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Understanding the Role of Zn2+ in the hydrolysis of Glycylserine. A mechanistic study by using Density Functional Theory.

Jose R. Moraa,b,*, Oswaldo Nuñezc, Luis Rincóna,b,d, F. Javier Torresa,b a Universidad San Francisco de Quito (USFQ), Instituto de Simulación Computacional (ISC-USFQ), Diego de Robles y Vía Interoceánica, Quito, Ecuador, 17-1200-841 b Universidad San Francisco de Quito (USFQ), Grupo de Química Computacional y Teórica (QCT-USFQ), Dpto. de Ingeniería Química, Quito, Ecuador, 17-1200-841. c Laboratorio de Fisicoquímica orgánica y Química ambiental, Universidad Simón Bolívar, Caracas, Venezuela d Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, La Hechicera, Mérida-5101, Venezuela.

Supporting Information

Figure S1. Mechanism 2. Multi-step reaction mechanism for the hydrolysis of S2 glycylserine catalyzed by Zn2+ at M06/6-311+g(2df,2p) level of theory

1. Cartesian coordinates for TS4-2H2O S3

2. Cartesian coordinates for TS4a-2H2O S3

3. Cartesian coordinates for TS1-2H2O S4

4. Cartesian coordinates for TS1a-2H2O S5

5. Cartesian coordinates for TS1b-2H2O S6

6. Cartesian coordinates for TS1c-2H2O S6

Figure S1. Mechanism 2. Multi-step reaction mechanism for the hydrolysis of glycylserine catalyzed by Zn2+ at M06/6-311+g(2df,2p) level of theory.

S1 1. Cartesian coordinates for TS4-2H2O N 1.46551500 -0.09494500 1.55161800 C 0.17793800 -0.47077600 0.95852700 C 0.09459100 0.07254100 -0.45839600 N -1.06907900 -0.23735100 -1.15475700 O 1.16793200 -0.04916100 -1.18528500 C -2.43432400 -0.30247200 -0.67026100 H 1.40524400 0.83485700 1.95459700 H 0.13786800 -1.55835900 0.88350100 H -0.65858300 -0.13493100 1.57310500 H -0.98865200 0.04046800 -2.12259200 C -2.73739000 -1.59408800 0.09719500 H -2.20337000 -2.41367900 -0.38580800 O 0.02343000 1.72992000 -0.08606400 H -1.13748700 1.89550900 0.02937800 H 1.70678200 -0.73476200 2.29950300 H -3.04722100 -0.36000100 -1.57536200 C -3.01459900 0.90028600 0.07811900 O -2.32683500 1.96602900 0.23228700 O -4.17366100 0.79307700 0.49037600 H -2.38207600 -1.52481400 1.13279300 O -4.11353800 -1.91015400 0.07313400 H -4.57247100 -1.09897600 0.34384800 H 0.30837100 2.15579000 -0.90453500 Zn 2.78050800 -0.07400800 -0.06158100 O 4.75406900 -0.35001400 -0.08085900 H 4.98876800 -1.15588700 -0.55649500 H 5.08407200 -0.46941500 0.81766000

2. Cartesian coordinates for TS4a-2H2O N 2.33877600 1.52209800 0.54123100 C 0.98765200 1.59348800 1.10278800 C 0.06583900 0.87498700 0.11210200 N -1.35511800 0.89153400 0.82429100 O 0.44088800 -0.37559500 -0.12012200 C -2.31163200 -0.12199600 0.35928200 H 2.43104100 2.17829200 -0.22829900 H 0.98398300 1.05958100 2.05493100 H 0.66187700 2.62282000 1.26837400 H -1.22309200 0.75564000 1.82806500 C -2.51806100 -0.08986300 -1.14373100 S2 H -2.73091000 0.93630600 -1.45430800 O -0.09781400 1.61817500 -1.03819300 H -2.90140700 -2.28019200 -0.46928800 H 3.03195400 1.76877200 1.23801000 H -3.27775400 0.11827100 0.82097900 C -1.93100900 -1.46685200 0.95354400 O -2.35415300 -2.53909800 0.30700400 O -1.34096100 -1.56012500 2.00120500 H -1.63013300 -0.43785500 -1.67387400 O -3.62311800 -0.94146100 -1.40329300 H -3.68423700 -1.09036800 -2.35235200 H -0.73224500 2.45572800 -0.80340400 Zn 2.39803500 -0.45348200 -0.15312700 O -1.65092900 3.35703000 -0.26410000 H -2.43945000 3.32215000 -0.80834400 H -1.71618900 1.86437900 0.62768900 O 3.72078400 -1.77153600 -0.81037900 H 4.51757200 -1.33532700 -1.13458200 H 3.36802900 -2.26688500 -1.55934200

