Search

Research is presented describing the study of protonated triglycine to determine its tautomerism and migration of protons.

Density functional theory (DFT) calculations were performed to examine the potential of the RuC nanosheet as a biosensor towards the aromatic amino acids (AAA; tryptophan (TRP), histidine (HIS), tyrosine (TYR), and phenylalanine (PHE)). The AAA molecules were placed vertically and horizontally with respect to the RuC surface and then subjected to geometrical relaxation. According to the geometry relaxation results, it was found that all AAA molecules preferred to be adsorbed on the RuC surface in a horizontal configuration rather than a vertical one, except the HIS molecule, which desired to be vertically adsorbed on the RuC nanosheet. From the energy manifestations, the adsorption process within the TRP⋯RuC complexes had the greatest desired negative adsorption energy ( E ads ), followed by HIS⋯, TYR⋯, and then PHE⋯RuC complexes ( E ads = -40.22, -36.54, -23.95, and -16.62 kcal mol -1 , respectively). As indicated by the FMO data, changes in the E HOMO , E LUMO , and E gap values of the RuC nanosheet following the adsorption process demonstrated the capacity of the RuC nanosheet to adsorb the AAA molecules. The outcomes of Bader charge transfer revealed that the RuC nanosheet had the ability to donate electrons to the AAA molecules during the adsorption process, supported by the positive Q t values. Consistent with the E ads conclusions, the TRP⋯RuC complexes had the largest Q t values, indicating the potential affinity of the RuC nanosheet to adsorb the TRP molecule. Following the adsorption of AAA molecules on the RuC nanosheet, new peaks and bands were discovered based on the DOS and the band structure plots, respectively, revealing the validity of the adsorption process. Additionally, the current adsorption findings on the RuC nanosheet were compared to those on the graphene (GN) nanosheet. The outcomes of the comparison demonstrated the outperformance of the RuC nanosheet over the GN nanosheet in adsorbing the AAA molecules. These outcomes provide a solid foundation for further research on the RuC nanosheets to detect small biomolecules., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

