braid of wires. The explosion may produce a high heat transfer rate, as it generates a cloud of microbubbles. The number, size, and departure rate of the bubbles from the heater wire were measured and compared with theoretical models as a function of time. The temperature measurements revealed a complex temperature distribution in the fluid chamber due to bubbles ejected from the wire that carried thermal energy close to the temperature sensors. Drag forces on departing bubbles were calculated based on bubble movement and used to predict bubble propagation. Results from this experiment provided further understanding of nucleate boiling dynamics in microgravity for the eventual design and implementation of two-phase heat transfer systems in space applications.     

General and scalable amide bond formation with epimerization-prone substrates using T3P and pyridine

The mild combination of T3P (n-propanephosphonic acid anhydride) and pyridine has been developed for low-epimerization amide bond formation and implemented for the synthesis of a key intermediate to a glucokinase activator. This robust method is general for the coupling of various racemization-prone acid substrates and amines, including relatively non-nucleophilic anilines, and provides amides in high yields with very low epimerization. With easy reaction setup and product isolation, this protocol offers several practical and experimental benefits.