  An ability to precisely regulate the quantity and location of molecular flux
is of value in applications such as nanoscale 3D printing, catalysis, and
sensor design. Barrier materials containing pores with molecular dimensions
have previously been used to manipulate molecular compositions in the gas
phase, but have so far been unable to offer controlled gas transport through
individual pores. Here, we show that gas flux through discrete angstrom-sized
pores in monolayer graphene can be detected and then controlled using
nanometer-sized gold clusters, which are formed on the surface of the graphene
and can migrate and partially block a pore. In samples without gold clusters,
we observe stochastic switching of the magnitude of the gas permeance, which we
attribute to molecular rearrangements of the pore. Our molecular valves could
be used, for example, to develop unique approaches to molecular synthesis that
are based on the controllable switching of a molecular gas flux, reminiscent of
ion channels in biological cell membranes and solid state nanopores.
