9This article summarizes the recent efforts in the High Pressure Processes Group labs at UVa 10 regarding the fundamentals of biomass hydrolysis in pressurized water medium. At extremely 11 low reaction times (0.02 s), cellulose was hydrolyzed in supercritical water (400ºC and 25 12 MPa) obtaining a sugars yield higher than 95% w·w -1 while 5-HMF yield was lower than 13 0.01% w·w -1 . When the reaction times was increased up to 1 s, the main product was 14 glycolaldehyde (60% w·w -1 ). Independently of the reaction time, the yield of 5-HMF was 15 always lower than 0.01% w·w -1 . In order to evaluate the reaction pathway and mechanism of 16 plant biomass in pressurized water, several parameters (temperature, pressure, reaction time 17 and reaction medium) were studied for different biomasses (cellulose, glucose, fructose and 18 wheat bran). It was considered that the reactions of glucose isomerization to fructose as well 19 as fructose dehydration to 5-HMF take place via proton or hydroxide anion association. So, 20 their concentration was taken into account as reagent concentration in the reaction 21 evaluations. It was found that the proton and hydroxide anion concentration in the medium 22 due water dissociation is the determining factor in the selectivity of the process. The reaction 23 of glucose isomerization to fructose and its further dehydration to produce 5-HMF are highly 24 dependent on ions concentration. By increasing pOH/pH, these reactions were minimized 25 allowing the control of 5-HMF production. At this condition, the retro-aldol condensation 26 pathway was enhanced instead of isomerization/dehydration pathway. 27 3 INTRODUCTION 28