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Hydrogen bonds, aromatic stacking contacts and σ-hole interactions are all noncovalent interactions commonly observed in biological systems. Structural data derived from the Protein Data Bank showed that methionine residues can interact with oxygen atoms through directional S...O contacts in the protein core. In the present work, the Cambridge Structural Database (CSD) was used in conjunction with ab initio calculations to explore the σ-hole interaction properties of small-molecule compounds containing divalent sulfur. CSD surveys showed that 7095 structures contained R 1 -S-R 2 groups that interact with electronegative atoms like N, O, S and Cl. Frequencies of occurrence and geometries of the interaction were dependent on the nature of R 1 and R 2 , and the hybridization of carbon atoms in C,C-S, and C,S-S fragments. The most common interactions in terms of frequency of occurrence were C,C-S...O, C,C-S...N and C,C-S...S with predominance of Csp 2 . The strength of the chalcogen interaction increased when enhancing the electron-withdrawing character of the substituents. The most positive electrostatic potentials (V S,max ; illustrating positive σ-holes) calculated on R 1 -S-R 2 groups were located on the S atom, in the S-R 1 and S-R 2 extensions, and increased with electron-withdrawing R 1 and R 2 substituents like the interaction strength did. As with geometric data derived from the CSD, interaction geometries calculated for some model systems and representative CSD compounds suggested that the interactions were directed in the extensions of S-R 1 and S-R 2 bonds. The values of complexation energies supported attractive interactions between σ-hole bond donors and acceptors, enhanced by dispersion. The interactions of R 1 -S-R 2 with large V S,max and nucleophiles with large negative V S,min coherently provided more negative energies. According to NBO analysis, chalcogen interactions consisted of charge transfer from a nucleophile lone pair to an S-R 1 or S-R 2 antibonding orbital. The directional σ-hole interactions at R 1 -S-R 2 can be useful in crystal engineering and the area of supramolecular biochemistry.

Although the United Nations General Assembly recognized in 2010 the right to safe and clean drinking water and sanitation as a human right that is essential to the full enjoyment of life and all other human rights, the contamination of water supplies with faecal pathogens is still a major and unsolved problem in many parts of the world. In this study, faecal indicator bacteria (FIB), including Escherichia coli (E. coli) and Enterococcus (ENT), were quantified over the period of June/July 2014 and June/July 2015 to assess the quality of hospital effluents (n = 3: H1, H2 and H3) and of rivers receiving wastewaters from the city of Kinshasa, Democratic Republic of Congo. The water and sediment samples from the river-receiving systems were collected in, upstream and downstream of the hospital outlet pipe (HOP) discharge. The analysis of E. coli and ENT in water and sediment suspension was performed using the cultural membrane filter method. The FIB characterization was performed for general E. coli, Enterococcus faecalis(E. faecalis) and human-specific Bacteroides by PCR using specific primers. The results revealed very high FIB concentration in the hospital effluent waters, with E. coli reaching the values of 4.2 × 10(5), 16.1 × 10(5) and 5.9 × 10(5) CFU 100 mL(-1), for the hospital effluents from H1, H2, and H3, respectively; and Enterococcus reaching the values of 2.3 × 10(4), 10.9 × 10(4) and 4.1 × 10(4) CFU 100 mL(-1), respectively. Interestingly, the FIB levels in the water and sediment samples from river-receiving systems are spatially and temporally highly variable and present in some samples with higher values than the hospital effluents. The PCR assays for human-specific Bacteroides HF183/HF134 further indicate that more than 98% of bacteria were from human origin. The results of this research therefore confirm the hypothesis of our previous studies, indicating that in developing countries (e.g., Democratic Republic of Congo and South India), the hospital effluent waters can be a significant source of the deterioration of the bacteriological quality for urban rivers. The approach used in this investigation can be further used to decipher the pollution of water resources by human faecal contamination. The results of this research will help to better understand the microbiological pollution problems in river-receiving systems and will guide municipality decisions on improving the urban water quality.

In recent years there has been considerable interest in chalcogen and hydrogen bonding involving Se atoms, but a general understanding of their nature and behaviour has yet to emerge. In the present work, the hydrogen-bonding ability and nature of Se atoms in selenourea derivatives, selenoamides and selones has been explored using analysis of the Cambridge Structural Database and ab initio calculations. In the CSD there are 70 C=Se structures forming hydrogen bonds, all of them selenourea derivatives or selenoamides. Analysis of intramolecular geometries and ab initio partial charges show that this bonding stems from resonance-induced C(δ+)=Se(δ-) dipoles, much like hydrogen bonding to C=S acceptors. C=Se acceptors are in many respects similar to C=S acceptors, with similar vdW-normalized hydrogen-bond lengths and calculated interaction strengths. The similarity between the C=S and C=Se acceptors for hydrogen bonding should inform and guide the use of C=Se in crystal engineering.