bio

Enzymes that catalyze carbon-silicon bond formation are unknown in nature, despite the
natural abundance of both elements. Such enzymes would expand the catalytic repertoire of
biology, enabling living systems to access chemical space previously only open to synthetic
chemistry. We have discovered that heme proteins catalyze the formation of organosilicon
compounds under physiological conditions via carbene insertion into silicon-hydrogen bonds.
The reaction proceeds both in vitro and in vivo, accommodating a broad range of substrates
with high chemo- and enantioselectivity. Using directed evolution, we enhanced the catalytic
function of cytochrome c from Rhodothermus marinus to achieve more than 15-fold higher
turnover than state-of-the-art synthetic catalysts. This carbon-silicon bond-forming biocatalyst
offers an environmentally friendly and highly efficient route to producing enantiopure
organosilicon molecules.

Silicon constitutes almost 30% of the mass of Earth’s crust, yet no life form is known to
have the ability to forge carbon-silicon bonds. Despite the absence of organosilicon compounds
in the biological world, synthetic chemistry has enabled us to appreciate the distinctive and
desirable properties that have led to their broad applications in chemistry and material science.
As a biocompatible carbon isostere, silicon can also be used to optimize and repurpose the
pharmaceutical properties of bioactive molecules.

The natural supply of silicon may be abundant, but sustainable methods for synthesizing
organosilicon compounds are not. Carbon -silicon motifs to organic molecules enantioselectively
rely on multistep synthetic campaigns to prepare and optimize chiral reagents or catalysts;
precious metals are also sometimes needed to achieve the desired activity. Synthetic
methodologies such as carbene insertion into silanes can be rendered enantioselective using
chiral transition metal complexes based on rhodium, iridium, and copper. These catalysts can
provide optically pure products, but not without limitations: They require halogenated solvents
and sometimes low temperatures to function optimally and have limited turnovers.

Because of their ability to accelerate chemical transformations with exquisite specificity

and selectivity, enzymes are increasingly sought-after complements to, or even replacements
for, chemical synthesis methods. Biocatalysts that are fully genetically encoded and assembled
inside of cells are readily tunable with molecular biology techniques. They can be produced at
low cost from renewable resources in microbial systems and perform catalysis under mild
conditions. Although nature does not use enzymes to form carbon-silicon bonds, the protein
machineries of living systems are often “promiscuous” - that is, capable of catalyzing reactions
distinct from their biological functions. Evolution, natural or in the laboratory, can use these
promiscuous functions to generate catalytic novelty. For example, heme proteins can catalyze a
variety of non-natural carbene-transfer reactions in aqueous media, including N-H and S-H
insertions, which can be greatly enhanced and made exquisitely selective by directed evolution.
 One of the most pervasive problems afflicting people throughout the world is inadequate
access to clean water and sanitation. Problems with water are expected to grow worse in the
coming decades, with water scarcity occurring globally, even in regions currently considered
water-rich. Addressing these problems calls out for a tremendous amount of research to be
conducted to identify robust new methods of purifying water at lower cost and with less energy,
while at the same time minimizing the use of chemicals and impact on the environment. Here
we highlight some of the science and technology being developed to improve the disinfection
and decontamination of water, as well as efforts to increase water supplies through the safe re-
use of wastewater and efficient desalination of sea and brackish water.

The many problems worldwide associated with the lack of clean, fresh water are well
known: 1.2 billion people lack access to safe drinking water, 2.6 billion have little or no
sanitation, millions of people die annually- 3,900 children a day- from diseases transmitted
through unsafe water or human excreta. Countless more are sickened from disease and
contamination. Intestinal parasitic infections and diarrheal diseases caused by waterborne
bacteria and enteric viruses have become a leading cause of malnutrition owing to poor
digestion of the food eaten by people sickened by water. In both developing and industrialized
nations, a growing number of contaminants are entering water supplies from human activity:
from traditional compounds such as heavy metals and distillates to emerging micropollutants
such as endocrine disrupters and nitrosoamines. Increasingly, public health and environmental
concerns drive efforts to decontaminate waters previously considered clean. More effective,
lower-cost, robust methods to disinfect and decontaminate waters from source to point-of-use
are needed, without further stressing the environment or endangering human health by the
treatment itself.

Water also strongly affects energy and food production, industrial output, and the quality
of our environment, affecting the economies of both developing and industrialized nations. Many
freshwater aquifers are being contaminated and overdrawn in populous regions- some
irreversibly- or suffer saltwater intrusion along coastal regions. With agriculture, livestock and
energy consuming more than 80% of all water for human use, demand for fresh water is
expected to increase with population growth, further stressing traditional sources. The shift to
biofuels for energy may add further demands for irrigation and refining. Alarmingly, within 30
years receding glaciers may cause major rivers such as the Brahmaputra, Ganges, Yellow
(which at times no longer runs the sea) and Mekong rivers, which serve China, India and
Southeast Asia, to become intermittent, imperiling over 1.5 billion people during the dry months.
Even industrialized nations in North America and Europe, and those in Andean counries in
South America, could see major disruptions to agriculture, hydroelectric and thermoelectric
generation, and municipal water supplies from reductions in snowmelt and/or loss of glaciers In
the coming decades, water scarcity may be a watchword that prompts action ranging from
wholesale population migration to war, unless new ways to supply clean water are found.