Mechanistic insight into the degradation of sulfadiazine by electro-Fenton system: Role of different reactive species.

Sulfadiazine (SDZ), a widely used effective antibiotic, is resistant to conventional biological treatment, which is concerning since untreated SDZ discharge can pose a significant environmental risk. Electro-Fenton (EF) technology is a promising advanced oxidation technology for efficiently removing SDZ. However, due to the limitations of traditional experimental methods, there is a lack of in-depth study on the mechanism of ·OH-dominated SDZ degradation in EF process. In this study, an EF system was established for SDZ degradation and the transformation products (TPs) were detected by mass spectrometry. Dynamic thermodynamic, kinetic and wave function analysis of reactants, transition states and intermediates were proposed by density functional theory calculations, which was applied to elucidate the underlying mechanism of SDZ degradation. Experimental results showed that amino, benzene, and pyrimidine sites in SDZ were oxidized by ·OH, producing TPs through hydrogen abstraction and addition reactions. ·OH was kinetically more likely to attack SDZ- than SDZ. Fe(IV) dominated the single-electron transfer oxidation reaction of SDZ, and the formed organic radicals can spontaneously generate the de-SO2 product via Smiles rearrangement. Toxicity experiments showed the toxicity of SDZ and TPs can be greatly reduced. The results of this study promote the understanding of SDZ degradation mechanism in-depth. ENVIRONMENTAL IMPLICATION: Sulfadiazine (SDZ) is one of the antibiotics widely used around the world. However, it has posed a significant environmental risk due to its overuse and cannot be efficiently removed by traditional treatment methods. The lack of in-depth study on SDZ degradation mechanism under reactive species limits the improvement of SDZ degradation efficiency. Therefore, this work focused on SDZ degradation mechanism in-depth under electro-Fenton system through reactive species investigation, mass spectrometry analysis, and theoretical calculation. The results in this study can provide a theoretical basis for improving the SDZ degradation efficiency which will contribute to solving SDZ pollution problems.

Elucidating microalgae-mediated metabolism for sulfadiazine removal mechanism and transformation pathways.

Sulfadiazine (SDZ) as a typical sulfonamide antibiotic is commonly detected in wastewater, and its removal mechanism and transformation pathways in microalgae-mediated system remain unclear. In this study, the SDZ removal through hydrolysis, photodegradation, and biodegradation by Chlorella pyrenoidosa was investigated. Higher superoxide dismutase activity and biochemical components accumulation were obtained under SDZ stress. The SDZ removal efficiencies at different initial concentrations were 65.9-67.6%, and the removal rate followed pseudo first-order kinetic model. Batch tests and HPLC-MS/MS analyses suggested that biodegradation and photodegradation through the reactions of amine group oxidation, ring opening, hydroxylation, and the cleavage of S-N, C-N, C-S bond were dominant removal mechanisms and pathways. Characteristics of transformation products were evaluated to analyze their environmental impacts. High-value products of lipid, carbohydrate, and protein in microalgae biomass presented economic potential of microalgae-mediated metabolism for SDZ removal. The findings of this study broadened the knowledge for the microalgae self-protection from SDZ stress and provided a deep insight into SDZ removal mechanism and transformation pathways.

Piezo-promoted persulfate activation by SrBi2B2O7 for efficient sulfadiazine degradation from water.

Combining piezoelectric effect and persulfate (PS) activation is a newly developed strategy for refractory emerging contaminants removal. In this work, borate SrBi2B2O7 (SBBO) is firstly developed as a piezoelectric material to piezo-assisted activation of PS for the removal of sulfadiazine (SDZ) under ultrasonic irradiation (US). SDZ could be efficiently degraded by 85.61 % in the system of PS/SBBO/US with a pseudo-first-order rate constant of 0.0520 min-1, which is faster than that in the systems of PS/SBBO (0.0210 min-1), SBBO/US (0.0041 min-1), PS/US (0.0074 min-1), and PS/BaTiO3/US (0.0120 min-1). The excellent degradation performance of the PS/SBBO/US system is mainly attributed to the piezoelectric effect of the SBBO which plays an important role in PS activation and accelerating reaction. Two oxidation processes, radical process (•O2- and •SO4-) and non-radical process (1O2 and electron transfer), exist during the SDZ degradation. The system of PS/SBBO/US also attains excellent removal efficiency in different SDZ contained water bodies. The possible degradation pathways mainly include cleavage of bonds, ring-opening, and hydroxylation process, and the toxicity of intermediates was predicted by T.E.S.T. software. This study provides new insight into piezoelectric catalysis associated with PS activation for SDZ removal.