3. Cartesian coordinates for TS1-2H2O N 1.83233500 -1.78299400 -0.01589700 C 0.64228300 -1.58481400 0.82130900 C -0.02278700 -0.27319000 0.40895300 N -0.85211000 -0.42575300 -0.76881800 O 0.81040200 0.74568100 0.34612100 C -2.17452800 -0.89697400 -0.36951800 H 2.46032200 -2.45481400 0.40957800 H -0.04386700 -2.42968800 0.74147900 H 0.96333300 -1.49089200 1.85839000 H -0.96088600 0.51438200 -1.14483300 C -2.18280400 -0.81040600 1.17499800 H -3.07502600 -0.32725300 1.57540900 H -2.07565800 -1.78889900 1.64140000 O -1.05059300 -0.00191800 1.50265800 H -1.41538700 1.21850000 1.35803200 H 1.56354300 -2.15649400 -0.92182900 Zn 2.58591800 0.13240500 -0.23426200 H -2.35238500 -1.92653000 -0.67960200 C -3.30071700 -0.02401800 -0.92958100 O -3.08595300 1.21781100 -1.01970500 O -4.36812100 -0.59315900 -1.21043200 H -2.36832900 2.00934800 0.22574500 S3 O -1.84987700 2.23659200 1.05928000 H -2.47965800 2.53726200 1.72819200 O 4.31227000 1.01216200 -0.70906100 H 4.36854700 1.87667200 -0.28439200 H 5.06264200 0.50653400 -0.37455600

4. Cartesian coordinates for TS1a-2H2O N 1.90984000 1.47496500 0.88208800 C 0.73322800 2.23784200 0.45208700 C -0.31658600 1.28530500 -0.09897300 N -1.00379800 0.54147000 1.02421900 O 0.15630600 0.40805100 -0.99030400 C -2.31500200 0.18300000 0.44440700 H 2.74680300 2.04371500 0.83593100 H 0.31801800 2.84588100 1.25818900 H 1.02258600 2.89856400 -0.36461600 H -1.15911600 1.19096700 1.79255100 C -2.50754500 1.21790600 -0.68556100 H -2.56664500 0.72671300 -1.65921900 H -3.39882100 1.82687100 -0.54723000 O -1.37400300 2.06581700 -0.61337800 H 1.80759100 1.16891500 1.84515600 Zn 1.90139500 -0.21030100 -0.38465900 H -3.07678200 0.31179600 1.21442000 C -2.50623900 -1.24485100 -0.05735500 O -1.70146100 -2.18403700 0.26426500 O -3.51467600 -1.42881900 -0.73897000 H -0.68277600 -1.94705500 0.93033600 O 0.24419700 -1.53742100 1.49149700 H 0.20804200 -1.82025700 2.41119700 H -0.28319200 -0.46263300 1.38614600 O 3.26452600 -1.61986400 -0.70308600 H 3.70042000 -1.86782400 0.12111400 H 2.85347400 -2.42670200 -1.03618500

5. Cartesian coordinates for TS1b-2H2O N 2.57335500 1.51160800 0.26551200 C 1.30844500 1.98376400 -0.29581700 C 0.28570100 0.87540500 -0.21598200 N -2.06876500 -0.50593600 1.34555600 O 0.64902400 -0.31098300 -0.46593800 C -2.82487500 0.17820200 0.28949300 S4 H 3.35174200 2.02983700 -0.12589800 H 0.94290000 2.88788900 0.19036200 H 1.45165000 2.19670200 -1.35636700 H -2.64400000 -0.59278700 2.17827000 C -1.95193000 0.39556200 -0.92931800 H -1.54000300 -0.55324000 -1.28343300 H -2.55280300 0.83038000 -1.72619600 O -0.90123300 1.33011400 -0.69013800 H 2.58651600 1.66023700 1.27009400 Zn 2.62359500 -0.51273900 -0.11308100 H -3.13684700 1.15166200 0.67492800 C -4.07791600 -0.59252800 -0.15512400 O -4.13775600 -1.80574000 0.13200400 O -4.92268900 0.07019400 -0.79556200 H -1.86162000 -1.45454600 1.03878500 H -0.95890300 0.18464200 1.55891400 O 0.00887000 0.85063200 1.54554300 H -0.28341800 1.73297100 1.80868000 O 4.01006100 -1.91627000 -0.11886000 H 4.68165400 -1.73955300 -0.78845100 H 3.63637600 -2.77771400 -0.34064600

6. Cartesian coordinates for TS1c-2H2O N 1.85530200 0.73647200 -1.27258800 C 1.73639000 1.90409500 -0.40308700 C 1.31279000 1.45422200 0.96640500 N -3.70054300 0.47463000 -0.86979900 O 1.76160100 0.41072600 1.43380800 C -2.75540200 -0.65970600 -0.70874600 H 0.90174200 0.52558600 -1.59046400 H 2.71746600 2.36744200 -0.26883000 H 1.06312100 2.65740100 -0.80623000 H -4.47264400 0.25673100 -1.49751700 C -1.40881800 -0.04774400 -0.31133200 H -1.51332300 0.30838700 0.73424800 H -0.68284000 -0.87637100 -0.28131400 O -1.04217100 0.96615600 -1.16778300 H 2.42638900 0.95141400 -2.08237000 Zn 2.55507500 -0.80462900 -0.14086300 H -2.66941800 -1.16425900 -1.67037600 C -3.25168600 -1.60806100 0.37454200 O -4.12469800 -1.16956500 1.15534100 S5 O -2.69568400 -2.72481600 0.41281600 H -4.09432800 0.68904500 0.05242500 H -3.17370500 1.27703700 -1.23545600 O 0.51680400 2.20561800 1.65586900 H -0.12364900 2.73354100 1.04567000 O -1.29006200 3.04674000 0.09392100 H -1.08217500 3.78980900 -0.47761000 H -1.19720100 2.14477500 -0.52056400 O 2.88485400 -2.75371800 -0.12157900 H 3.82506200 -2.94988600 -0.02824500 H 2.45514200 -3.15546100 0.64341800