The structures of two lamellar silver
thiolate coordination polymers [Ag(p-SPhCO2H)]
n
(1) and [Ag(p-SPhCO2Me)]
n
(2) are described for the first time. Their inorganic part
is composed of distorted Ag3S3 honeycomb networks
separated by noninterpenetrated thiolate ligands. The main difference
between the two compounds arises from dimeric hydrogen bonds present
for the carboxylic acids. Indepth photophysical studies show that
the silver thiolates exhibit multiemission properties, implying luminescence
thermochromism. More interestingly, the synthesis of a heterometallic
lamellar compound, [Ag0.85Cu0.15(p-SPhCO2H)]
n
(3), allows to obtain mixed metal thiolate coordination polymers and
to tune the photophysical properties with the excitation wavelengths
from a green vibronic luminescence to a single red emission band.
We report an original MS-based hyphenated method for the elucidation of the epimerization in GAG fragments. It consists of measuring simultaneously the MS/MS spectrum and the gas phase IR spectrum to gain direct structural information. This is possible using a customized MS instrument, modified to allow injection of a tunable IR laser inside of the instrument for in situ spectroscopy of trapped ions. The proof of principle of this approach is performed in the case of a hyaluronic acid tetrasaccharide standard. In addition, we provide the reference IR fingerprint of glucuronic and Iduronic monosaccharide standards. Remarkably, we show that the gas phase IR fingerprint of reference hexuronic acid monosaccharides proves to be transposable to oligosaccharides. Therefore, the method presented here is predictive and allows structural elucidation of unknown GAG fragments, even in the absence of referenced standards.
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