Sulfide-modified zero-valent iron activated periodate for sulfadiazine removal: Performance and dominant routine of reactive species production.

In this work, sulfide-modified zero-valent iron (S-Fe0) was used to activate periodate (IO4-, PI) for sulfadiazine (SDZ) removal. 60 µM SDZ could be completely removed within only 1 min by S-Fe0/PI process. Compared with other oxidants including H2O2, peroxymonosulfate (PMS), peroxydisulfate (PDS), S-Fe0 activated PI exhibited better performance for SDZ removal but with lower Fe leaching. Compared with Fe0/PI process, S-Fe0/PI process could reduce more than 80% Fe0 and PI dosage. Inorganic ions and nature organic matters had negligible effect on SDZ removal in S-Fe0/PI system inducing its good SDZ removal efficiency in natural fresh water. 80.2% SDZ still could be removed within 2 min after 7th run. S-Fe0/PI process also exhibited 2.5 - 20.1 folds enhancement for various pollutants removal compared with Fe0/PI process. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemical tests, and density functional theory (DFT) calculation were conducted to confirm the presence of sulfurs could enhance the reactivity of S-Fe0 thus increased the efficiency of PI activation for antibiotics removal. Electron paramagnetic resonance spectroscopy (EPR) tests, radical quenching experiments, quantitative detection and DFT calculation were performed to illustrate the role of multiple reactive species in SDZ removal and the dominant pathway of multiple reactive species production. IO3·, ·OH, O2-·, 1O2, FeIV, and SO4·- all participated in SDZ removal. ·OH played the major role in SDZ removal and the dominant routine of ·OH production was IO4- â†’ O2-· â†’ H2O2 â†’ ·OH. Meanwhile, S-Fe0/PI process could efficiently mineralize SDZ and reduce the toxicity. Comparison with other PI activation approaches and SDZ treatment techniques further demonstrated S-Fe0 was an efficient catalyst for PI activation and present study process was a promising approach for antibiotics removal.

Performance and mechanisms of sulfadiazine removal using persulfate activated by Fe3O4@CuOx hollow spheres.

A Fe-Cu bimetal catalyst (FCHS) was synthesized by depositing Fe3O4 on the shell of CuOx hollow spheres, which were prepared via a soft template method. Several characterization methods, including XRD, SEM-EDS&mapping, TEM, FTIR, and XPS, were used to reveal the morphology and surface properties of FCHS. The characterization results demonstrated that the double-shell hollow structure is formed with a dense coating of Fe3O4 nanoparticles on the surface of CuOx hollow spheres. FCHS can exhibit excellent catalytic activity to degrade sulfadiazine (SDZ) with the oxidant of persulfate (PS). The optimal SDZ removal performance was explored by adjusting reaction parameters, including catalyst dosage, oxidant dosage, and solution pH. The SDZ removal efficiency in the FCHS + PS system could reach 95% at the optimal reaction condition ([catalyst]0 = 0.2 g/L, [PS]0 = 2 mM, pH = 7.0) with 5 mg/L of SDZ. Meanwhile, the degradation efficiency decreased with the coexistence of phosphate or carbonate anions. According to the results of radicals scavenging experiments and the electron paramagnetic resonance analysis, the radicals of SO4·-, O2·- and ·OH generated in the FCHS + PS system contribute to the degradation of SDZ. Moreover, the results of XPS revealed that the solid-state charge-transfer redox couple of Fe(III)/Fe(II) and Cu(I)/Cu(II) can promote the activation of PS. It means that the cooperation effect between Cu oxides and Fe oxides in the double-shell structure is beneficial to the catalytic degradation of SDZ. Furthermore, four possible pathways for SDZ degradation were proposed according to the analysis of intermediate products detected by the LCMS-IT-TOF.

