Raman spectroscopy based on a single-crystal sapphire fiber

We demonstrate the advantages of using a single-crystal sapphire fiber to perform Raman spectroscopy over using a standard glass fiber. The narrow Raman peaks and the low background signal of a single-crystal sapphire fiber allow for the detection of weaker Raman signals or Raman signals much closer to the incident laser wavelength than with a standard glass fiber, which has a strong broadband Raman spectrum of its own. The Raman spectra of calcite, single-walled carbon nanotubes, and aqueous sodium carbonate solution were collected using a 50 cm long, 200 μm diameter sapphire fiber, and then they were compared with the results using a 50 cm long, 100 μm diameter glass fiber. The Raman spectrum of each tested material becomes indistinguishable due to the background Raman signal of the glass fiber but can easily be seen using the sapphire fiber, which has only a few narrow Raman peaks of its own.     

In vivo imaging of intrinsic optical signals in chicken retina with functional optical coherence tomography

Visually evoked intrinsic optical signals (IOSs) were measured in vivo for the first time to our knowledge from all retina layers of the chicken retina with a combined functional optical coherence tomography and electroretinography (ERG) system. IOS traces were recorded from a small volume in the retina with 3.5 μm axial resolution and 7 ms time resolution. Comparison of the IOS and ERG traces shows a correlation between the positive and negative IOS measured from different retinal layers and the timing of the a and b waves in the ERG recording.     

Cooper pairs? magnetic moment in MCFL color superconductivity

We investigate the effect of the alignment of the magnetic moments of Cooper pairs of charged quarks that form at high density in three-flavor quark matter. The high-density phase of this matter in the presence of a magnetic field is known to be the Magnetic Color-Flavor-Locked (MCFL) phase of color superconductivity. We derive the Fierz identities of the theory and show how the explicit breaking of the rotational symmetry by the uniform magnetic field opens new channels of interactions and allows the formation of a new diquark condensate. The new order parameter is a spin-1 condensate proportional to the component in the field direction of the average magnetic moment of the pairs of charged quarks. The magnitude of the spin-1 condensate becomes comparable to the larger of the two scalar gaps in the region of large fields. The existence of the spin-1 condensate is unavoidable, as in the presence of a magnetic field there is no solution of the gap equations with nonzero scalar gaps and zero magnetic moment condensate. This is consistent with the fact that the extra condensate does not break any symmetry that has not already been broken by the known MCFL gaps. The spin-1 condensate enhances the condensation energy of pairs formed by charged quarks and the magnetization of the system. We discuss the possible consequences of the new order parameter on the issue of the chromomagnetic instability that appears in color superconductivity at moderate density.     

Synthesis of tetrahydroisoquinoline (TIQ)–oxazoline ligands and their application in enantioselective Henry reactions

A novel family of eleven new tetrahydroisoquinoline (TIQ)–oxazoline intermediates and five corresponding copper(II) catalysts has been developed and applied to the catalytic asymmetric Henry reaction of various aldehydes with nitromethane to provide β-hydroxy nitroalkanes in high conversion (>99%). This paper describes the synthesis of the TIQ compounds from l-dihydroxyphenylalanine (l-DOPA) as the starting material. The chiral ligands were complexed in situ with various transition metals such as Cu, Sc, Co, Zn, Ni and Mn and tested as a chiral catalyst for the Henry reaction. The reaction was optimized in terms of the metal, counter ion, solvent, temperature and over a range of substrates. The corresponding catalyst with copper(II) acetate and 2-propanol as the solvent provides the best enantioselectivities (up to 77% ee) of the corresponding nitroalcohol for 4-chlorobenzaldehyde.     

Unstrained C–C bond activation and directed fluorination through photocatalytically-generated radical cations

Expanding the repertoire of controlled radical fluorination techniques, we present a photosensitized unstrained C–C bond activation/directed monofluorination method using Selectfluor and 9-fluorenone. The reaction is amenable to the opening of multiple 1-acetal-2-aryl substituted rings to yield ω-fluoro carboxylic acids, esters, alcohols, and ketones with relative ease. Initial mechanistic insight suggests radical ion intermediates.     

