Water's surface dielectric: Theoretical studies predict that the inhibition of rotational motion of water near a solid surface will decrease its local dielectric constant. Fumagalli et al. fabricated thin channels in insulating hexagonal boron nitride on top of conducting graphene layers (see the Perspective by Kalinin). The channels, which varied in height from 1 to 300 nanometers, were filled with water and capped with a boron nitride layer. Modeling of the capacitance measurements made with an atomic force microscope tip revealed a surface-layer dielectric constant of 2, compared with the bulk value of 80 for water. Science , this issue p. 1339 ; see also p. 1302

Water is essential for almost every aspect of life on our planet and, unsurprisingly, its properties have been studied in great detail¹. However, disproportionately little remains known about the electrical properties of interfacial and strongly confined water^2,3, in which the structure deviates from that of bulk water, becoming distinctly layered^4,5. The structural change is expected to affect the conductivity of water and particularly its polarizability, which in turn modifies intermolecular forces that play a crucial role in many physical and chemical processes^6–9. Here we use scanning dielectric microscopy (SDM)¹⁰ to probe the in-plane electrical properties of water confined between atomically flat surfaces separated by distances down to 1 nm. For confinement exceeding several nanometres, water exhibits an in-plane dielectric constant close to that of bulk water and its proton conductivity is notably enhanced, gradually increasing with decreasing water thickness. This trend abruptly changes when the confined water becomes only a few molecules thick. Its in-plane dielectric constant reaches large, ferroelectric-like values of about 1,000, whereas the conductivity peaks at several S m⁻¹, close to values characteristic of superionic liquids. We attribute the enhancement to strongly disordered hydrogen bonding induced by the few-layer confinement, which facilitates both easier in-plane polarization of molecular dipoles and faster proton exchange. This insight into the electrical properties of nanoconfined water is important for understanding many phenomena that occur at aqueous interfaces and in nanoscale pores.

Mapping the dielectric constant at the nanoscale of samples showing a complex topography, such as non-planar nanocomposite materials or single cells, poses formidable challenges to existing nanoscale dielectric microscopy techniques. Here we overcome these limitations by introducing Scanning Dielectric Force Volume Microscopy. This scanning probe microscopy technique is based on the acquisition of electrostatic force approach curves at every point of a sample and its post-processing and quantification by using a computational model that incorporates the actual measured sample topography. The technique provides quantitative nanoscale images of the local dielectric constant of the sample with unparalleled accuracy, spatial resolution and statistical significance, irrespectively of the complexity of its topography. We illustrate the potential of the technique by presenting a nanoscale dielectric constant map of a single bacterial cell, including its small-scale appendages. The bacterial cell shows three characteristic equivalent dielectric constant values, namely, ε_r,bac1 = 2.6 ± 0.2, ε_r,bac2 = 3.6 ± 0.4 and ε_r,bac3 = 4.9 ± 0.5, which enable identifying different dielectric properties of the cell wall and of the cytoplasmatic region, as well as, the existence of variations in the dielectric constant along the bacterial cell wall itself. Scanning Dielectric Force Volume Microscopy is expected to have an important impact in Materials and Life Sciences where the mapping of the dielectric properties of samples showing complex nanoscale topographies is often needed.

We show that the internal hydration properties of single Bacillus cereus endospores in air under different relative humidity (RH) conditions can be determined through the measurement of its electric permittivity by means of quantitative electrostatic force microscopy (EFM). We show that an increase in the RH from 0% to 80% induces a large increase in the equivalent homogeneous relative electric permittivity of the bacterial endospores, from ∼4 up to ∼17, accompanied only by a small increase in the endospore height, of just a few nanometers. These results correlate the increase of the moisture content of the endospore with the corresponding increase of environmental RH. Three-dimensional finite element numerical calculations, which include the internal structure of the endospores, indicate that the moisture is mainly accumulated in the external layers of the endospore, hence preserving the core of the endospore at low hydration levels. This mechanism is different from what we observe for vegetative bacterial cells of the same species, in which the cell wall at high humid atmospheric conditions is not able to preserve the cytoplasmic region at low hydration levels. These results show the potential of quantitative EFM under environmental humidity control to study the hygroscopic properties of small-scale biological (and nonbiological) entities and to determine its internal hydration state. A better understanding of nanohygroscopic properties can be of relevance in the study of essential biological processes and in the design of bionanotechnological applications.

The dielectric constant of flagellin proteins in flagellar bacterial filaments ∼10–20 nm in diameter is measured using scanning dielectric microscopy. We obtained for two different bacterial species (Shewanella oneidensis MR-1 and Pseudomonas aeruginosa PAO1) similar relative dielectric constant values ε_So = 4.3 ± 0.6 and ε_Pa = 4.5 ± 0.7, respectively, despite their different structure and amino acid sequence. The present results show the applicability of scanning dielectric microscopy to nanoscale filamentous protein complexes and to general 3D macromolecular protein geometries, thus opening new avenues to study the relationship between the dielectric response and protein structure and function.