Radical (R • ) and R • -hole site-based interactions are comparatively studied, for the first time, using ab initio methods. In this regard, R • -bearing molecules • XO 3 (where X = Cl, Br, and I) were subjected to direct interaction with NH 3 within dimeric and trimeric forms in the form of NH 3 ··· • XO 3 / • XO 3 ···NH 3 and NH 3 ··· • XO 3 ···NH 3 complexes, respectively. As confirmed by electrostatic potential analysis, the studied R • -bearing molecules • XO 3 had the outstanding potentiality to interact as Lewis acid centers via two positive sites dubbed as R • and R • -hole sites. Such an observation proposed the potentiality of the considered • XO 3 molecules to engage in unconventional R • and well-established R • -hole site-based interactions with Lewis bases. This was confirmed by negative interaction ( E int ) energies, ranging from -4.93 to -19.89 kcal/mol, with higher favorability for R • site-based interactions over the R • -hole site-based ones. MP2 energetic features furnished higher preferability for the R • site-based interactions than the R • -hole site-based ones in the case of chlorine- and bromine-bearing complexes, and the reverse was true for the iodine-bearing complexes. Moreover, elevated E int values were recorded for the NH 3 ··· • XO 3 ···NH 3 trimers over the NH 3 ··· • XO 3 and • XO 3 ···NH 3 dimers, outlining the higher preference of the • XO 3 molecules to engage in R • and R • -hole site-based interactions in the trimeric form over the dimeric one. These results might be considered a requisite linchpin for numerous forthcoming supramolecular chemistry and crystal engineering studies., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Herein, the potential of ZO 3 and ZF 2 aerogen-comprising molecules (where Z = Ar, Kr, and Xe) to engage in σ-, lp-, and π-hole site-based interactions was comparatively studied using various ab initio computations. For the first time, a premier in-depth elucidation of the external electric field (EEF) influence on the strength of the σ-, lp-, and π-hole site-based interactions within the ZO 3 /ZF 2 ⋯NH 3 and ⋯NCH complexes was addressed using oriented EEF with disparate magnitude. Upon the energetic features, σ-hole site-based interactions were noticed with the most prominent preferability in comparison to lp- and π-hole analogs. This finding was ensured by the negative interaction energy values of -11.65, -3.50, and -2.74 kcal mol -1 in the case of σ-, lp-, and π-hole site-based interactions within the XeO 3 ⋯ and XeF 2 ⋯NH 3 complexes, respectively. Detailedly, the strength of the σ- and lp-hole site-based interactions directly correlated with the atomic size of the aerogen atoms and the magnitude of the positively oriented EEF. Unexpectedly, an irregular correlation was noticed for the interaction energies of the π-hole site-based interactions with the size of the π-hole. Interestingly, the π-hole site-based interactions within Kr-comprising complexes exhibited higher negative interaction energies than the Ar- and Xe-comprising counterparts. Notwithstanding, a direct proportion between the interaction energies of the π-hole site-based interactions and π-hole size was obtained by employing EEF along the positive orientation with high strength. The present outcomes would be a fundamental basis for forthcoming progress in studying the σ-, lp-, and π-hole site-based interactions within aerogen-comprising complexes and their pertinent applications in materials science and crystal engineering., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Herein, attempts were made to explore the adsorption prospective of beryllium oxide (Be 12 O 12 ) and boron nitride (B 12 N 12 ) nanocarriers toward the temozolomide (TMZ) anticancer drug. A systematic investigation of the TMZ adsorption over nanocarriers was performed by using quantum chemical density functional theory (DFT). The favorability of Be 12 O 12 and B 12 N 12 nanocarriers toward loading TMZ was investigated through A↔D configurations. Substantial energetic features of the proposed configurations were confirmed by negative adsorption ( E ads ) energy values of up to -30.47 and -26.94 kcal/mol for TMZ•••Be 12 O 12 and •••B 12 N 12 complexes within configuration A, respectively. As per SAPT results, the dominant contribution beyond the studied adsorptions was found for the electrostatic forces ( E elst = -100.21 and -63.60 kcal/mol for TMZ•••B 12 N 12 and •••Be 12 O 12 complexes within configuration A, respectively). As a result of TMZ adsorption, changes in the energy of molecular orbitals followed by alterations in global reactivity descriptors were observed. Various intermolecular interactions within the studied complexes were assessed by QTAIM analysis. Notably, a favorable adsorption process was also observed under the effect of water with adsorption energy ( reaching -28.05 and -22.26 kcal/mol for TMZ•••B 12 N 12 and •••Be 12 O 12 complexes within configuration A, respectively. The drug adsorption efficiency of the studied nanocarriers was further examined by analyzing the IR and Raman spectra. From a sustained drug delivery point of view, the release pattern of TMZ from the nanocarrier surface was investigated by recovery time calculations. Additionally, the significant role of doping by heavy atoms (i.e., MgBe 11 O 12 and AlB 11 N 12 ) on the favorability of TMZ adsorption was investigated and compared to pure analogs (i.e., Be 12 O 12 and B 12 N 12 ). The obtained data from thermodynamic calculations highlighted that the adsorption process over pure and doped nanocarriers was spontaneous and exothermic. The emerging findings provide a theoretical base for future works related to nanocarrier applications in the drug delivery process, especially for the TMZ anticancer drug., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The feasibility of utilizing the mud solid waste (MSW) produced during the carbonation process of sugar refining as a cost-effective and environmentally friendly alternative for the water removal of methylene blue (MB) and Congo red (CR), being highly utilized organic dyes representing cationic and anionic species, respectively is presented. Prior to its use, the MSW was dried at 110 °C for 24 h and sieved through a 100-mesh screen. The chief constituent of the MSW utilized was CaCO 3 , with a point of zero charge (PZC) found at pH 8.4 and 7.96 m 2 g -1 total surface area. XRD and FTIR data indicate the presence of interactions between the dyes and the MSW surface, indicating effective adsorption. Different variables, such as initial dye concentration, MSW weight, solution pH, contact time, and temperature, were all examined to determine the optimal dye removal conditions. A central composite design (CCD) approach based on response surface methodology (RSM) modeling was utilized to identify statistically significant parameters for MB and CR adsorption capacities onto the MSW adsorbent. The removal equilibrium was typically reached in 120 minutes, with the greatest removal efficiency of CR taking place at pH 2 and 328 K, while the highest MB removal efficiency was obtained at pH 12 and 296 K. Kinetic studies suggest the adsorption of both dyes on the MSW follow pseudo-second-order rates, as evident through the high correlations obtained. Linearized and non-linearized Langmuir models showed strong correlations indicating maximum adsorption capacities of 86.6 and 72.3 mg g -1 for MB and CR, respectively. High regeneration and reusability potential of the MSW was demonstrated especially for the adsorption of CR, where the removal efficiency was nearly constant throughout five adsorption cycles, ranging from 93 to 91%, while the reduction in the removal for MB was much more significantly impacted, diminishing from 95 to 79% after the five cycles., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The efficacy of aluminium phosphide (Al 12 P 12 ) nanocage toward sensing methanol (MeOH) and ethanol (EtOH) volatile organic compounds (VOCs) was herein thoroughly elucidated utilizing various density functional theory (DFT) computations. In this perspective, MeOH⋯ and EtOH⋯Al 12 P 12 complexes were investigated within all plausible configurations. According to the energetic features, the EtOH⋯Al 12 P 12 complexes exhibited larger negative values of adsorption and interaction energies with values up to -27.23 and -32.84 kcal mol -1 , respectively, in comparison to the MeOH⋯Al 12 P 12 complexes. Based on the symmetry-adapted perturbation theory (SAPT) results, the electrostatic forces were pinpointed as the predominant component beyond the adsorption process within the preferable MeOH⋯ and EtOH⋯Al 12 P 12 complexes. The findings of the noncovalent interaction (NCI) index and quantum theory of atoms in molecules (QTAIM) outlined the closed-shell nature of the interactions within the studied complexes. Substantial variations were found in the molecular orbitals distribution patterns of MeOH/EtOH molecules and Al 12 P 12 nanocage, outlining the occurrence of the adsorption process within the complexes under investigation. Thermodynamic parameters were denoted with negative values, demonstrating the spontaneous exothermic nature of the most favorable complexes. New energy states were observed within the extracted density of states plots, confirming the impact of adsorbing MeOH and EtOH molecules on the electronic properties of the Al 12 P 12 nanocage. The appearance of additional peaks in Infrared Radiation (IR) and Raman spectra revealed the apparent effect of the adsorption process on the features of the utilized sensor. The emerging results declared the potential uses of Al 12 P 12 nanocage as a promising candidate for sensing VOCs, particularly MeOH and EtOH., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The oxazaphosphorine cyclophosphamide (CP) is a DNA-alkylating agent commonly used in cancer chemotherapy. This anticancer agent is administered as a prodrug activated by a liver cytochrome P450-catalyzed 4-hydroxylation reaction that yields the active, cytotoxic metabolite. The primary metabolite, 4-hydroxycyclophosphamide, equilibrates with the ring-open aldophosphamide that undergoes β-elimination to yield the therapeutically active DNA cross-linking phosphoramide mustard and the byproduct acrolein. The present paper presents a DFT investigation of the different metabolic phases and an insight into the mechanism by which CP exerts its cytotoxic action. A detailed computational analysis of the energy profiles describing all the involved transformations and the mechanism of DNA alkylation is given with the aim to contribute to an increase of knowledge that, after more than 60 years of unsuccessful attempts, can lead to the design and development of a new generation of oxazaphosphorines., (© 2023 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

