A Vision of Sustainability and Growth in Savona, NY

Project Description: Alfred State completed a community visualization study of the Steuben County Village of Savona, New York in order to help the residents and municipal officials envision potential strategies for revitalizing their business district and surrounding neighborhoods. Abstract: Alfred State – SUNY College of Technology is located in Allegany County, one of the poorest areas in New York’s Appalachian Region. With a county-wide population approaching 50,000 residents, communities tend to be very small with limited resources and part-time governments. Local community organizations and municipalities in Allegany and adjacent Southern Tier counties are especially in need of assistance with respect to long-range planning to create strategies for sustainable development of projects ranging from façade improvements to large-scale infrastructure repair and replacement. In Fall 2014, Professor William Dean led the Architecture and Design Department’s senior Urban Design Studio in working with the Village of Savona, which is located in New York’s Southern Tier, as the subject for the semester’s community visualization study. Working individually and in small groups, students researched and documented the subject area and completed a site analysis which included a visual survey of the defined physical characteristics representing Urban Design Excellence and Design Linkages within the community. The report also identified the municipalities’ strengths, weaknesses, opportunities and threats based on conversations with area residents and local officials. In addition to municipal officials and town residents, the students had the opportunity to work with architects, planners and landscape architects from a local firm involved in authoring a comprehensive plan for the town. The expertise of these design professionals supplemented the faculty instruction in this integrated studio that seeks to align architectural design with the realities of contemporary practice. Initial meetings, both in Savona and via teleconference, occurred every two weeks or as necessary leading up to the start of the project. Once the project began, meetings for data gathering and to participate in a design workshop occurred in Savona. The final design presentation took place in Savona where students publicly presented their work at the end of the project to municipal officials and town residents. The information generated during the course of the project was used as a point of departure to illustrate and explain a positive vision for sustainability and growth of the Village of Savona through community engagement. The overall goal through student engagement of the community was to develop an inclusive community visualization study that included a series of design interventions based on the village’s recently-completed comprehensive plan. The study included a series of before and thematic after images intended to help local officials and residents envision possibilities for future development. Implementation will be possible through grant funding that will require the community to have a clearly defined vision to supplement the new comprehensive plan

Diastereoselective Synthesis of γ‑Lactones through Reaction of Enediolates with α,β-Unsaturated Sulfoxonium Salts

Studies of the reaction of lithium enediolates with α,β-unsaturated sulfoxonium salts are described. γ-Lactones were formed in very good to excellent yields (82% → 99% for 11 examples) and with very good to excellent diastereoselectivity (dr >90:10 for 10 examples), favoring the <i>trans</i>-diastereomer

Dhb Microcystins Discovered in USA Using an Online Concentration LC–MS/MS Platform

Based on current structural and statistical calculations, thousands of microcystins (MCs) can exist; yet, to date, only 246 MCs have been identified and only 12 commercial MC standards are available. Standard mass spectrometry workflows for known and unknown MCs need to be developed and validated for basic and applied harmful algal bloom research to advance. Our investigation focuses on samples taken in the spring of 2018 from an impoundment fed by Oser and Bischoff Reservoirs, Indiana, United States of America (USA). The dominant cyanobacterium found during sampling was Planktothrix agardhii. The goal of our study was to identify and quantify the MCs in the impoundment sample using chemical derivatization and mass spectrometry. Modifying these techniques to use online concentration liquid chromatography tandem mass spectrometry (LC&ndash;MS/MS), two untargeted MCs have been identified, [d-Asp3, Dhb7]-MC-LR and tentative [Dhb7]-MC-YR. [Dhb7]-MC-YR is not yet reported in the literature to date, and this was the first reported incidence of Dhb MCs in the United States. Furthermore, it was discovered that the commercially available [d-Asp3]-MC-RR standard was [d-Asp3, Dhb7]-MC-RR. This study highlights a workflow utilizing online concentration LC&ndash;MS/MS, high-resolution MS (HRMS), and chemical derivatization to identify isobaric MCs

Asymmetric Synthesis of γ‑Lactones through Koga Amine-Controlled Addition of Enediolates to α,β-Unsaturated Sulfoxonium Salts

A chiral Koga amine-controlled asymmetric synthesis of <i>cis</i>-γ-lactones through a formal [3 + 2] cycloaddition of enediolates with α,β-unsaturated sulfoxonium salts is described. The desired structural motif was formed in moderate to good yields (50–71% for 13 examples), with good to very good diastereoselectivity (dr 5:1 to 10:1 for 20 examples), favoring the <i>cis</i>-isomer, and good to excellent enantioselectivity (70–91% ee for 13 examples)

Toward Revealing Microcystin Distribution in Mouse Liver Tissue Using MALDI-MS Imaging

