a Copper-doped porous metal oxides catalyze the one-pot disassembly of biomass-derived lignin via C-O bond hydrogenolysis and hydrodeoxygenation in supercritical methanol. This catalytic system cleanly converts lignin as well as lignocellulose composites, such as sawdust, to organic liquids with little or no formation of intractable tars or chars. However, this catalyst based on Earth-abundant components also catalyzes less desirable aromatic ring hydrogenations and various methylations that contribute to the diversity of products. In this context, we undertook a quantitative experimental and computational evaluation of model reactions relevant to the reductive disassembly of lignin by this catalyst system in order to determine quantitatively the rates of desirable and less desirable chemical steps that define the overall product selectivities.Global fitting analysis methods were used to map the temporal evolution of key intermediates and products and to elucidate networks that provide guidelines regarding the eventual fates of reactive intermediates in this catalysis system. Phenolic compounds display multiple reaction pathways, but substrates such as benzene, toluene, and alkyl-and alkoxy-substituted aromatics are considerably more stable under these conditions. These results indicate that modifying this catalytic system in a way that controls and channels the reactivity of phenolic intermediates should improve selectivity toward producing valuable aromatic chemicals from biomass-derived lignin. To this end we demonstrate that the O-methylating agent dimethyl carbonate can intercept the phenol intermediate formed from hydrogenolysis of the model compound benzyl phenyl ether. Trapping the phenol as anisole thus gave much higher selectivity towards aromatic products.

ABSTRACT:The selective conversion of lignin into aromatic compounds has the potential to serve as a "green" alternative to the production of petrochemical aromatics. Herein, we evaluate the addition of dimethyl carbonate (DMC) to a biomass conversion system that uses a Cu-doped porous metal oxide (Cu 20 PMO) catalyst in supercritical methanol (sc-MeOH) to disassemble lignin with little to no char formation. While Cu 20 PMO catalyzes C-O hydrogenolysis of aryl-ether bonds linking lignin monomers, it also catalyzes arene methylation and hydrogenation, leading to product proliferation. The MeOH/DMC co-solvent system significantly suppresses arene hydrogenation of the phenolic intermediates responsible for much of the undesirable product diversity via Omethylation of phenolic -OH groups to form more stable aryl-OCH 3 species. Consequently, product proliferation was greatly reduced and aromatic yields greatly enhanced with lignin models, 2-methoxy-4-propylphenol, benzyl phenyl ether, and 2-phenoxy-1-phenylethan-1-ol. In addition, organosolv poplar lignin (OPL) was examined as a substrate in the MeOH/DMC co-solvent system. The products were characterized by nuclear magnetic resonance spectroscopy ( 31 P, 13 C, and 2D 1 H-13 C NMR) and gas chromatography-mass spectrometry techniques. The co-solvent system demonstrated enhanced yields of aromatic products. INTRODUCTION.

Lignin is the largest renewable source of aromatic chemical building blocks on the planet and has great potential for the production of value-added chemicals.Herein, we describe lignin hydrogenolysis/depolymerization of organosolv poplar lignin (OPL) in ethanol/iso-propanol solvent in the absence of added catalysts. Different EtOH/i-PrOH ratios as well as various reaction conditions were evaluated. OPL depolymerization was more effective in the mixed media than in ethanol or iso-propanol alone. Heating OPL at 270 °C for 4 h in 50:50 (v:v) EtOH/i-PrOH in a closed pressure vessel gave an overall oil yield of 70 wt% of which about 48% consisted of the monomers (E)-4-propenyl syringol and iso-eugenol. Notably, these catalyst-free reactions in ethanol/iso-propanol media show monomer yields comparable to those reported for lignin depolymerization using precious metal catalysts and dihydrogen, which suggests unexpectedly favorable H-donor ability of this mixed alcohol medium.

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In this paper, we present the first longitudinal measurement study of the underground ecosystem fueling credential theft and assess the risk it poses to millions of users. Over the course of March, 2016-March, 2017, we identify 788,000 potential victims of off-theshelf keyloggers; 12.4 million potential victims of phishing kits; and 1.9 billion usernames and passwords exposed via data breaches and traded on blackmarket forums. Using this dataset, we explore to what degree the stolen passwords-which originate from thousands of online services-enable an attacker to obtain a victim's valid email credentials-and thus complete control of their online identity due to transitive trust. Drawing upon Google as a case study, we find 7-25% of exposed passwords match a victim's Google account. For these accounts, we show how hardening authentication mechanisms to include additional risk signals such as a user's historical geolocations and device profiles helps to mitigate the risk of hijacking. Beyond these risk metrics, we delve into the global reach of the miscreants involved in credential theft and the blackhat tools they rely on. We observe a remarkable lack of external pressure on bad actors, with phishing kit playbooks and keylogger capabilities remaining largely unchanged since the mid-2000s.