Integration of Layered Redox Proteins and Conductive Supports for Bioelectronic Applications

Integration of redox enzymes with an electrode support and formation of an electrical contact between the biocatalysts and the electrode is the fundamental subject of bioelectronics and optobioelectronics. This review addresses the recent advances and the scientific progress in electrically contacted, layered enzyme electrodes, and discusses the future applications of the systems in various bioelectronic devices, for example, amperometric biosensors, sensoric arrays, logic gates, and optical memories. This review presents the methods for the immobilization of redox enzymes on electrodes and discusses the covalent linkage of proteins, the use of supramolecular affinity complexes, and the reconstitution of apo-redox enzymes for the nanoengineering of electrodes with protein monolayers of electrodes with protein monolayers and multilayers. Electrical contact in the layered enzyme electrode is achieved by the application of diffusional electron mediators, such as ferrocene derivatives, ferricyanide, quinones, and bipyridinium salts. Covalent tethering of electron relay units to layered enzyme electrodes, the cross-linking of affinity complexes formed between redox proteins and electrodes functionalized with relay-cofactor units, or surface reconstitution of apo-enzymes on relay-cofactor-functionalized electrodes yield bioelectrocatalytic electrodes. The application of the functionalized electrodes as biosensor devices is addressed and further application of electrically "wired" enzymes as catalytic interfaces in biofuel cells is discussed. The organization of sensor arrays, self-calibrated biosensors, or gated bioelectronic devices requires the microstructuring of biomaterials on solid supports in the form of ordered micro-patterns. For example, light-sensitive layers composed of azides, benzophenone, or diazine derivatives associated with solid supports can be irradiated through masks to enable the patterned covalent linkage of biomaterials to surfaces. Alternatively, patterning of biomaterials can be accomplished by noncovalent interactions (such as in affinity complexes between avidin and a photolabeled biotin, or between an antibody and a photoisomerizable antigen layer) to provide a means of organizing protein microstructures on surfaces. The organization of patterned hydrophilic/hydrophobic domains on surfaces, by using photolithography, stamping, or micromachining methods, allows the selective patterning of surfaces by hydrophobic, noncovalent interactions. Photoactivated layered enzyme electrodes act as light-switchable optobioelectronic systems for the amperometric transduction of recorded photonic information. These systems can act as optical memories, biomolecular amplifiers, or logic gates. The photoswitchable enzyme electrodes are generated by the tethering of photoisomerizable groups to the protein, the reconstitution of apo-enzymes with semisynthetic photoisomerizable cofactor units, or the coupling of photoisomerizable electron relay units.     

Time-varying spectral change in the vowels of children and adults

Recent studies have shown that time-varying changes in formant pattern contribute to the phonetic specification of vowels. This variation could be especially important in children's vowels, because children have higher fundamental frequencies (f0's) than adults, and formant-frequency estimation is generally less reliable when f0 is high. To investigate the contribution of time-varying changes in formant pattern to the identification of children's vowels, three experiments were carried out with natural and synthesized versions of 12 American English vowels spoken by children (ages 7, 5, and 3 years) as well as adult males and females. Experiment 1 showed that (i) vowels generated with a cascade formant synthesizer (with hand-tracked formants) were less accurately identified than natural versions; and (ii) vowels synthesized with steady-state formant frequencies were harder to identify than those which preserved the natural variation in formant pattern over time. The decline in intelligibility was similar across talker groups, and there was no evidence that formant movement plays a greater role in children's vowels compared to adults. Experiment 2 replicated these findings using a semi-automatic formant-tracking algorithm. Experiment 3 showed that the effects of formant movement were the same for vowels synthesized with noise excitation (as in whispered speech) and pulsed excitation (as in voiced speech), although, on average, the whispered vowels were less accurately identified than their voiced counterparts. Taken together, the results indicate that the cues provided by changes in the formant frequencies over time contribute materially to the intelligibility of vowels produced by children and adults, but these time-varying formant frequency cues do not interact with properties of the voicing source.     

