Electronic Chart of the Future: The Hampton Roads Project

ECDIS is evolving from a two-dimensional static display of chart-related data to a decision support system capable of providing real-time or forecast information. While there may not be consensus on how this will occur, it is clear that to do this, ENC data and the shipboard display environment must incorporate both depth and time in an intuitively understandable way. Currently, we have the ability to conduct high-density hydrographic surveys capable of producing ENCs with decimeter contour intervals or depth areas. Yet, our existing systems and specifications do not provide for a full utilization of this capability. Ideally, a mariner should be able to benefit from detailed hydrographic data, coupled with both forecast and real-time water levels, and presented in a variety of perspectives. With this information mariners will be able to plan and carry out transits with the benefit of precisely determined and easily perceived underkeel, overhead, and lateral clearances. This paper describes a Hampton Roads Demonstration Project to investigate the challenges and opportunities of developing the “Electronic Chart of the Future.” In particular, a three-phase demonstration project is being planned: 1. Compile test datasets from existing and new hydrographic surveys using advanced data processing and compilation procedures developed at the University of New Hampshire’s Center for Coastal and Ocean Mapping/Joint Hydrographic Center (CCOM/JHC); 2. Investigate innovative approaches being developed at the CCOM/JHC to produce an interactive time- and tide-aware navigation display, and to evaluate such a display on commercial and/or government vessels; 3. Integrate real-time/forecast water depth information and port information services transmitted via an AIS communications broadcast

Characterizing Mode Anharmonicity and Huang–Rhys Factors Using Models of Femtosecond Coherence Spectra

Femtosecond laser pulses readily produce coherent quantum beats in transient–absorption spectra. These oscillatory signals often arise from molecular vibrations and therefore may contain information about the excited-state potential energy surface near the Franck–Condon region. Here, by fitting the measured spectra of two laser dyes to microscopic models of femtosecond coherence spectra (FCS) arising from molecular vibrations, we classify coherent quantum-beat signals as fundamentals or overtones and quantify their Huang–Rhys factors and anharmonicity values. We discuss the extracted Huang–Rhys factors in the context of quantum-chemical computations. This work solidifies the use of FCS for analysis of coherent quantum beats arising from molecular vibrations, which will aid studies of molecular aggregates and photosynthetic proteins

The Influence of Supplemental Zinc and Ractopamine Hydrochloride on the Performance and Longissimus Thoracis Proteome of Finishing Beef Steers

To determine how Zn and ractopamine hydrochloride (RAC) supplementation affect the longissimus thoracis muscle proteome in beef cattle, 48 high percentage Angus steers (494±18.2 kg) were utilized in a 2×2 factorial study design. Steers were blocked by body weight (BW) and genetic gain potential (GeneMax; Zoetis, Parsippany, NJ) into control (CON; analyzed 36 mg Zn/kg dry matter [DM]) or supranutritional Zn (SUPZN; CON+60 mg Zn/kg DM from ZnSO4+60 mg Zn/kg DM from Zn-amino acid complex; Availa Zn, Zinpro, Eden Prairie, MN) dietary treatments (ZNTRT). Starting 28 d prior to harvest, steers were blocked by BW within ZNTRT to RAC treatments (RACTRT) of 0 (NO) or 300 mg·steer−1·d−1 (RAC; Actogain 45, Zoetis). After 15 d on RACTRT, longissimus thoracis biopsies were collected from all steers for proteomic analysis. Twenty-eight steers (n=7 per treatment) were harvested at a commercial abattoir on Day 90. A ZNTRT×RACTRT effect showed SUPZN-RAC steers had a greater dressing percentage than other treatments (P≤0.02). Steers fed SUPZN had a greater hot carcass weight, carcass-adjusted final BW, overall average daily gain, and overall gain to feed (P≤0.05). Differentially abundant proteins involved in energy metabolism, muscle structure, and protein synthesis potentially indicate muscle fiber characteristic differences because of Zn and RAC supplementation.Both myosin light chain kinase 2 and eukaryotic translation initiation factor 5A-1 were more abundant in SUPZN-RAC steers than SUPZN-NO (P≤0.05) or CON-NO (P≤0.04) steers when analyzed for phosphorylation modifications. L-lactate dehydrogenase B was more abundant in SUPZN-NO steers than CON-NO (P=0.03) or CON-RAC (P=0.01) steers. In conclusion, increased Zn supplementation may be needed to optimize the hypertrophic effects of RAC through its effects on the longissimus thoracis proteome

