Ramped-amplitude NOVEL.

We present a pulsed dynamic nuclear polarization (DNP) study using a ramped-amplitude nuclear orientation via electron spin locking (RA-NOVEL) sequence that utilizes a fast arbitrary waveform generator (AWG) to modulate the microwave pulses together with samples doped with narrow-line radicals such as 1,3-bisdiphenylene-2-phenylallyl (BDPA), sulfonated-BDPA (SA-BDPA), and trityl-OX063. Similar to ramped-amplitude cross polarization in solid-state nuclear magnetic resonance, RA-NOVEL improves the DNP efficiency by a factor of up to 1.6 compared to constant-amplitude NOVEL (CA-NOVEL) but requires a longer mixing time. For example, at τmix = 8 µs, the DNP efficiency reaches a plateau at a ramp amplitude of ∼20 MHz for both SA-BDPA and trityl-OX063, regardless of the ramp profile (linear vs. tangent). At shorter mixing times (τmix = 0.8 µs), we found that the tangent ramp is superior to its linear counterpart and in both cases there exists an optimum ramp size and therefore ramp rate. Our results suggest that RA-NOVEL should be used instead of CA-NOVEL as long as the electronic spin lattice relaxation T1e is sufficiently long and/or the duty cycle of the microwave amplifier is not exceeded. To the best of our knowledge, this is the first example of a time domain DNP experiment that utilizes modulated microwave pulses. Our results also suggest that a precise modulation of the microwave pulses can play an important role in optimizing the efficiency of pulsed DNP experiments and an AWG is an elegant instrumental solution for this purpose.

Time domain DNP with the NOVEL sequence.

We present results of a pulsed dynamic nuclear polarization (DNP) study at 0.35 T (9.7 GHz/14.7 MHz for electron/(1)H Larmor frequency) using a lab frame-rotating frame cross polarization experiment that employs electron spin locking fields that match the (1)H nuclear Larmor frequency, the so called NOVEL (nuclear orientation via electron spin locking) condition. We apply the method to a series of DNP samples including a single crystal of diphenyl nitroxide (DPNO) doped benzophenone (BzP), 1,3-bisdiphenylene-2-phenylallyl (BDPA) doped polystyrene (PS), and sulfonated-BDPA (SA-BDPA) doped glycerol/water glassy matrices. The optimal Hartman-Hahn matching condition is achieved when the nutation frequency of the electron matches the Larmor frequency of the proton, ω(1S) = ω(0I), together with possible higher order matching conditions at lower efficiencies. The magnetization transfer from electron to protons occurs on the time scale of ∼100 ns, consistent with the electron-proton couplings on the order of 1-10 MHz in these samples. In a fully protonated single crystal DPNO/BzP, at 270 K, we obtained a maximum signal enhancement of ε = 165 and the corresponding gain in sensitivity of ε(T1/T(B))(1/2)=230 due to the reduction in the buildup time under DNP. In a sample of partially deuterated PS doped with BDPA, we obtained an enhancement of 323 which is a factor of ∼3.2 higher compared to the protonated version of the same sample and accounts for 49% of the theoretical limit. For the SA-BDPA doped glycerol/water glassy matrix at 80 K, the sample condition used in most applications of DNP in nuclear magnetic resonance, we also observed a significant enhancement. Our findings demonstrate that pulsed DNP via the NOVEL sequence is highly efficient and can potentially surpass continuous wave DNP mechanisms such as the solid effect and cross effect which scale unfavorably with increasing magnetic field. Furthermore, pulsed DNP is also a promising avenue for DNP at high temperature.

Overhauser effects in insulating solids.

We report magic angle spinning, dynamic nuclear polarization (DNP) experiments at magnetic fields of 9.4 T, 14.1 T, and 18.8 T using the narrow line polarizing agents 1,3-bisdiphenylene-2-phenylallyl (BDPA) dispersed in polystyrene, and sulfonated-BDPA (SA-BDPA) and trityl OX063 in glassy glycerol/water matrices. The (1)H DNP enhancement field profiles of the BDPA radicals exhibit a significant DNP Overhauser effect (OE) as well as a solid effect (SE) despite the fact that these samples are insulating solids. In contrast, trityl exhibits only a SE enhancement. Data suggest that the appearance of the OE is due to rather strong electron-nuclear hyperfine couplings present in BDPA and SA-BDPA, which are absent in trityl and perdeuterated BDPA (d21-BDPA). In addition, and in contrast to other DNP mechanisms such as the solid effect or cross effect, the experimental data suggest that the OE in non-conducting solids scales favorably with magnetic field, increasing in magnitude in going from 5 T, to 9.4 T, to 14.1 T, and to 18.8 T. Simulations using a model two spin system consisting of an electron hyperfine coupled to a (1)H reproduce the essential features of the field profiles and indicate that the OE in these samples originates from the zero and double quantum cross relaxation induced by fluctuating hyperfine interactions between the intramolecular delocalized unpaired electrons and their neighboring nuclei, and that the size of these hyperfine couplings is crucial to the magnitude of the enhancements. Microwave power dependent studies show that the OE saturates at considerably lower power levels than the solid effect in the same samples. Our results provide new insights into the mechanism of the Overhauser effect, and also provide a new approach to perform DNP experiments in chemical, biophysical, and physical systems at high magnetic fields.

