Digital painter and concept artist Piotr Jabłoński creates brutally detailed paintings for videogames and comic books which often veer into the realm of horror, but in his spare time dabbles in somewhat tamer sketches and other random ideas that he shares with fans on Facebook. A few months ago he stumbled onto the idea of two small brothers in futuristic space helmets who explore the world with a feline pal, a giant cat mural that follows them everywhere, provided there’s a wall. The response online has been incredible, with fans demanding an art book or even an entire comic book series. While nothing is concrete yet you can see more on Behance, and a few of the panels are available now as prints.
A new framework derived from the commercially available diterpenoid alkaloid lappaconitine was evaluated as a Brønsted base catalyst for the enantioselective α-hydroxylation of β-dicarbonyl compounds by using 30 % hydrogen peroxide as a green and highly practical source of oxygen. This protocol allows convenient access to the corresponding α-hydroxy-β-oxo esters, α-hydroxy-β-oxo amides and (–)-kjellmanianone with up to 98 % yield and 92 % ee.
Ten new organocatalysts derived from the diterpenoid alkaloid lappaconitine are described. Activities for the enantioselective α-hydroxylation of β-dicarbonyl compounds with 30 % hydrogen peroxide as a green and practical source of oxygen is described. This protocol allows convenient access to the corresponding α-hydroxy-β-dicarbonyl compounds with up to 98 % yield and 92 % ee under mild conditions.
The importance of aromatic CO, CN, and CS bonds necessitates increasingly efficient strategies for their formation. Herein, we report a biomimetic approach that converts phenolic CH bonds into CO, CN, and CS bonds at the sole expense of reducing dioxygen (O2) to water (H2O). Our method hinges on a regio- and chemoselective copper-catalyzed aerobic oxygenation to provide ortho-quinones. ortho-Quinones are versatile intermediates, whose direct catalytic aerobic synthesis from phenols enables a mild and efficient means of synthesizing polyfunctional aromatic rings.
The direct approach: Polyfunctional aromatic rings have been generated by direct functionalization of CH bonds to CO, CN, and CS bonds at the sole expense of reducing O2 to H2O. The method hinges on a regio- and chemoselective, copper-catalyzed aerobic oxygenation of phenols to provide ortho-quinones (see scheme), thus mimicking the ubiquitous biosynthetic pathway of melanogenesis.
Metal-bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen-activating metalloenzymes. In the nonheme iron α-ketoglutarate dependent oxygenases and pterin-dependent hydroxylases, however, FeIII–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a CuII–superoxide complex (1) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α-ketoglutarate dependent and pterin-dependent enzymes.
Nucleophilic superoxide: A copper(II)-superoxide complex has been found to be a highly reactive nucleophile. The complex reacts readily with certain electrophiles and is capable of the nucleophilic deformylation of electron-rich aldehydes (Baeyer–Villiger oxidation). These observations provide experimental support for the postulated nucleophilic reactivity of metal-superoxide intermediates in the catalytic cycles of certain nonheme iron enzymes.
Bad Ass Black Goths: A Photoset For You To Reblog & Throw In People’s Faces
by Nuestra Hermana
In case you didn’t know, there has always been a lot of backwards ass racist sentiments towards black goths. Statements like, “there aren’t any black goths”, “black people just don’t look right as goth”, “Black goths are scary”, “Black people shouldn’t be goth” are prominent throughout the internet and within clubs and community circles.
Translated, these statements in their simplest root read something along the lines of: Black people cannot be gothic because they are not white.
Of course, not every non-black goth is this way but you will see more than plenty proclaim any of the above without a thought of how erasing and racist it is towards black goths.
Recently, I read someone posting something along the very same sentiment, claiming they had never seen a black person “pull off” being goth.
This here, is for all of you dears who truly believe that. I’m here to simply show you that Black goths do it real fucking well & are just as dark souled & artistically amazingly magnificent in the goth community (if not even more, yes, I did just say that to you.)
If you don’t know much about this or simply don’t believe me, you can read more for yourself here , where someone is asking for advice on “on how you would approach one” and here, where someone claims that black people make terrible vampires (TW: racist slurs)… and here where a black goth is attacked for simply asking if there are any other black goths in his area.
If you’re black and goth and want some support:
Black/African-American Goths (364 members! Yes.)
Ps: I had a bunch more pictures but I couldn’t fit them in to this photoset.
The poor look of terror on that doomed girl’s face.
Hitchcock’s “The Peeps”
Located within the Andes Mountains of northern Chile, El Tatio is the largest geyser field in the southern hemisphere and the third largest in the world. The field has over 80 active geysers and attracts tens of thousands of tourists each year who flock to see the incredible mineral formations and to bathe in hot geyser water. British Columbia-based interactive web designer and visual artist Owen Perry recently visited El Tatio and returned with these spectacular shots. Perry has a beautiful collection of travel and landscape photography you can explore over on Circa 1983. (via Colossal Submissions)