Probing DNA Structural Heterogeneity by Identifying Conformational Subensembles of a Bicovalently Bound Cyanine Dye

DNA is a re-configurable, biological information-storage unit, and much remains to be learned about its heterogeneous structural dynamics. For example, while it is known that molecular dyes templated onto DNA exhibit increased photostability, the mechanism by which the structural dynamics of DNA affect the dye photophysics remains unknown. Here, we use femtosecond, two-dimensional electronic spectroscopy measurements of a cyanine dye, Cy5, to probe local conformations in samples of single-stranded DNA (ssDNA–Cy5), double-stranded DNA (dsDNA–Cy5), and Holliday junction DNA (HJ–DNA–Cy5). A line shape analysis of the 2D spectra reveals a strong excitation–emission correlation present in only the dsDNA–Cy5 complex, which is a signature of inhomogeneous broadening. Molecular dynamics simulations support the conclusion that this inhomogeneous broadening arises from a nearly degenerate conformer found only in the dsDNA–Cy5 complex. These insights will support future studies on DNA’s structural heterogeneity

Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates

Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates

Tuning Between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates

Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging through the local generation of heat via rapid excited-state quenching. Here we show how to tune between energy transfer and quenching for heterodimers of the same pair of cyanine dyes by altering their spatial configuration on a DNA template. We assemble “transverse” and “adjacent” heterodimers of Cy5 and Cy5.5 using DNA Holliday junctions. We find that the transverse heterodimers exhibit optical properties consistent with excitonically interacting dyes and fluorescence quenching, while the adjacent heterodimers exhibit optical properties consistent with nonexcitonically interacting dyes and disproportionately large Cy5.5 emission, suggestive of energy transfer between dyes. We use transient absorption spectroscopy to show that quenching in the transverse heterodimer occurs via rapid nonradiative decay to the ground state (∼31 ps) and that in the adjacent heterodimer rapid energy transfer from Cy5 to Cy5.5 (∼420 fs) is followed by Cy5.5 excited-state relaxation (∼700 ps). Accessing such drastically different photophysics, which may be tuned on demand for different target applications, highlights the utility of DNA as a template for dye aggregation

Investigation of the Sarcoplasmic Proteome Contribution to the Development of Pork Loin Tenderness

The study objectives were to determine the extent to which the sarcoplasmic proteome explains variations in aged pork loin star probe value. Pork loins (n=12) were categorized by differences in star probe at 21 d post mortem from a larger set of loins. Loins were categorized into low star probe (LSP) group (n=6; star probe<5.80 kg) and high star probe (HSP) group (n=6; star probe>7.00 kg) based on 21-d star probe value with inclusion criteria of marbling score (1.0–3.0) and 24-h pH (5.69–5.98). Quality traits were measured at 1-, 8-, 14-, and 21-d aging. Desmin and troponin-T degradation, peroxiredoxin-2 abundance, calpain-1 autolysis, and sarcomere length were determined. Two-dimensional difference gel electrophoresis and mass spectrometry were used to identify proteins that differed in abundance due to category. Star probe values were lower (P<0.01) in LSP at each day of aging compared with HSP. Greater pH values were observed (P<0.05)in LSP compared with HSP at each day of aging. Marbling score was greater (P<0.05) in LSP compared with HSP at each day of aging. Greater (P<0.05) desmin and troponin-T degradation was detected in LSP chops at 14- and 21-d aging and 8-, 14-, and 21-d aging, respectively. Greater (P<0.05) sarcomere length was determined in LSP compared with HSP at 1-,8-, and 21-d aging. Sarcoplasmic proteins from HSP chops had greater abundance (P<0.10) of metabolic and regulatory proteins, whereas the LSP chops had greater abundance (P<0.10) of stress response proteins. Star probe values were affected by pH, marbling score, protein degradation, sarcomere length, and sarcoplasmic proteome