Tandem Thio-Michael Addition/Remote Lactone Activation of 5-Hydroxymethylfurfural-Derived δ-Lactone-Fused Cyclopentenones

Funding Information: We thank the Fundação para a Ciência e a Tecnologia (SFRH/BD/120829/2016, SFRH/BD/148211/2019, UIDB/04138/2020, UIDP/04138/2020, PTDC/QUI‐QOR/32008/2017 and GHTM‐UID/04413/2020). The project leading to this application has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 951996. J. A. S. C. thanks the Fundação para a Ciência e a Tecnologia (FCT) for Scientific Employment Stimulus 2020/02383/CEECIND. Publisher Copyright: © 2022 The Authors. ChemSusChem published by Wiley-VCH GmbH.The creation of structurally diverse chemical entities from fairly simple biorefinery products remains a challenge. In this work 5-hydroxymethylfurfural (HMF) was identified as a key synthon for preparing highly complex cyclopentenones (CP) via tandem 1,4-addition/elimination/remote lactone activation to external O- and N-nucleophiles in δ-lactone-fused-CPs hotspots. This scaffold was also reactive enough to be incorporated into model cysteine-peptides in low concentrations, paving the way to a potential translation generating complexity in the synthesis of small peptides. The new enones also exhibited activity against intraerythrocytic Plasmodium falciparum (IC50=1.32 μm).publishersversionpublishe

The road to deterministic matrices with the restricted isometry property

The restricted isometry property (RIP) is a well-known matrix condition that provides state-of-the-art reconstruction guarantees for compressed sensing. While random matrices are known to satisfy this property with high probability, deterministic constructions have found less success. In this paper, we consider various techniques for demonstrating RIP deterministically, some popular and some novel, and we evaluate their performance. In evaluating some techniques, we apply random matrix theory and inadvertently find a simple alternative proof that certain random matrices are RIP. Later, we propose a particular class of matrices as candidates for being RIP, namely, equiangular tight frames (ETFs). Using the known correspondence between real ETFs and strongly regular graphs, we investigate certain combinatorial implications of a real ETF being RIP. Specifically, we give probabilistic intuition for a new bound on the clique number of Paley graphs of prime order, and we conjecture that the corresponding ETFs are RIP in a manner similar to random matrices.Comment: 24 page

Soil and crop residue CO2-C emission under tillage systems in sugarcane-producing areas of southern Brazil

Appropriate management of agricultural crop residues could result in increases on soil organic carbon (SOC) and help to mitigate gas effect. To distinguish the contributions of SOC and sugarcane (Saccharum spp.) residues to the short-term CO2-C loss, we studied the influence of several tillage systems: heavy offset disk harrow (HO), chisel plow (CP), rotary tiller (RT), and sugarcane mill tiller (SM) in 2008, and CP, RT, SM, moldboard (MP), and subsoiler (SUB) in 2009, with and without sugarcane residues relative to no-till (NT) in the sugarcane producing region of Brazil. Soil CO2-C emissions were measured daily for two weeks after tillage using portable soil respiration systems. Daily CO2-C emissions declined after tillage regardless of tillage system. In 2008, total CO2-C from SOC and/or residue decomposition was greater for RT and lowest for CP. In 2009, emission was greatest for MP and CP with residues, and smallest for NT. SOC and residue contributed 47 % and 41 %, respectively, to total CO2-C emissions. Regarding the estimated emissions from sugarcane residue and SOC decomposition within the measurement period, CO2-C factor was similar to sugarcane residue and soil organic carbon decomposition, depending on the tillage system applied. Our approach may define new emission factors that are associated to tillage operations on bare or sugarcane-residue-covered soils to estimate the total carbon loss