Co-delivery of superfine nano-silver and solubilized sulfadiazine for enhanced antibacterial functions.

For the effective treatment of bacterial infection, it is essential to find a new strategy to deliver antibacterial agents. In the present study, the co-delivery of superfine nano-silver with solubilized sulfadiazine (SD) using cyclodextrin metal-organic frameworks (CD-MOF) as a carrier exhibited superior antibacterial efficacy to insoluble silver sulfadiazine. The abundant hydroxyl moieties in CD-MOF were utilized to reduce Ag precursor into silver nanoparticles (Ag NPs) of 4-5 nm and immobilized within the nano-sized cavities. Microporous CD-MOF facilitated the inclusion of SD molecules in the hydrophobic cavities of γ-cyclodextrin (γ-CD) molecular pairs. The hydrophilic CD-MOF can easily dissolve within exudates at the wound region to release the drug. This approach improved the aqueous solubility of SD by 50 folds which subsequently enhanced SD release and their antibacterial activity. The CD framework also prevented the aggregation of nano-silver particles, stabilizing the particle size and enhancing the curative effects. Hence, the incorporation of superfine nano-silver with solubilized SD using CD-MOF could be an alternate strategy to co-deliver silver and SD with higher efficacy.

Sulfadiazine Masquerading as a Natural Product from Scilla madeirensis (Scilloideae).

The structure of 2,4-(4'-aminobenzenamine)pyrimidine (1), a pyrimidine alkaloid previously isolated from the bulbs of Scilla madeirensis (Asparagaceae, synonym Autonoë madeirensis), has been revised. These conclusions were met via comparison of reported NMR and EIMS data with those obtained from synthetic standards. The corrected structure is the antibiotic sulfadiazine (2), which has likely been isolated as a contaminant from the site of collection. The reported bioactivity of 1 as an α1-adrenoceptor antagonist should instead be ascribed to sulfadiazine. Our findings appear to show another example of an anthropogenic contaminant being identified as a natural product and emphasize the importance of considering the biosynthetic origins of isolated compounds within a phylogenetic context.

Removal of sulfadiazine and ciprofloxacin by clays and manganese oxides: Coupled sorption-oxidation kinetic model.

Sorption onto clays (montmorillonite and kaolinite), oxidation and sorption by manganese oxides (synthesized MnO and natural MnO), and coupled sorption-oxidation experiments were conducted for the removal of antibiotics sulfadiazine (SDZ) and ciprofloxacin (CIP) at pH 5 and 8. Individual sorption and oxidation modelling were carried out using the first-order kinetic model. A coupled sorption-oxidation kinetic model was developed to predict the simultaneous sorption and oxidation process. The coupled sorption-oxidation enhanced the antibiotic sorption, with the first-order sorption rate constants in the simultaneous presence of clays and manganese oxides (ksorp) being higher than those with clays only (ksorp0). In contrast, a depression was observed; the first-order oxidation and sorption combination rate constants in the simultaneous presence of manganese oxides and clays (kMnO) were lower than those with manganese oxides only (kMnO0). In the coupled sorption-oxidation reaction, 13.5-62.5% of SDZ and CIP removal was attributed to the sorption. The SDZ and CIP species distributions at pH 5 affected the coupled sorption and oxidation systems more than those at pH 8. The best removal efficiency was achieved by the montmorillonite-synthesized MnO combination, mainly due to the higher surface area (ABET) and pore size of montmorillonite and synthesized MnO combination compared to other clays and manganese oxides combinations.

Effects of pine bark amendment on the transport of sulfonamide antibiotics in soils.