Cyanotoxins can be found in water and air during cyanobacterial harmful algal blooms (cHABs) in lakes and rivers. Therefore, it is very important to monitor their potential uptake by animals and humans as well as their health effects and distribution in affected organs. Herein, the distribution of hepatotoxic peptide microcystin-LR (MC-LR) is investigated in liver tissues of mice gavaged with this most common MC congener. Preliminary matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) imaging experiments performed using a non-automated MALDI matrix deposition device and a MALDI-time-of-flight (TOF) mass spectrometer yielded ambiguous results in terms of MC-LR distribution in liver samples obtained from MC-LR-gavaged mice. The tissue preparation for MALDI-MS imaging was improved by using an automated sprayer for matrix deposition, and liver sections were imaged using an Nd:YAG MALDI laser coupled to a 15 Tesla Fourier-transform ion cyclotron resonance (FT-ICR)-mass spectrometer. MALDI-FT-ICR-MS imaging provided unambiguous detection of protonated MC-LR (calculated m/z 995.5560, z = +1) and the sodium adduct of MC-LR (m/z 1017.5380, z = +1) in liver sections from gavaged mice with great mass accuracy and ultra-high mass resolution. Since both covalently bound and free MC-LR can be found in liver of mice exposed to this toxin, the present results indicate that the distribution of free microcystins in tissue sections from affected organs, such as liver, can be monitored with high-resolution MALDI-MS imaging

Discovery and Structural Elucidation of Novel Microcystins Using MS and MSn with Python Code

Microcystins (MCs) are cyclic heptapeptide hepatotoxins with a vast structural diversity (\u3e300 congeners). However, many more congeners are theoretically possible, and a workflow was developed for putative identification of novel MCs using liquid chromatography (LC) coupled to high-resolution mass spectrometry (HRMS) and MSn with Python code. Water samples collected from Lake Erie were sonicated and filtered, and solid-phase extraction was performed. A portion of the water sample was reacted with mercaptoethanol using the method developed by Miles et al. for structural elucidation. Extracted MCs were analyzed using UHPLC coupled to an Orbitrap Fusion instrument for HRMS. Collision-induced dissociation (CID) and higher-energy CID (HCD) were used for MSn analyses. A total of 33 MCs were found in lake water samples, including two unknown MCs. Two Python codes were developed to elucidate the structures of MCs. Code 1 was written to generate a list of masses of theoretically possible MC congeners. Code 2 was written to compare the experimentally obtained masses of MC fragment ions to the theoretical fragment masses. Using Codes 1 and 2, the two unknown MCs with m/z values of 526.7980 (z=+2) and 1025.5302 (z=+1) were putatively identified as MC-HarR and MC-E(OMe)R, respectively

Do Microcystis laboratory cultures hold clues to bacterial microcystin degradation?

Microcystins do not accumulate in freshwater ecosystems, and their degradation rates in freshwater suggest that both biotic and abiotic factors play critical roles in their removal. Most Microcystis aeruginosa laboratory cultures harbor a microbiome made up of heterotrophic bacteria that use Microcystis-produced organic matter for growth. We analyzed the microbiome of two M. aeruginosa cultures from Lake Erie with metagenomic sequencing, and found that some of their metagenome-assembled genomes included known genes for microcystin degradation. We tested whether these mixed communities can degrade microcystins by incubating them with Microcystis lysate (freeze-thawed cells) and monitoring dissolved microcystins by liquid chromatography mass spectrometry (LC/MS). We also tested whether these bacterial populations could incorporate carbon and nitrogen from microcystin-LR (MC-LR), the most common and most toxic of the microcystins, as well as bacteria from non-toxic Microcystis culture as a control. To accomplish this, we first labeled a M. aeruginosa culture with 13C and 15N stable isotopes, purified extracted MC-LR from the cell pellets, and added this labeled substrate back to Microcystis-bacteria co-cultures. Using nanoscale imaging mass spectrometry (NanoSIMS), we quantified the net incorporation of 15N and 13C into heterotrophic bacteria as well as the Microcystis cells to identify the fate of MC-LR C and N in this microbial ecosystem

Catalytic Asymmetric Synthesis of Ketene Heterodimer β‑Lactones: Scope and Limitations

In this article we describe extensive studies of the catalytic asymmetric heterodimerization of ketenes to give ketene heterodimer β-lactones. The optimal catalytic system was determined to be a cinchona alkaloid derivative (TMS-quinine or Me-quinidine). The desired ketene heterodimer β-lactones were obtained in good to excellent yields (up to 90%), with excellent levels of enantioselectivity (≥90% ee for 33 <i>Z</i> and <i>E</i> isomer examples), good to excellent (<i>Z</i>)-olefin isomer selectivity (≥90:10 for 20 examples), and excellent regioselectivity (only one regioisomer formed). Full details of catalyst development studies, catalyst loading investigations, substrate scope exploration, protocol innovations (including double in situ ketene generation for 7 examples), and an application to a cinnabaramide A intermediate are described. The addition of lithium perchlorate (1–2 equiv) as an additive to the alkaloid catalyst system was found to favor formation of the <i>E</i> isomer of the ketene heterodimer. Ten examples were formed with moderate to excellent (<i>E</i>)-olefin isomer selectivity (74:25 to 97:3) and with excellent enantioselectivity (84–98% ee)

Diastereoselective Reaction of Sulfoxonium Ylides, Aldehydes and Ketenes: An Approach to <i>trans</i>-γ-Lactones

In this paper, a novel approach to γ-lactones from the reaction of sulfoxonium ylides, aldehydes, and ketenes is described. The new ylide-based method provides access to γ-lactones from disubstituted ketenes, in good yields, and with good diastereoselectivity favoring the <i>trans</i>-diastereomer (11 examples with dr ≥ 82:18, dr up to 92:8)