A joint theoretical and experimental investigation on the 13C and 1H NMR chemical shifts of coumarin derivatives

¹H and ¹³C NMR chemical shifts of coumarin derivatives have been determined using first principles approaches with and without accounting for the effects of the solvent and compared to experiment in order to assess their reliability. Good linear relationships are obtained between theory and experiment, which allows correcting the calculated values for systematic errors. This is particularly the case when using the PCM scheme to model the solvent effects because the δ values larger than 150 ppm are more difficult to reproduce. The final accuracy of the method amounts to about 1 ppm for ¹³C and 0.05 ppm for ¹H.     

Molecular signal suppression by in situ microextraction in nuclear magnetic resonance spectroscopy

The detailed characterization of complex mixtures by NMR is often hampered by the presence of signals from uninformative compounds, the resonances of which overlap with those of the molecules of interest. We provide here a proof of principle for an approach to NMR signal suppression in complex samples using Molecularly Imprinted Polymers (MIPS). Addition of a few milligrams of polymer to a solution traps the target molecule in typical micromolar to millimolar concentration, thus achieving in situ signal suppression, without altering any other spectral features. This method minimized any manipulation or perturbation of the spectrum and was applied to a complex mixture of known compounds and to a plant extract, in both cases spiked with a compound (bisphenol A), which was subsequently removed by selective binding to a complementary MIP. What is described in this report is comparable with microextraction and may in due course be applied to a large number of analytical challenges. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation of Well‐Defined Poly[(ethylene oxide)‐block‐(sodium 2‐acrylamido‐2‐methyl‐1‐propane sulfonate)] Diblock Copolymers by Water‐Based Atom Transfer Radical Polymerization

Summary: Well‐defined poly[(ethylene oxide)‐block‐(sodium 2‐acrylamido‐2‐methyl‐1‐propane sulfonate)] diblock copolymers [P(EO_m‐b‐AMPS_n)], have been obtained by water‐based ATRP using α‐methoxy‐ω‐(2‐methylbromoisobutyrate) poly(ethylene oxide)s (MeO‐P[EO]_m‐BrⁱB with m ranging from 12 to 113) and CuBr · 2Bpy (Bpy for 2,2′‐bipyridyl) as macroinitiator and catalytic complex, respectively. Compared to direct polymerization in water, it has been demonstrated that the water/methanol (3:1, v/v) mixture is better suited for predicting the final number‐average molar mass from the initial monomer‐to‐macroinitiator molar ratio and achieving a quite narrow polydispersity, even at high monomer conversion ( ≈ 1.4 at 80% conversion). The effect of temperature, solvent mixture composition and addition of NaCl salt on the polymerization rate and extent of control over the copolymer molecular parameters have been highlighted as well.

     

Chromatographic separation simulation of metal‐chelating peptides from surface plasmon resonance binding parameters

Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental t_R with the simulated t_R obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of t_R were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance.     

Cis and trans selective 1,4-addition of a lithium dithioester enolate to 4-O-TBS-2-cyclohexenone

The 1,4-addition of the lithium enolate of methyldithioacetate (LMDTA) to (+/-)-4-O-TBS-2-cyclohexenone (3) can be varied from being highly 3,4-trans selective to being highly 3,4-cis selective simply by varying the reaction temperature. This stereodivergency allows expedient syntheses of the corresponding trans and cis methyl esters 6t and 6c and derived bicyclic ketolactones 7t and 7c.     

Ligand-receptor interactions in chains of colloids: when reactions are limited by rotational diffusion

We discuss the theory of ligand receptor reactions between two freely rotating colloids in close proximity to one other. Such reactions, limited by rotational diffusion, arise in magnetic bead suspensions where the beads are driven into close contact by an applied magnetic field as they align in chainlike structures. By a combination of reaction-diffusion theory, numerical simulations, and heuristic arguments, we compute the time required for a reaction to occur in a number of experimentally relevant situations. We find in all cases that the time required for a reaction to occur is larger than the characteristic rotation time of the diffusion motion tau(rot). When the colloids carry one ligand only and a number n of receptors, we find that the reaction time is, in units of tau(rot), a function simply of n and of the relative surface alpha occupied by one reaction patch alpha = pirC2/(4pir2), where rC is the ligand receptor capture radius and r is the radius of the colloid.     

Low-temperature H2 sensing in self-assembled organotin thin films

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.     

HRMAS NMR spectroscopy combined with chemometrics as an alternative analytical tool to control cigarette authenticity

In this paper, we present for the first time the use of high-resolution magic angle spinning nuclear magnetic resonance (HRMAS NMR) spectroscopy combined with chemometrics as an alternative tool for the characterization of tobacco products from different commercial international brands as well as for the identification of counterfeits. Although cigarette filling is a very complex chemical mixture, we were able to discriminate between dark, bright, and additive-free cigarette blends belonging to six different filter-cigarette brands, commercially available, using an approach for which no extraction procedure is required. Second, we focused our study on a specific worldwide-distributed brand for which established counterfeits were available. We discriminated those from their genuine counterparts with 100 % accuracy using unsupervised multivariate statistical analysis. The counterfeits that we analyzed showed a higher amount of nicotine and solanesol and a lower content of sugars, all endogenous tobacco leaf metabolites. This preliminary study demonstrates the great potential of HRMAS NMR spectroscopy to help in controlling cigarette authenticity.

Highly Enantioselective Rhodium(I)‐Catalyzed Carbonyl Carboacylations Initiated by C?C Bond Activation

The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom‐economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of C C bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)‐catalyzed transformation is induced by an enantiotopic C C bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones.     

Influence of deposition conditions on the optical properties of erbium-doped yttrium oxide films grown by aerosol-UV assisted MOCVD

Erbium-doped Y₂O₃ films were prepared by aerosol-UV assisted metal-organic chemical vapour deposition (MOCVD) at 410 °C. The effects of humidity of carrier gas and UV-assistance on their structure and optical properties were investigated on the as-deposited and thermal annealed films using infrared spectroscopy, X-ray diffraction and transmission electron microscopy. It was found that the as-deposited Er:Y₂O₃ films crystallise in the Y₂O₃ cubic structure and present a very low organic contamination when the deposition takes place under high air humidity and, even better, with UV-assistance. After annealing, two different structural phases are observed corresponding to the cubic and the monoclinic structures of Y₂O₃. The Er³⁺ luminescence analysed in the visible and IR regions, shows the classical green transitions. The best optical properties were obtained with as-deposited and annealed Er:Y₂O₃ films grown under high air humidity with UV-assistance. Under such deposition conditions, ⁴I_13/2 lifetimes was found to be 3.07 and 6.1 ms for films annealed at 800 and 1000 °C, respectively, and up-conversion phenomena were underlined. This indicates that the deposition conditions, in particular air humidity, play an important role in the luminescent properties even after annealing.