In the present work, laboratory column experiments were carried out to study the effect of pine bark amendment (at doses of 0, 12, 48 and 96 Mg ha-1) on the transport of three sulfonamide antibiotics (sulfadiazine -SDZ-, sulfamethazine -SMT-, and sulfachloropyridazine -SCP-) through two crop soils. All three sulfonamides showed high mobility in the unamend soils, with absence of retention in most cases. However, some differences were detected regarding the degree of interactions between sulfonamides and soils, being higher for soil 1, which was attributed to its higher organic carbon content. For both soils, interactions with the antibiotics studied followed the sequence SDZ < SMT < SCP, indicating an increase as a function of the hydrophobicity of sulfonamides. Pine bark amendment significantly increased the retention of the three sulfonamides in both soils. Specifically, in the case of soil 1, the incorporation of the highest dose of pine bark (96 Mg ha-1) caused that retention increased from 0% to 70.3% for SDZ, from 2.7% to 71.3% for SMT, and from 0% to 85.4% for SCP. This effect of pine bark is mainly attributed to its high organic carbon content (48.6%), including substances with potential to interact and retain antibiotics, as well as to its acidic pH (4.5). Therefore, pine bark amendment would be an effective alternative to reduce the transport of sulfonamides in soils and, thus, decrease risks of passing to other environmental compartments, as well as harmful effects on the environment and public health.

Catalytic ozonation of the antibiotic sulfadiazine: Reaction kinetics and transformation mechanisms.

In this work, ozone has been used to study the transformation of the antibiotic sulfadiazine (SDZ). SDZ and its transformation products was investigated using liquid chromatography coupled to mass spectrometry and using NMR. The results revealed that 6% of SDZ is transformed into 2-aminopyrimidine. A significant amount of SDZ undergoes a rearrangement reaction followed by ring-closing reactions. One of these products, SDZ-P15, is the main product after 240 min of ozonation. Almost 30% of SDZ transforms into SDZ-P15. SDZ was also transformed via the addition of one or more hydroxyl groups, via the oxidation of an amine group to a nitro group as well as via a bond cleavage reaction. Most of the intermediate products presented in this study have not previously been reported as SDZ transformation products formed using ozonation technology.

Dramatic enhancement effects of l-cysteine on the degradation of sulfadiazine in Fe3+/CaO2 system.

Excessive sulfonamides accumulated in soil and groundwater seriously menace the ecological environment and human health. The performance of a Fenton-like system applying Fe3+ and calcium peroxide (CaO2) in the presence of l-cysteine(l-cys) for sulfadiazine (SDZ) degradation was investigated. Compared with other chelating agents such as citric acid, butyric acid and Ethylenediaminetetraacetic acid, l-cys could effectively promote the SDZ removal in Fe3+/CaO2 system. With the addition of 0.5 mM l-cys, the SDZ degradation increased from 2.14% to 66.53% in 60 min. High concentration of HCO3- inhibited the degradation of SDZ while slightly negative effects on SDZ degradation were observed in the presence of Cl- or humic acid (HA) in l-cys/Fe3+/CaO2 system. Electron paramagnetic resonance (EPR) analysis and radicals scavenge tests affirmed the generation of OH and O2- in l-cys/Fe3+/CaO2 system. Possible degradation pathway of SDZ was speculated and the toxicity of SDZ intermediates was further evaluated. l-cys could enhance the reduction of Fe3+ to Fe2+ and reduced the Fe3+ precipitation due to the l-cys could form stable complexes with Fe3+. l-cys/Fe3+/CaO2 system exhibited high mineralization ability. Overall, these results indicated that l-cys is a promising chelating agent for sulfadiazine wastewater treatment.

Stability of extemporaneous sulfadiazine oral suspensions from commercially available tablets for treatment of congenital toxoplasmosis.

OBJECTIVES: To determine the physicochemical and microbiological stability of sulfadiazine suspensions (100 mg/mL) in simple syrup (A) and sorbitol (B) formulations prepared from commercially available tablets. METHODS: An ultra-performance liquid chromatographic assay was developed and validated to determine the chemical stability of sulfadiazine. Three samples were prepared and stored at 5 and 25 °C and assayed at 0, 7, 14 and 30 days. Physical parameters (appearance, pH, particle size and viscosity) were also monitored. Microbiological examination was performed through the suitable counting method. RESULTS: The formulations presented a sulfadiazine concentration of around 95% at the beginning at both temperatures. There was some variation in pH, viscosity and particle size distribution over time. The samples met the pharmacopoeia criteria of microbiological quality over 30 days, but only sulfadiazine formulated in syrup stored at 25 °C was suitable for use after one week. CONCLUSION: The sulfadiazine suspension in simple syrup was chosen as the most suitable formulation because it demonstrated stability for 14 days at room temperature, providing an alternative liquid dosage form of sulfadiazine for congenital toxoplasmosis treatment.

