Mark E. Newton

On the existence of positively charged single-substitutional nitrogen in diamond

Infra-red (IR) absorption results on irradiated and annealed synthetic diamond are presented which confirm an earlier proposal that a component found in the defect-induced one-phonon region of some diamonds arises from positively charged single-substitutional nitrogen . The concentration ratio of to neutral substitutional nitrogen centres may be changed by shining light of various energies onto the examined samples. By correlating changes in absorption of the IR component associated with centres with changes in the component, and using a previously determined relation between the concentration of centres and peak absorption coefficient at 1130 , the relationship between peak absorption at 1332 and concentration of centres has been derived, namely 1 of absorption is produced by ppm centres. Other defects may also give rise to absorption at 1332 , but the component is uniquely identified by further peaks at 1046 and 950 . The significance of this component is demonstrated by the fact that some samples can contain in excess of 80 ppm centres, and this must consequently be accounted for when assaying the total nitrogen concentration in such samples. Using the above relationship useful parameters relating the concentration of neutral vacancies, negative vacancies and negatively charged nitrogen-vacancy centres to their respective zero-phonon line integrated absorptions have been derived.

A spectrometer designed for 6.7 and 14.1 T DNP-enhanced solid-state MAS NMR using quasi-optical microwave transmission

A Dynamic Nuclear Polarisation (DNP) enhanced solid-state Magic Angle Spinning (MAS) NMR spectrometer operating at 6.7 T is described and demonstrated. The 187 GHz TE(13) fundamental mode of the FU CW VII gyrotron is used as the microwave source for this magnetic field strength and 284 MHz (1)H DNP-NMR. The spectrometer is designed for use with microwave frequencies up to 395 GHz (the TE(16) second-harmonic mode of the gyrotron) for DNP at 14.1T (600 MHz (1)H NMR). The pulsed microwave output from the gyrotron is converted to a quasi-optical Gaussian beam using a Vlasov antenna and transmitted to the NMR probe via an optical bench, with beam splitters for monitoring and adjusting the microwave power, a ferrite rotator to isolate the gyrotron from the reflected power and a Martin-Puplett interferometer for adjusting the polarisation. The Gaussian beam is reflected by curved mirrors inside the DNP-MAS-NMR probe to be incident at the sample along the MAS rotation axis. The beam is focussed to a ~1 mm waist at the top of the rotor and then gradually diverges to give much more efficient coupling throughout the sample than designs using direct waveguide irradiation. The probe can be used in triple channel HXY mode for 600 MHz (1)H and double channel HX mode for 284 MHz (1)H, with MAS sample temperatures ≥85 K. Initial data at 6.7 T and ~1 W pulsed microwave power are presented with (13)C enhancements of 60 for a frozen urea solution ((1)H-(13)C CP), 16 for bacteriorhodopsin in purple membrane ((1)H-(13)C CP) and 22 for (15)N in a frozen glycine solution ((1)H-(15)N CP) being obtained. In comparison with designs which irradiate perpendicular to the rotation axis the approach used here provides a highly efficient use of the incident microwave beam and an NMR-optimised coil design.

Amperometric Oxygen Sensor Based on a Platinum Nanoparticle- Modified Polycrystalline Boron Doped Diamond Disk Electrode

Pt nanoparticle (NP)-modified polycrystalline boron-doped diamond (pBDD) disk electrodes have been fabricated and employed as amperometric sensors for the determination of dissolved oxygen concentration in aqueous solution. pBDD columns were cut using laser micromachining techniques and sealed in glass, in order to make disk electrodes which were then characterized electrochemically. Electrodeposition of Pt onto the diamond electrodes was optimized so as to give the maximum oxygen reduction peak current with the lowest background signal. Pt NPs, >0-10 nm diameter, were found to deposit randomly across the pBDD electrode, with no preference for grain boundaries. The more conductive grains were found to promote the formation of smaller nanoparticles at higher density. With the use of potential step chronoamperometry, in which the potential was stepped to a diffusion-limited value, a four electron oxygen reduction process was found to occur at the Pt NP-modified pBDD electrode. Furthermore the chronoamperometric response scaled linearly with dissolved oxygen concentration, varied by changing the oxygen/nitrogen ratio of gas flowed into solution. The sensor was used to detect dissolved oxygen concentrations with high precision over the pH range 4-10.

Electrochemical Mapping Reveals Direct Correlation between Heterogeneous Electron-Transfer Kinetics and Local Density of States in Diamond Electrodes

Conducting carbon materials: a multi-microscopy approach shows that local heterogeneous electron-transfer rates at conducting diamond electrodes correlate with the local density of electronic states. This model of electroactivity is of considerable value for the rational design of conducting diamond electrochemical technologies, and also provides key general insights on electrode structure controls in electrochemical kinetics.