σ-Hole site-based interactions in the trigonal bipyramidal geometrical structure of hypervalent pnicogen, halogen, and aerogen-bearing molecules with pyridine and NCH Lewis bases (LBs) were comparatively examined. In this respect, the ZF 5 ···, XF 3 O 2 ···, and AeF 2 O 3 ···LB complexes (where Z = As, Sb; X = Br, I; Ae = Kr, Xe; and LB = pyridine and NCH) were investigated. The electrostatic potential (EP) analysis affirmations outlined the occurrence of σ-holes on the systems under consideration with disparate magnitudes that increased according to the following order: AeF 2 O 3 < XF 3 O 2 < ZF 5 . In line with EP outcomes, the proficiency of σ-hole site-based interactions increased as the atomic size of the central atom increased with a higher favorability for the pyridine-based complexes over NCH-based ones. The interaction energy showed the most favorable negative values of -35.97, -44.53, and -56.06 kcal/mol for the XeF 2 O 3 ···, IF 3 O 2 ···, and SbF 5 ···pyridine complexes, respectively. The preferentiality pattern of the studied interactions could be explained as a consequence of (i) the dramatic rearrangement of ZF 5 molecules from the trigonal bipyramid geometry to the square pyramidal one, (ii) the significant and tiny deformation energy in the case of the interaction of XF 3 O 2 molecules with pyridine and NCH, respectively, and (iii) the absence of geometrical deformation within the AeF 2 O 3 ···pyridine and ···NCH complexes other than the XeF 2 O 3 ···pyridine one. Quantum theory of atoms in molecules and noncovalent interaction index findings reveal the partially covalent nature of most of the investigated interactions. Symmetry-adapted perturbation theory affirmations declared that the electrostatic component was the driving force beyond the occurrence of the considered interactions. The obtained findings will help in improving our understanding of the effect of geometrical deformation on intermolecular interactions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this work, a novel double-network composite hydrogel (SA/TA), composed of sodium alginate (SA) and tannic acid (TA), was designed and fabricated by a successive cross-linking method using Ti(IV) and Ca(II) as crosslinkers. SA/TA exhibited reinforced mechanical strength and anti-swelling properties because of the double-network structure. SA/TA was used as an adsorbent for removal of a popular antiviral drug, chloroquine phosphate (CQ), in water. The adsorption performance of SA/TA was systematically investigated, to study various effects including those of TA mass content, solution pH, adsorption time, and initial CQ concentration. Adsorption was also examined in presence of inorganic and organic coexisting substances commonly found in wastewater, and under different actual water samples. Batch experimental results indicated that SA/TA could maintain higher and more stable CQ uptakes within a wide solution pH range from 3.0 to 10.0, compared to its precursor, SA hydrogel, owing to the addition of TA-Ti(IV) coordination network. The maximum experimental CQ uptake exhibited by the 1:1 (by wt) SA/TA (SA/TA2) was as high as 0.699 mmol/g at the initial pH of 9.0. A high concentration of coexisting NaCl evidently reduced the CQ uptakes of SA/TA2 due to the electrostatic shielding effect, moreover, divalent cations including Ca(II) and Mg(II) also inhibited the adsorption of CQ due to competitive adsorption. However, humic acid had little effect on this adsorption. Considering the apparent adsorption performance, the aforementioned effects of various factors and the spectroscopic characterizations, multi-interactions are suggested for adsorption including chelation, electrostatic interactions, π-π electron donor-acceptor interaction and hydrogen bonding. SA/TA showed a slight loss in adsorption capacity toward CQ and sustained physicochemical structural stability, even after six adsorption-desorption cycles. In addition to CQ, SA/TA could be efficiently used for adsorption of two other antivirus drugs, namely, hydroxychloroquine sulfate and oseltamivir phosphate. This work provides an effective strategy for the design and fabrication of novel adsorbents that can effectively adsorb antiviral drugs over a wide pH range., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