Clostridium difficile as a cause of healthcare-associated diarrhoea among children in Auckland, New Zealand: clinical and molecular epidemiology.

We aimed to determine the incidence of Clostridium difficile infection (CDI), the molecular epidemiology of circulating C. difficile strains and risk factors for CDI among hospitalised children in the Auckland region. A cross-sectional study was undertaken of hospitalised children <15 years of age in two hospitals investigated for healthcare-associated diarrhoea between November 2011 and June 2012. Stool specimens were analysed for the presence of C. difficile using a two-step testing algorithm including polymerase chain reaction (PCR). C. difficile was cultured and PCR ribotyping performed. Demographic data, illness characteristics and risk factors were compared between children with and without CDI. Non-duplicate stool specimens were collected from 320 children with a median age of 1.2 years (range 3 days to 15 years). Forty-six patients (14 %) tested met the definition for CDI. The overall incidence of CDI was 2.0 per 10,000 bed days. The percentage of positive tests among neonates was only 2.6 %. PCR ribotyping showed a range of strains, with ribotype 014 being the most common. Significant risk factors for CDI were treatment with proton pump inhibitors [risk ratio (RR) 1.74, 95 % confidence interval (CI) 1.09-5.59; p = 0.002], presence of underlying malignancy (RR 2.71, 95 % CI 1.65-4.62; p = 0.001), receiving chemotherapy (RR 2.70, 95 % CI 1.41-4.83; p = 0.003) and exposure to antibiotics (RR 1.17, 95 % CI 0.99-1.17; p = 0.03). C. difficile is an important cause of healthcare-associated diarrhoea in this paediatric population. The notion that neonatal populations will always have high rates of colonisation with C. difficile may not be correct. Several risk factors associated with CDI among adults were also found to be significant.

Measuring local optical properties: near-field polarimetry of photonic block copolymer morphology.

Ultrahigh molecular weight polystyrene-b-polyisoprene block copolymers (BCs), noted for their photonic behavior, were imaged using transmission near-field scanning optical microscopy (NSOM) and NSOM polarimetry. Our improved scheme for polarization modulation (PM) polarimetry, which accounts for optical anisotropies of the NSOM aperture probe, enables mapping of the local diattenuation and birefringence (with separately aligned diattenuating and fast axes) in these specimens with subdiffraction limited resolution. PM-NSOM micrographs illuminate the mesoscopic optical nature of these BC specimens by resolving individual microphase domains and defect structures.

Conjugated polymers containing 2,3-dialkoxybenzene and iptycene building blocks.

[structure: see text]. New poly(phenylene ethynylene)s (PPEs) and poly(phenylene vinylene)s (PPVs) that are highly emissive in solution and thin films were prepared utilizing palladium-catalyzed cross-coupling between new 1,4-diiodo-2,3-dialkoxybenzene- and iptycene-containing monomers. The absorption and emission spectra of the resulting polymers consistently showed a significant blue shift relative to the corresponding polymer analogues containing 2,5-dialkoxyphenylenes.

Control of conformational and interpolymer effects in conjugated polymers.

The role of conjugated polymers in emerging electronic, sensor and display technologies is rapidly expanding. In spite of extensive investigations, the intrinsic spectroscopic properties of conjugated polymers in precise conformational and spatial arrangements have remained elusive. The difficulties of obtaining such information are endemic to polymers, which often resist assembly into single crystals or organized structures owing to entropic and polydispersity considerations. Here we show that the conformation of individual polymers and interpolymer interactions in conjugated polymers can be controlled through the use of designed surfactant poly(p-phenylene-ethynylene) Langmuir films. We show that by mechanically inducing reversible conformational changes of these Langmuir monolayers, we can obtain the precise interrelationship of the intrinsic optical properties of a conjugated polymer and a single chain's conformation and/or interpolymer interactions. This method for controlling the structure of conjugated polymers and establishing their intrinsic spectroscopic properties should permit a more comprehensive understanding of fluorescent conjugated materials.

Molecular photonic and electronic circuitry for ultra-sensitive chemical sensors.

Molecular wires have progressed from an intellectual curiosity to become the basis for chemical sensors with unprecedented sensitivity. Particularly exciting opportunities are those that make use of biological superstructures to effect conduction through assemblies of molecular wires.