OBJECTIFS: Déterminer la stabilité physicochimique et microbiologique de suspensions de sulfadiazine (100 mg/mL) dans des formulations de sirop simple (A) et de sorbitol (B) préparées à partir de comprimés disponibles dans le commerce. MÉTHODES: Un test de chromatographie liquide ultra-performante a été développé et validé pour déterminer la stabilité chimique de la sulfadiazine. Trois échantillons ont été préparés et stockés à 5 ºC et à 25 ºC et analysés à 0, 7, 14 et 30 jours. Les paramètres physiques (apparence, pH, granulométrie et viscosité) ont également été contrôlés. Un examen microbiologique a été effectué par la méthode de comptage appropriée. RÉSULTATS: Les formulations présentaient une concentration en sulfadiazine d'environ 95% au début aux deux températures. Il y avait une certaine variation du pH, de la viscosité et de la distribution de la taille des particules au fil du temps. Les échantillons répondaient aux critères de pharmacopée pour la qualité microbiologique aprè 30 jours, mais seule la sulfadiazine formulée dans du sirop conservé à 25 ºC pouvait être utilisée après une semaine. CONCLUSION: La suspension de sulfadiazine dans un sirop simple a été choisie comme la formulation la plus appropriée car elle a démontré une stabilité à 14 jours à température ambiante, fournissant une forme galénique liquide alternative de sulfadiazine pour le traitement de la toxoplasmose congénitale.

Efficient sulfadiazine degradation via in-situ epitaxial grow of Graphitic Carbon Nitride (g-C3N4) on carbon dots heterostructures under visible light irradiation: Synthesis, mechanisms and toxicity evaluation.

The synthesis of environmental-friendly metal-free photocatalysts has great significance in photocatalytic technology. In this work, we firstly report the successful synthesis of in situ epitaxial growth of g-C3N4 on carbon dots through a facile thermal polymerization technique. Characterization and density functional theory (DFT) calculations were conducted to clarify the structure engineering and the electronic/chemical properties of the in-plane interconnected carbon dots/g-C3N4 (C-CN) heterostructures. With the optimal carbon dots content, the C-CN exhibited 3.2 times higher degradation rate for sulfadiazine (SDZ) than that of g-C3N4. Besides, the C-CN heterostructures displayed excellent stability and reusability in five consecutive cycles. The enhanced photocatalytic activity was related to the narrowed band gap and the local electronic density of valance band and conduction band orbitals of the unique plane heterostructures, corroborated by the spectroscopic characterizations and theoretical calculations. Photogenerated holes dominated the degradation of SDZ, while OH showed a negligible contribution. Moreover, DFT calculation succeeded to predict that the atoms with high Fukin index (f0) on SDZ molecule were more vulnerable to radicals attack. SDZ degradation pathway mainly included smiles-type rearrangement, SO2 extrusion, ring hydroxylation and SN bond cleavage processes. The eco-toxicity assessment revealed the generation of less toxic intermediates after photocatalysis. Our findings not only afford a new technique for constructing g-C3N4-based in-plane heterostructures with high and stable photocatalytic efficiency, but also highlight the feasible application of metal-free photocatalysts in environmental remediation.

Adsorption/desorption and transport of sulfadiazine, sulfachloropyridazine, and sulfamethazine, in acid agricultural soils.

Batch-type experiments were used to study adsorption-desorption of three sulfonamides: sulfadiazine (SDZ) sulfachloropyridazine (SCP), and sulfamethazine (SMT), in five crop soils, whereas laboratory soil column experiments were employed to obtain data on transport processes. Adsorption results were satisfactorily adjusted to Linear and Feundlich equations, with R2 values above 0.95. Adsorption followed the sequence SDZ < SMT < SCP, showing higher values for soils with higher levels of organic carbon (OC) content. Conversely, desorption was higher in soils with less OC, and lower in soils with higher OC contents. The temporal moment analysis method gave values for the transport parameters τ and R which were significantly correlated with soil parameters related to organic matter, specifically OC and N concentrations. The higher retention of the three sulfonamides in soils with high organic matter content is a relevant fact, with value when programming management practices in agricultural soils, and specifically in relation to the spreading of animal manures, slurries, or waste containing these emerging pollutants.