Iterated Homology of Simplicial Complexes

We develop an iterated homology theory for simplicial complexes. Thistheory is a variation on one due to Kalai. For a simplicial complex of dimension d – 1, and each r = 0, ...,d, we define rth iterated homology groups of . When r = 0, this corresponds to ordinary homology. If is a cone over , then when r = 1, we get the homology of . If a simplicial complex is (nonpure) shellable, then its iterated Betti numbers give the restriction numbers, h _k,j , of the shelling. Iterated Betti numbers are preserved by algebraic shifting, and may be interpreted combinatorially in terms of the algebraically shifted complex in several ways. In addition, the depth of a simplicial complex can be characterized in terms of its iterated Betti numbers.     

From the Becker–Döring to the Lifshitz–Slyozov–Wagner Equations

Connections between two classical models of phase transitions, the Becker–Döring (BD) equations and the Lifshitz–Slyozov–Wagner (LSW) equations, are investigated. Homogeneous coefficients are considered and a scaling of the BD equations is introduced in the spirit of the previous works by Penrose and Collet, Goudon, Poupaud and Vasseur. Convergence of the solutions to these rescaled BD equations towards a solution to the LSW equations is shown. For general coefficients an approach in the spirit of numerical analysis allows to approximate the LSW equations by a sequence of BD equations. A new uniqueness result for the BD equations is also provided.     

An efficient synthesis of juvabione and todomatuic acid via hydroboration-carbonylation

An efficient synthesis of juvabione (1a) and todomatuic acid (4), the key step of which involves a one-step conversion of methyl perillate (3) to a mixture consisting of 1a and epijuvabione (1b) via hydroboration-carbonylation is reported.     

Temperature-dependent Sellmeier equation for the refractive index of stoichiometric lithium tantalate

We present a temperature-dependent Sellmeier equation for the refractive index of stoichiometric LiTaO3. The extraordinary refractive index, for the range 0.39-4.1 microm and for temperatures of 30-200 degrees C, are based on previously published data [Jpn. J. Appl. Phys. 41, 465 (2002)] and on measured data derived from quasi-phase-matched (QPM) resonances. We used the new Sellmeier coefficients that we obtained to calculate the QPM wavelengths for an optical parametric oscillator (OPO) based on periodically poled stoichiometric LiTaO3 pumped at 1064 nm. The measured wavelengths of the OPO were in good agreement with our predictions.     

Prediction of total cerebral tissue volumes in normal appearing brain from sub-sampled segmentation volumes

The need for anatomical coverage and multi-spectral information must be balanced against examination and processing time to ensure high-quality, feasible imaging protocols for clinical research of cerebral development in normal-appearing brains. The focus of this study was to create and assess models to estimate total cerebral volumes of gray matter, white matter, and cerebrospinal fluid (CSF) from anatomically defined sub-samples of full clinical examinations. Pediatric patients (18F, 11M; aged 1.7 to 18.7, median 5.2 years) underwent a clinical imaging protocol consisting of 3 mm contiguous T1-, T2-, PD-, and FLAIR-weighted images after obtaining informed consent. Magnetic resonance imaging (MRI) sets were registered, RF-corrected, and then analyzed with a hybrid neural network segmentation and classification algorithm to identify normal brain parenchyma. The correlation between the image subsets and the total cerebral volumes of gray matter, white matter and CSF were examined through linear regression analyses. Five sub-sampled sets were defined and assessed in each patient to produce estimation models which were all significantly correlated (p < 0.001) with the total cerebral volumes of gray matter, white matter, and CSF. Volumes were estimated from as little as a single representative slice requiring minimal processing time, 27 min, but with an average estimation error of approximately 6%. Larger sub-samples of approximately three-quarters of the full cerebral volume required much more processing time, 2 h and 4 min, but produced estimates with an average error less than 2%. This study demonstrated that investigators can choose the amount of cerebrum sampled to optimize the acquisition and processing time against the degree of accuracy needed in the total cerebral volume estimates.