Two-time champion Svetlana Kuznetsova crashed out of the Kremlin Cup after being handed a straight-sets defeat by Karolina Muchova in the opening round.
Home favourite Kuznetsova – who won the WTA Tour tournament in 2015 before returning to successfully defend her title the following year – managed just 13 winners as Muchova triumphed 6-2 6-3 to set up a second-round clash with fourth seed Donna Vekic.
Anastasija Sevastova had no such problems in her opening encounter, easing past Aliaksandra Sasnovich 6-1 7-5, while Anna Kalinskaya overcame Anastasia Potapova 6-0 3-6 6-4 via a tense final set that saw the two players combine to produce seven breaks of serve.
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Elina Svitolina and Kiki Bertens are the top seeds for the tournament, though neither are in action during Tuesday's play in Russia.
At the Luxembourg Open, Viktoria Kuzmova rallied from a set down to defeat teenager Katie Volynets 6-7 (4-7) 7-6 (7-1) 6-1.
The sixth seed let slip a 5-2 lead in the second set before eventually prevailing in a tie-break, while she dropped just 10 points in the decider to triumph after two hours, 33 minutes on court.
Margarita Gasparyan, Tatjana Maria and Denisa Allertova also recorded three-set wins in the main draw, the latter coming through via a tense tie-break against Mandy Minella.
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