Synthesis and In Vitro Anti-Toxoplasma gondii Activity of Novel Thiazolidin-4-one Derivatives.

Recent findings on the biological activity of thiazolidin-4-ones and taking into account the lack of effective drugs used in the treatment of toxoplasmosis, their numerous side effects, as well as the problem of drug resistance of parasites prompted us to look for new agents. We designed and synthesized a series of new thiazolidin-4-one derivatives through a two-step reaction between 4-substituted thiosemicarbazides with hydroxybenzaldehydes followed by the treatment with ethyl bromoacetate; maleic anhydride and dimethyl acetylenedicarboxylate afforded target compounds. The thiazolidin-4-one derivatives were used to assess the inhibition of Toxoplasma gondii growth in vitro. All active thiazolidine-4-one derivatives (12 compounds) inhibited T. gondii proliferation in vitro much better than used references drugs both sulfadiazine as well as the synergistic effect of sulfadiazine + trimethoprim (weight ratio 5:1). Most active among them derivatives 94 and 95 showed inhibition of proliferation at about 392-fold better than sulfadiazine and 18-fold better than sulfadiazine with trimethoprim. All active compounds (82-88 and 91-95) against T. gondii represent values from 1.75 to 15.86 (CC30/IC50) lower than no cytotoxic value (CC30).

Size-dependent adsorption of antibiotics onto nanoparticles in a field-scale wastewater treatment plant.

This work present aims to evaluate the effect of a conventional wastewater treatment process on the number of nanoparticles, and the role of nanoparticles as a carrier of antibiotics. A set of methods based on asymmetrical flow field flow fractionation coupled with multi-angle light scattering to separate and quantify nanoparticles in real wastewater was established. The characterization of nanoparticles was conducted by transmission electron microscopy, energy dispersive spectrometer, UV-visible spectrophotometer and three-dimensional excitation-emission matrix fluorescence spectroscopy. The adsorption of different sizes of nanoparticles separated from the real wastewater for four targeted antibiotics (sulfadiazine, ofloxacin, tylosin and tetracycline) was studied. The results show that the number of nanoparticles were increased in the wastewater treatment process and the size range between 60 and 80 nm was predominant in wastewater samples. The nanoparticles were mainly composed of O, Si, Al and Ca elements and organic components were in the size range of 0-10 nm. Targeted antibiotics were dominantly adsorbed onto nanoparticles with 60-80 nm size range at each stage. The concentrations of tetracycline adsorbed on nanoparticles were surprisingly increased in the end of the treatment process, while ofloxacin and tylosin had the completely opposite phenomenon to tetracycline. The pH and ionic strength definitely affected the aggregation of nanoparticles and interaction with the antibiotics. It is of great significance to give insights into nanoparticle-antibiotic assemblages for the effective treatment and avoiding the water risks due to nanoparticles' ubiquitous and their risks of carrying antibiotics.

Simultaneous sulfadiazines degradation and disinfection from municipal secondary effluent by a flow-through electro-Fenton process with graphene-modified cathode.

Conventionally the deep treatment and disinfection are fulfilled by different processes for municipal wastewater treatment, this work verified a breakthrough by one process of novel flow-through electro-Fenton (EF) with graphene-modified cathode, which is usually seemed to be ineffective. This process was firstly confirmed to be cost-effective for simultaneous sulfadiazines (SDZs) degradation and disinfection from municipal secondary effluent with a very low electrical energy consumption (EEC) of 0.21 kW h/m3, attributed to the high H2O2 production of 4.41 mg/h/cm2 on the novel graphite felt cathode modified by electrochemically exfoliated graphene (EEGr) with a low EEC of 3.08 kW h/(kg H2O2). Compared with the ineffective SDZs degradation by the conventional flow EF, this process was more cost-effective and overcame the harsh requirements on electrolyte concentration. It also showed good effectiveness in the degradation of different antibiotics, and the graphene-modified cathode still kept stable performance after eight consecutive runs. Account for the combined action of OH and active chlorine, the formation of hydroxylated and chlorine containing by-products was confirmed, and a possible degradation mechanism for SDZs was proposed. This flow-through EF process provided an alternative method for the disinfection and antibiotics degradation by one process for the treatment and reuse of municipal secondary effluent.