σ-Hole and lone-pair (lp)-hole interactions of aerogen oxides with Lewis bases (LB) were comparatively inspected in terms of quantum mechanics calculations. The ZO n ⋯ LB complexes (where Z = Kr and Xe, n = 1, 2, 3 and 4, and LB = NH 3 and NCH) showed favourable negative interaction energies. The complexation features were explained in light of σ-hole and lp-hole interactions within optimum distances lower than the sum of the respective van der Waals radii. The emerging findings outlined that σ-hole interaction energies generally enhanced according to the following order: KrO 4 ⋯ < KrO⋯ < KrO 3 ⋯ < KrO 2 ⋯LB and XeO 4 ⋯ < XeO⋯ < XeO 2 ⋯ < XeO 3 ⋯LB complexes with values ranging from -2.23 to -12.84 kcal mol -1 . Lp-hole interactions with values up to -5.91 kcal mol -1 were shown. Symmetry-adapted perturbation theory findings revealed the significant contributions of electrostatic forces accounting for 50-65% of the total attractive forces within most of the ZO n ⋯LB complexes. The obtained observations would be useful for the understanding of hole interactions, particularly for the aerogen oxides, with application in supramolecular chemistry and crystal engineering., Competing Interests: We declare we have no competing interests., (© 2023 The Authors.)

The potentiality of the 6-mercaptopurine (MP) and 6-thioguanine (TG) expired drugs toward the corrosion inhibition of the aluminium (Al) (111) surface was widely investigated using a series of density functional theory (DFT) calculations. A competition between the anti-corrosive features of the studied drugs in the gas and aqueous phases was conducted on both neutral and protonated forms by means of quantum mechanical descriptors. The results of the electrostatic potential analysis demonstrated the prominent nucleophilic nature of the sulfur and nitrogen atoms over the structures of the examined drugs. The frontier molecular orbital theory findings outlined the higher preferability of TG over MP as a corrosion inhibitor. Upon determining the most beneficial configurations of the MP/TG⋯Al (111) complexes, first-principles molecular dynamics simulations were executed. Interestingly, the competence of the TG drug in the corrosion inhibition process of Al (111) was more extensive than that of the MP one, which was confirmed by the interaction energy values of -1.79 and -1.64 eV, respectively. Upon obtaining the relaxed complexes, the effect of the presence of water solvent on the adsorption process was studied. These findings provide a foundation for developing green anti-corrosive inhibitors for the aluminium surface., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