Examination of the Factors Affecting the Electrochemical Performance of Oxygen-Terminated Polycrystalline Boron-Doped Diamond Electrodes

In order to produce polycrystalline oxygen-terminated boron-doped diamond (BDD) electrodes suitable for electroanalysis (i.e., widest solvent window, lowest capacitive currents, stable and reproducible current responses, and capable of demonstrating fast electron transfer) for outer sphere redox couples, the following factors must be considered. The material must contain enough boron that the electrode shows metal-like conductivity; electrical measurements demonstrate that this is achieved at [B] > 10(20) B atoms cm(-3). Even though BDD contains a lower density of states than a metal, it is not necessary to use extreme doping levels to achieve fast heterogeneous electron transfer (HET). An average [B] ~ 3 × 10(20) B atoms cm(-3) was found to be optimal; increasing [B] results in higher capacitive values and increases the likelihood of nondiamond carbon (NDC) incorporation. Hydrogen-termination causes a semiconducting BDD electrode to behave metal-like due to the additional surface conductivity hydrogen termination brings. Thus, unless [B] of the material is known, the electrical properties of the electrode may be incorrectly interpreted. Note, this layer (formed on a lapped electrode) is electrochemically unstable, an effect which is exacerbated at increased potentials. It is essential during growth that NDC is minimized as it acts to increase capacitive currents and decrease the solvent window. We found complete removal of NDC after growth using aggressive acid cleans, acid cycling, and diamond polishing impossible. Although hydrogen termination can mask the NDC signature in the solvent window and lower capacitive currents, this is not a practical procedure for improving sensitivity in electroanalysis. Finally, alumina polishing of lapped, NDC free, freestanding, BDD electrodes was found to be an effective way to produce well-defined, stable, and reproducible surfaces, which support fast (reversible) HET for Fe(CN)6(4-) electrolysis, the first time this has been reported at an oxygen-terminated surface.

Phonon Raman scattering of RCrO_{3} perovskites (R=Y, La, Pr, Sm, Gd, Dy, Ho, Yb, Lu)

We report a systematic investigation of orthorhombic perovskite-type RCrO3 powder samples by Raman scattering for nine different rare earth R3+ cations (R = Y, La, Pr, Sm, Gd, Dy, Ho, Yb, and Lu). The room-temperature Raman spectra and the associated phonon mode assignment provide reference data for structural investigation of the whole series of RCrO3 orthochromites and phonon ab-initio calculations. The assignment of the chromite spectra and comparison with Raman data on other orthorhombic perovskites allows correlating the phonon modes with the structural distortions in the RCrO3 series. In particular, two Ag modes are identified as octahedra rotation soft modes, as their positions scale linearly with the octahedra tilt angle of the CrO6 octahedra.

Tryptophan Switch for a Photoactivated Platinum Anticancer Complex

The octahedral Pt(IV) complex trans,trans,trans-[Pt(N(3))(2)(OH)(2)(py)(2)] (1) is potently cytotoxic to cancer cells when irradiated with visible (blue) light. We show that the acute photocytotoxicity can be switched off by low doses (500 μM) of the amino acid l-tryptophan. EPR and NMR spectroscopic experiments using spin traps show that l-Trp quenches the formation of azidyl radicals, probably by acting as an electron donor. l-Trp is well-known as a mediator of electron transfer between distant electron acceptor/donor centers in proteins, and such properties may make the free amino acid clinically useful for controlling the activity of photochemotherapeutic azido Pt(IV) drugs. Since previous work has demonstrated the ability of photoactivated 1 to platinate DNA, this suggests that the high potency of such photoactive platinum complexes is related to their dual attack on cancer cells by radicals and Pt(II) photoproducts.

Increasing the coherence time of single electron spins in diamond by high temperature annealing

Negatively charged nitrogen-vacancy (NV−) centers in diamond produced by ion implantation often show properties different from NVs created during the crystal growth. We observe that NVs created from nitrogen ion implantation at 30–300 keV show much shorter electron spin coherence time T2 as compared to the “natural” NVs and about 20% of them show switching from NV− to NV0. We show that annealing the diamond at T=1200 °C substantially increases T2 and at the same time the fraction of NVs converting from NV− to NV0 is greatly reduced.

Reduction of Quinones by NADH Catalyzed by Organoiridium Complexes

One electron at a time: Half-sandwich organometallic cyclopentadienyl–IrIII complexes containing N,N-chelated ligands can catalyze the reduction of quinones (Q), such as vitamin K3, to semiquinones (Q.ˉ) by coenzyme NADH (see picture). DFT calculations suggest that the mechanism involves hydride transfer followed by two one-electron transfers and the unusual IrII oxidation state as a key transient intermediate.

Production of oriented nitrogen-vacancy color centers in synthetic diamond

The negatively charged nitrogen-vacancy (