One
prominent aspect of metal organic frameworks (MOFs) is the
ability to tune the size, shape, and chemical characteristics of their
pores. MOF-5, with its open cubic connectivity of Zn4O
clusters joined by two-dimensional, terephthalate linkers, is the
archetypal example: both functionalized and elongated linkers produce
isoreticular frameworks that define pores with new shapes and chemical
environments. The recent scalable synthesis of cubane-1,4-dicarboxylic
acid (1,4-H2cdc) allows the first opportunity to explore
its application in leading reticular architectures. Herein we describe
the use of 1,4-H2cdc to construct [Zn4O(1,4-cdc)3], referred to as CUB-5. Isoreticular with MOF-5, CUB-5 adopts
a cubic architecture but features aliphatic, rather than aromatic,
pore surfaces. Methine units point directly into the pores, delivering
new and unconventional adsorption locations. Our results show that
CUB-5 is capable of selectively adsorbing high amounts of benzene
at low partial pressures, promising for future investigations into
the industrial separation of benzene from gasoline using aliphatic
MOF materials. These results present an effective design strategy
for the generation of new MOF materials with aliphatic pore environments
and properties previously unattainable in conventional frameworks.
Using a continuous flow reactor, the dehydration of Dfructose and other carbohydrates to 5-(chloromethyl)-furfural (1) is achieved in reaction times as short as 60 s. The biphasic flow process allows for high-yielding multigram scale production of CMF (1) which is obtained with excellent purity after a simple extractive work-up. Efficient conversion of D-fructose into 5-(hydroxymethyl)furfural (2) and levulinic acid (6) is also demonstrated using flow reactor techniques.
Pharmaceutical and agrochemical discovery programs are under considerable pressure to meet increasing global demand and thus require constant innovation. Classical hydrocarbon scaffolds have long assisted in bringing new molecules to the market place, but an obvious omission is that of the Platonic solid cubane. Eaton, however, suggested that this molecule has the potential to act as a benzene bioisostere. Herein, we report the validation of Eaton's hypothesis with cubane derivatives of five molecules that are used clinically or as agrochemicals. Two cubane analogues showed increased bioactivity compared to their benzene counterparts whereas two further analogues displayed equal bioactivity, and the fifth one demonstrated only partial efficacy. Ramifications from this study are best realized by reflecting on the number of bioactive molecules that contain a benzene ring. Substitution with the cubane scaffold where possible could revitalize these systems, and thus expedite much needed lead candidate identification.
The RAFT agents offerĐ< 1.1 for MAMs, methyl acrylate (MA),N,N-dimethylacrylamide (DMA) and styrene, andĐ< 1.3 for LAMs, vinyl acetate (VAc); versatility and end-group fidelity was proved with synthesis both polyDMA-block-polyMA and polyDMA-block-polyVAc.
Catalytic static mixers were used for the continuous flow hydrogenation of alkenes, alkynes, carbonyls, nitro-and diazo-compounds, nitriles, imines, and halides. This technique relies on tubular reactors fitted with 3D printed static mixers which are coated with a catalytic metal layer, either Pd or Ni. Additive manufacturing of the metal mixer scaffold results in maximum design flexibility and is compatible with deposition methods such as metal cold spraying which allow for mass production and linear process scale up. High to full conversion was achieved for the majority of substrates, demonstrating the flexibility and versatility of the catalytic static mixer technology. In the example of an alkyne reduction, the selectivity of the flow reactor could be directed to either yield an alkene or alkane product by simply changing the reactor pressure.
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