Hydroxylation of the silica in microfabricated thin layer chromatography plates as probed by time‐of‐flight secondary ion mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy

Microfabricated silica thin layer chromatography (TLC) plates have previously been prepared on patterned carbon nanotube forests. The high temperatures used in their fabrication reduce the number of hydroxyl groups on their surfaces. Fortunately, silica can be rehydroxylated. In diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), a silanol peak below 3740 cm^?1 indicates a well‐hydroxylated silica surface that is fit for chromatography. Hydroxylations of our materials with HF are so effective that it is not possible to discern the position of this peak. In contrast, this signal is discernable when the plates are treated with NH₄OH. To find a more convenient method for studying the surfaces of TLC plates, time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) was considered. ToF‐SIMS is advantageous because multiple microfabricated TLC plates must be scraped to obtain enough silica for one DRIFT analysis, while static SIMS can be performed on very small regions (500 × 500 µm² or less) of individual plates. Ratios of the SiOH⁺ and Si⁺ ToF‐SIMS signals for microfabricated TLC plates correlated well with ~3740 cm^?1 silanol peaks from DRIFT. Thus, SIMS allows direct analysis of all of our treated and untreated plates, including those hydroxylated with HF. The best hydroxylation condition for HF, which was better than any studied for NH₄OH, was around 150 ppm at room temperature. The best hydroxylation condition for NH₄OH was 50 °C for 72 h. ToF‐SIMS versus DRIFT results of commercial TLC plates were also obtained and evaluated. Copyright © 2014 John Wiley & Sons, Ltd.     

New approach for natural products screening by real-time monitoring of hemoglobin hydrolysis using quartz crystal microbalance

The hemoglobin (Hb) released from erythrocytes is a primary nutritive component for many blood-feeding parasites. The aspartic protease cathepsin D is a hemoglobinase that is involved in the Hb degradation process and is considered an interesting target for chemotherapy intervention. However, traditional enzymatic assays for studying Hb degradation utilize spectrophotometric techniques, which do not allow real-time monitoring and can present serious interference problems. Herein, we describe a biosensor using simple approach for the real-time monitoring of Hb hydrolysis as well as an efficient screening method for natural products as enzymatic inhibitors using a quartz crystal microbalance (QCM) technique. Hemoglobin was anchored on the quartz crystal surface using mixed self-assembled monolayers. The addition of the enzyme caused a mass change (frequency shift) due to Hb hydrolysis, which was monitored in real time. From the frequency change patterns of the Hb-functionalized QCM, we evaluated the enzymatic reaction by determining the kinetic parameters of product formation (k_cat). The QCM enzymatic assay using immobilized human Hb was shown to be an excellent approach for screening possible inhibitors in complex mixtures, opening up a new avenue for the discovery of novel inhibitors.     

Dual Esterase‐ and Steroid‐Responsive Energy Transfer Modulation of Ruthenium(II) and Rhenium(I) Complex Functionalized Gold Nanoparticles

A number of adamantane‐containing ruthenium(II) and rhenium(I) complexes have been synthesized, characterized, and noncovalently functionalized with β‐cyclodextrin‐capped gold nanoparticles (β‐CD–GNPs) through the host–guest interaction between cyclodextrin and adamantane. The resultant nanoconjugates have been characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray analysis (EDX), and 2D ROESY ¹H NMR experiments. The Förster resonance energy transfer (FRET) properties of the nanoconjugates can be modulated by both esterase‐accelerated hydrolysis and competitive displacement of steroid, by monitoring the emission intensity and luminescence lifetime. The FRET efficiencies are found to vary with the nature of the chromophores and the length of the spacer between the transition metal complexes and the GNPs. This work constitutes a “proof‐of‐principle” assay method for the dual‐functional detection of important classes of biomolecules, such as enzymes and steroids.     

Cleavage of a PN Bond in a Urea‐Containing (Ph2P(R)PPh2)‐Bridged Dinuclear Gold(I) Thiolate Complex by Fluoride and a Mechanistic Insight

A urea‐containing, (Ph₂P(R)PPh₂)‐bridged, dinuclear, gold(I) thiolate complex, [Au₂{Ph₂PN(C₆H₄OMe‐4)PPh₂}(SC₆H₄NHCONHC₆H₅)₂] ( 1 ) was designed and synthesized and its photophysical and anion recognition properties studied. The results show that 1 has a high selectivity toward F^?. Upon addition of F^?, the yellow solution was decolorized, and drastic changes of emission and ¹H and ³¹P{¹H} NMR signals were observed. Interestingly, these changes are attributed to fluoride‐assisted P?N bond hydrolysis, instead of the expected hydrogen‐bonding interactions with the urea receptor. Similar changes were observed for two other basic anions, AcO^? and H₂PO₄^?, but to a much lesser extent; and these anions were found to bind to the urea receptor at the same time. On the other hand, Cl^? was found to only bind to the urea moiety through hydrogen‐bonding interactions. Further studies with the control complex [Au₂{Ph₂PN(C₆H₄OMe‐4)PPh₂}Cl₂] ( 2 ) indicate that F^? assists the hydrolysis process via cleavage of the P?N bond. DFT calculations were performed to study the reaction mechanism for the fluoride‐assisted P?N bond hydrolysis of 2 ; these provide a better insight into the role of fluoride in the hydrolysis.