Water Networks as Hydrophobic Recognition Motifs in Proteins

S Serena G. Piticchio (Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) M Miriam Martínez‐Cartró (Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) S Salvatore Scaffidi (Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) S Sergio Rodríguez‐Arévalo (Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) A Andrea Bagán (Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) A Ainoa Sánchez‐Arfelis (Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) S Sarah Picaud (Nuffield Department of Medicine, Oxford University Old Road Campus Research Building Oxford OX2 7DQ UK) T Tobias Krojer (Structural Genomics Consortium, Nuffield Department of Medicine Oxford University, Old Road Campus Research Building Roosevelt Drive Oxford OX3 7DQ UK) P Panagis Filippakopoulos (Nuffield Department of Medicine, Oxford University Old Road Campus Research Building Oxford OX2 7DQ UK) F Frank von Delft C Carmen Escolano (Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) C Carles Galdeano (Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain) X Xavier Barril (Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain)

Abstract

Abstract The hydrophobic effect is a central force in molecular recognition, typically attributed to the ordering of water molecules around apolar groups. Hydrophobic interaction sites on proteins are therefore readily predicted based on surface polarity. Yet, in the bromodomain‐containing protein 4 (BRD4), a well‐known hydrophobic hot spot is paradoxically lined by a network of water molecules. Here we combine binding assays, structural data, molecular dynamics, and free‐energy calculations to resolve this apparent contradiction. We show that the water network functions as a hydrophobic recognition motif that cannot accommodate polar groups without disruption. Instead, as the protein pre‐organizes the water network, apolar groups can bind with minimal entropic cost. In turn, they reinforce the surrounding hydrogen‐bond network, limiting the mobility of the entire protein–water assembly. With this perspective, we identify water networks potentially functioning as hydrophobic motifs in other pharmacological targets, revealing a general but overlooked recognition element with broad implications in drug discovery and protein design.

Article Details

Volume / Issue Vol. 65, Issue 2
Published January 09, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (13)

S

Serena G. Piticchio

Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

M

Miriam Martínez‐Cartró

Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

S

Salvatore Scaffidi

Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

S

Sergio Rodríguez‐Arévalo

Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

A

Andrea Bagán

Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

A

Ainoa Sánchez‐Arfelis

Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

S

Sarah Picaud

Nuffield Department of Medicine, Oxford University Old Road Campus Research Building Oxford OX2 7DQ UK

T

Tobias Krojer

Structural Genomics Consortium, Nuffield Department of Medicine Oxford University, Old Road Campus Research Building Roosevelt Drive Oxford OX3 7DQ UK

P

Panagis Filippakopoulos

Nuffield Department of Medicine, Oxford University Old Road Campus Research Building Oxford OX2 7DQ UK

F

Frank von Delft

C

Carmen Escolano

Laboratory of Medicinal Chemistry Department of Pharmacology, Toxicology and Medicinal Chemistry Faculty of Pharmacy and Food Sciences and Institute of Biomedicine (IBUB) University of Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

C

Carles Galdeano

Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain

X

Xavier Barril

Departament de Farmacia i Tecnología Farmacèutica, i Fisicoquímica Institut de Biomedicina (IBUB), Universitat de Barcelona Av. Joan XXIII, 27‐31, E‐08028 Barcelona Spain