116 4.2  Super-Resolution Microscopy

Irreversible photobleaching, primarily due to free radical formation, can be suppressed by

chemical means using quenchers. In essence, these are chemicals that mop up free radicals

and prevent them from binding to fluorophores and inactivating their ability to fluorescence.

The most widely used is based on a combination of the sugar glucose (G) and two enzymes

called “glucose oxidase” (GOD) and “catalase” (CAT). The G/​GOD/​CAT freeradical quencher

works through a reaction with molecular oxygen (O.):

(4.5)

G

O

GA+H O

H O

H O

O

GOD

CAT

+

+





2

2

2

2

2

2

2

2

where glucose is a substrate for GOD, which transfers electrons in glucose to form a product

glucuronic acid (GA), and hydrogen peroxide (H2O2). In a second reaction, CAT transfers

electrons from two molecules of hydrogen peroxide to form water and oxygen gas. The

downside is that as GA accumulates, the pH of the solution potentially drops, and so strong

pH buffers are required to prevent this, though there are some newer quencher systems avail­

able that have less effect on pH.

As a rough guide, at video-​rate imaging of a typical FP such as GFP, a high-​magnification

fluorescence microscope optimized for single-​molecule localization microscopy can achieve

a localization precision in the lateral xy focal plane of a few tens of nanometers, with irrevers­

ible photobleaching occurring after 5–​10 image frames per GFP, or ~200–​400 ms at video-​

rate sampling. If faster sampling time is required, for example, to overcome motion blurring

of the fluorophore in cytoplasmic environments, then detection may need to be more in the

range of 1–​5 ms per image frame, and so the total duration that a typical FP can be imaged

is in the range ~5–​50 ms. However, as discussed in the previous section, strobing can be

implemented to space out this limited photon emission budget to access longer time scales

where appropriate for the biological process under investigation.

4.2.4  ADVANCED APPLICATIONS OF LOCALIZATION MICROSCOPY

Localization microscopy super-​resolution approaches have been successively applied to multi­

color fluorescence imaging in cells, especially dual-​color imaging, also known as colocalization

microscopy, where one biomolecule of interest is labeled with one-​color fluorophore, while

a different protein in the same cell is labeled with a different color fluorophore, and the two

emission signals from each are split optically on the basis of wavelength to be detected in

two separate channels (see Chapter 8 for robust computational methods to determine if two

fluorophores are colocalized or not). This has led to a surplus of acronyms for techniques that

essentially have the same core physical basis. These include single-​molecule high-​resolution

colocalization that can estimate separations of different colored fluorophores larger than

~10 nm (Warshaw et al., 2005, for the technique’s invention; Churchman et al., 2005, for

invention of the acronym). Also, techniques called “single-​molecule high-​resolution imaging

with photobleaching” (Gordon et al., 2004) and “nanometer-​localized multiple single-​

molecule fluorescence microscopy” (Qu et al., 2004) both use photobleaching to localize two

nearby fluorophores to a precision of a few nanometers up to a few tens of nanometers.

Single-​particle tracking localization microscopy (TALM) uses localization microscopy of

specifically mobile-​tagged proteins (Appelhans et al., 2012).

4.2.5  LIMITING CONCENTRATIONS FOR LOCALIZATION MICROSCOPY

Localization microscopy super-​resolution techniques are effective if the mean nearest-​

neighbor separation of fluorophores in the sample is greater than the optical resolution limit,

permitting the PSF associated with a single fluorophore to be discriminated from others in

solution. Therefore, there is a limiting concentration of fluorescently tagged molecules in a