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals.

Comprehension of the nanomechanical response of crystalline materials requires the understanding of the elastic and plastic deformation mechanisms in terms of the underlying crystal structures. Nanoindentation data were combined with structural and computational inputs to derive a molecular-level understanding of the nanomechanical response in eight prototypical sulfa drug molecular crystals. The magnitude of the modulus, E, was strongly connected to the non-covalent bond features, that is, the bond strength, the relative orientation with the measured crystal facet and their disposition in the crystal lattice. Additional features derived from the current study are the following. Firstly, robust synthons well isolated by weak and dispersive interactions reduce the material stiffness; in contrast, the interweaving of interactions with diverse energetics fortifies the crystal packing. Secondly, mere observation of layered structures with orthogonal distribution of strong and weak interactions is a prerequisite, but inadequate, to attain higher plasticity. Thirdly, interlocked molecular arrangements prevent long-range sliding of molecular planes and, hence, lead to enhanced E values. In a broader perspective, the observations are remarkable in deriving a molecular basis of the mechanical properties of crystalline solids, which can be exploited through crystal engineering for the purposeful design of materials with specific properties.

Selective adsorption behavior/mechanism of antibiotic contaminants on novel boron nitride bundles.

The novel hexagonal boron nitride (BN) bundles, assembled by a plenty of BN fibers with high adsorption capacity and outstanding recyclability, were prepared easily as an efficient adsorbent for antibiotics. It is an excellent substitute for carbonaceous adsorbent to overcome the shortcoming in low adsorption capacity and poor recyclability. Its high surface area can reach up to 871.456 m2 g-1. The adsorption capacity and removal percentage to sulfadiazine (SDZ, 0.328 mmol g-1, 82.192%), oxytetracycline (OTC, 0.202 mmol g-1, 92.890%) and erythromycin (EM, 0.126 mmol g-1, 90.140%) are superior compared with activated carbon and graphene nanoplatelets. It is interesting that BN bundles have a better adsorption to small molecules since huge molecules are easily restricted to enter the micropores, which was defined as micropore-filling effect. Moreover, the adsorption isotherms are well fitted by the Langmuir and Tempkin model, while pseudo-second-order model can better describe the adsorption kinetics. The adsorption mechanisms were deduced to be mainly π-π electron-donor-accepter interaction while electrostatic force and hydrophobic interaction played a significant role. The excellent reusability can be seen from the high removal efficiency after five recycles suggesting the BN bundles was a promising adsorbent for the efficient removal of antibiotics pollutants.

Modelled phototransformation kinetics of the antibiotic sulfadiazine in organic matter-rich lakes.

Xenobiotic compounds are commonly detected in inland waters. Sunlight-induced photochemical reactions contribute to xenobiotic degradation, but the role of different photoreactions on large geographic scales remains poorly understood. Here, we used a combination of photochemical modelling and large-scale field data from 1020 lakes across Sweden to elucidate the photodegradation kinetics of the commonly used antibiotic sulfadiazine (SDZ) in organic matter-rich lakes. SDZ occurs in two forms, namely acidic HSDZ (pKa = 6.5) and basic/deprotonated SDZ-. Both species are oxidised fast by the photogenerated triplet states of natural organic matter (3NOM*). However, they also undergo efficient back reactions because the partially oxidised HSDZ (and SDZ- to a larger extent) can be reduced back to the initial compounds by the phenolic moieties contained in NOM. Typical lakes in Sweden are rich in NOM and have low pH, with the consequence that SDZ photochemistry would be dominated by HSDZ. Our simulation results showed that SDZ photodegradation kinetics in Swedish lakes would become significantly slower with increasing water depth and pH, while it depended little on latitude, which affects irradiance, or on organic matter content. As a consequence, SDZ would be particularly persistent in lakewater in some densely populated areas with relatively deep and high-pH lakes such as, most notably, the Stockholm region. Here the surface waters could be more heavily contaminated by pharmaceuticals compared to the scarcely populated regions in the centre-north of the country, where lakewater could otherwise promote an efficient photodegradation of SDZ.