  In recent years we have seen an important increase in the number of
protonated molecules detected in cold dense clouds. Here we report the
detection in TMC-1 of HCCNCH+, the protonated form of HCCNC, which is a
metastable isomer of HC3N. This is the first protonated form of a metastable
isomer detected in a cold dense cloud. The detection was based on observations
carried out with the Yebes 40m and IRAM 30m telescopes, which revealed four
harmonically related lines. We derive a rotational constant B = 4664.431891 +/-
0.000692 MHz and a centrifugal distortion constant D = 519.14 +/- 4.14 Hz. From
a high-level ab initio screening of potential carriers we confidently assign
the series of lines to the ion HCCNCH+. We derive a column density of (3.0 +/-
0.5)e10 cm-2 for HCCNCH+, which results in a HCCNCH+/HCCNC abundance ratio of
0.010 +/- 0.002. This value is well reproduced by a state-of-the-art chemical
model, which however is subject to important uncertainties regarding the
chemistry of HCCNCH+. The observational and theoretical status of protonated
molecules in cold dense clouds indicate that there exists a global trend in
which protonated-to-neutral abundance ratios MH+/M increase with increasing
proton affinity of the neutral M, although if one restricts to species M with
high proton affinities (>700 kJ/mol), MH+/M ratios fall in the range 0.001-0.1,
with no apparent correlation with proton affinity. We suggest various
protonated molecules that are good candidates for detection in cold dense
clouds in the near future.
