Introduction Nitroaromatic compounds (NACs) resist microbial degradation due to their electron deficiency. Further substitution with electronwithdrawing groups, such as chloro group, increases the electron deficiency and recalcitrance. NACs and the closely related chloronitroaromatics (CNACs) are widely used in several industries, and are toxic and mutagenic, posing an ecological threat. Since the occurrence of natural NACs is limited, microbes have only recently been exposed to the anthropogenic burden of NACs. However, within this short exposure time, several microbes have evolved the capability to metabolise NACs. The enzymes initiating metabolism of NACs warrant special attention due to the thermodynamic and xenobiotic considerations involved. The current article reviews the state-ofthe-art knowledge on some of the important enzymes that catalyse the initial step of NAC degradation. Conclusion Looking at the recent progress, dioxygenases hold a lot of promise for NAC degradation. In the near future, the structure–function relationship of the dioxygenases will be better understood. This will allow researchers to generate dioxygenases with desired specificity at will and, of course, at the mercy of the enzyme flexibility. Introduction Nitroaromatic compounds (NACs) contain at least one nitro group attached to an aromatic ring. The aromatic ring is relatively inert due to the delocalisation of π electrons. The nitro group, being a strong electrophile, further deactivates the ring towards electrophilic substitution through inductive effect and conjugation. Figure 1 shows the effect of various substituents on the reactivity of benzene ring1. In general, increasing electronegativity of the substituents increases the degree of deactivation. Due to the electron deficiency over the aromatic ring, oxidative metabolism of NACs is very difficult. The presence of additional substituents also affects the reactivity of NACs. Electron-withdrawing groups increase the electron deficiency and consequently, deactivate the NACs, whereas electron-donating groups activate NACs towards oxidative metabolism (Figure 1). Thus, electron-withdrawing substituents like nitro and chloro groups make polynitroaromatics and chloronitroaromatics (CNACs) resistant to aerobic microbial degradation. It is, however, observed that the nitro group in NACs is easily reducible, and substitution with electron-withdrawing groups, like chloride or another nitro group, greatly increases the rate of reduction. For example, trinitrotoluene (TNT) readily undergoes reductive metabolism, which results in reduction of one nitro group to amino group. However, amino group, being electron-donating, decreases the electron deficiency, due to which the reduction of remaining nitro groups is less rapid and requires lower redox potential2. Majority of the NACs are produced and released into the environment by anthropogenic activities. They are widely used in the production of pesticides, dyes, polymers, pharmaceuticals, explosives, agrochemicals and speciality chemicals. CNACs are used as precursors for the synthesis of important chemicals, such as drugs, herbicides and dyes. Due to their recalcitrant nature, these compounds are discharged into the environment, where they accumulate and cause serious pollution. Several NACs and the closely related CNACs are listed as priority pollutants by the U.S. Environmental Protection Agency3. Many of the NACs are toxic, mutagenic and established carcinogens. They show acute ecotoxicity towards algae and aquatic invertebrates, and are phytotoxic4. Several NACs are associated with methaemoglobinaemia, anaemia, hepatic toxicity, neurotoxicity, nephrotoxicity, and splenic, reproductive and respiratory disorders in * Corresponding author Email: abafana@rediffmail.com 1 Environmental Health Division, National Environmental Engineering Research Institute (NEERI), Council of Scientific and Industrial Research (CSIR), Nagpur-440020, India Figure 1: Aromatic ring substituents in the order of their electron withdrawing and consequently, electrophilic substitution-deactivating effect.