Diving into the vertical dimension of elasmobranch movement ecology

Knowledge of the three-dimensional movement patterns of elasmobranchs is vital to understand their ecological roles and exposure to anthropogenic pressures. To date, comparative studies among species at global scales have mostly focused on horizontal movements. Our study addresses the knowledge gap of vertical movements by compiling the first global synthesis of vertical habitat use by elasmobranchs from data obtained by deployment of 989 biotelemetry tags on 38 elasmobranch species. Elasmobranchs displayed high intra- and interspecific variability in vertical movement patterns. Substantial vertical overlap was observed for many epipelagic elasmobranchs, indicating an increased likelihood to display spatial overlap, biologically interact, and share similar risk to anthropogenic threats that vary on a vertical gradient. We highlight the critical next steps toward incorporating vertical movement into global management and monitoring strategies for elasmobranchs, emphasizing the need to address geographic and taxonomic biases in deployments and to concurrently consider both horizontal and vertical movements

First-order decay models to describe soil C-CO2 Loss after rotary tillage

To further understand the impact of tillage on CO2 emission, the applicability of two conceptual models was tested, which describe the CO2 emission after tillage as a function of the non-tilled emission plus a correction due to the tillage disturbance. Models assume that C in readily decomposable organic matter follows a first-order reaction kinetics equation as: dCsoil (t) / dt = -k Csoil (t), and that soil C-CO2 emission is proportional to the C decay rate in soil, where Csoil(t) is the available labile soil C (g m-2) at any time (t) and k is the decay constant (time-1). Two possible assumptions were tested to determine the tilled (F T) fluxes: the decay constants (k) of labile soil C before and after tillage are different (Model 1) or not (Model 2). Accordingly, C flux relationships between non-tilled (F NT) and tilled (F T) conditions are given by: F T = F NT + a1 e-a2t (model 1) and F T = a3 F NT e-a4t (model 2), where t is time after tillage. Predicted and observed CO2 fluxes presented good agreement based on the coefficient of determination (R² = 0.91). Model comparison revealed a slightly improved statistical fit of model 2, where all C pools are assigned with the same k constant. Rotary speed was related to increases in the amount of labile C available and to changes of the mean resident labile C pool available after tillage. This approach allows describing the temporal variability of tillage-induced emissions by a simple analytical function, including non-tilled emission plus an exponential term modulated by tillage and environmentally dependent parameters.Para entendimento do impacto do preparo do solo sobre as emissões de CO2 desenvolvemos e aplicamos dois modelos conceituais que são capazes de prever a emissão de CO2 do solo após seu preparo em função da emissão da parcela sem distúrbio, acrescida de uma correção devido ao preparo. Os modelos assumem que o carbono presente na matéria orgânica lábil segue uma cinética de decaimento de primeira ordem, dada pela seguinte equação: dCsoil (t) / dt = -k Csoil (t), e que a emissão de C-CO2 é proporcional a taxa de decaimento do C no solo, onde Csolo(t) é a quantidade de carbono lábil disponível no tempo (t) e k é a constante de decaimento (tempo-1). Duas suposições foram testadas para determinação das emissões após o preparo do solo (Fp): a constante de decaimento do carbono lábil do solo (k) antes e após o preparo é igual (Modelo 1) ou desigual (Modelo 2). Conseqüentemente, a relação entre os fluxos de C das parcelas sem distúrbio (F SD) e onde o preparo do solo foi conduzido (F P) são dadas por: F P = F SD + a1 e-a2t (modelo 1) e F P = a3 F SD e-a4t (modelo 2), onde t é o tempo após o preparo. Fluxos de CO2 previstos e observados relevam um bom ajuste dos resultados com coeficiente de determinação (R²) tão alto quanto 0,91. O modelo 2 produz um ajuste ligeiramente superior quando comparado com o outro modelo. A velocidade das pás da enxada rotativa foi relacionada a um aumento na quantidade de carbono lábil e nas modificações do tempo de residência médio do carbono lábil do solo após preparo. A vantagem desta metodologia é que a variabilidade temporal das emissões induzidas pelo preparo do solo pode ser descrita a partir de uma função analítica simples, que inclui a emissão da parcela sem distúrbio e um termo exponencial modulado por parâmetros dependentes do preparo e de condições ambientais onde o experimento foi conduzido