For the first time, sigma (σ)- and lone-pair (lp)-hole site-based interactions of SF 4 and SeF 4 molecules in seesaw geometry with NH 3 and FH Lewis bases were herein comparatively investigated. The obtained findings from the electrostatic potential analysis outlined the emergence of sundry holes on the molecular entity of the SF 4 and SeF 4 molecules, dubbed the σ- and lp-holes. The energetic viewpoint announced splendid negative binding energy values for σ-hole site-based interactions succeeded by lp-hole analogues, which were found to be -9.21 and -0.50 kcal/mol, respectively, for SeF 4 ···NH 3 complex as a case study. Conspicuously, a proper concurrence between the strength of chalcogen σ-hole site-based interactions and the chalcogen's atomic size was obtained, whereas a reverse pattern was proclaimed for the lp-hole counterparts. Further, a higher preference for the YF 4 ···NH 3 complexes with elevated negative binding energy was promulgated over the YF 4 ···FH ones, indicating the eminent role of Lewis basicity. The indications of the quantum theory of atoms in molecules generally asserted the closed-shell nature of all the considered interactions. The observation of symmetry-adapted perturbation theory revealed the substantial contributing role of the electrostatic forces beyond the occurrence of σ-hole site-based interactions. In comparison, the dispersion forces were specified to govern the lp-hole counterparts. Such emerging findings would be a gate for the fruitful forthcoming applications of chalcogen bonding interactions in crystal engineering and biological systems., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

BRD4 (bromodomain-containing protein 4) is an epigenetic reader that realizes histone proteins and promotes the transcription of genes linked to cancer progression and non-cancer diseases such as acute heart failure and severe inflammation. The highly conserved N -terminal bromodomain (BD1) recognizes acylated lysine residues to organize the expression of genes. As such, BD1 is essential for disrupting BRD4 interactions and is a promising target for cancer treatment. To identify new BD1 inhibitors, a SuperDRUG2 database that contains more than 4600 pharmaceutical compounds was screened using in silico techniques. The efficiency of the AutoDock Vina1.1.2 software to anticipate inhibitor-BRD4-BD1 binding poses was first evaluated based on the co-crystallized R6S ligand in complex with BRD4-BD1. From database screening, the most promising BRD4-BD1 inhibitors were subsequently submitted to molecular dynamics (MD) simulations integrated with an MM-GBSA approach. MM-GBSA computations indicated promising BD1 binding with a benzonaphthyridine derivative, pyronaridine (SD003509), with an energy prediction (Δ G binding ) of -42.7 kcal/mol in comparison with -41.5 kcal/mol for a positive control inhibitor (R6S). Pharmacokinetic properties predicted oral bioavailability for both ligands, while post-dynamic analyses of the BRD4-BD1 binding pocket demonstrated greater stability for pyronaridine. These results confirm that in silico studies can provide insight into novel protein-ligand regulators, specifically that pyronaridine is a potential cancer drug candidate.

Adsorption amplitude of the aluminum phosphide (Al 12 P 12 ) nanocage toward the 2-Mercaptopyridine (MCP) drug was herein monitored based on density functional theory (DFT) calculations. The adsorption process through MCP⋅⋅⋅Al 12 P 12 complex in various configurations was elucidated by means of adsorption ( E ads ) energies. According to the energetic affirmations, the Al 12 P 12 nanocage demonstrated potential versatility toward adsorbing the MCP drug within the investigated configurations and exhibited significant negative adsorption energies up to -27.71 kcal/mol. Upon the results of SAPT analysis, the electrostatic forces showed the highest contributions to the overall adsorption process with energetic values up to -74.36 kcal/mol. Concurrently, variations of molecular orbitals distribution along with alterations in the energy gap ( E gap ) and Fermi level ( E FL ) of the studied nanocage were denoted after adsorbing the MCP drug. The favorable impact of water solvent within the MCP⋅⋅⋅Al 12 P 12 complexes was unveiled and confirmed by negative solvation energy (Δ E solv ) values up to -17.75 kcal/mol. According to thermodynamic parameters, the spontaneous and exothermic natures of the considered adsorption process were proclaimed by negative values of Δ G and Δ H parameters. Significant changes in the IR and Raman peaks, along with the appearance of new peaks, were noticed, confirming the occurrence of the targeted adsorption process. Furthermore, the adsorption features of the MCP drug on the Al 12 N 12 nanocage were elucidated and compared to the Al 12 P 12 analog. The obtained results demonstrated the higher preferability of Al 12 P 12 nanocage than the Al 12 N 12 candidate towards adsorbing the MCP drug without structural distortion., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

An in-line smartphone connected to a screen-printed selective electrode hand-held device was used to determine the concentration of distigmine bromide (DB) in its pure and dosage forms as well as its degradation kinetics by continuously measuring the change in the produced emf over time. The main objective, supported by the data presented, is to produce a highly reliable smartphone integrated selective sensor as a portable analyzer with potential high cloud connectivity combining a wide linear dynamic range, the fastest response time with the lowest limits of detection and quantitation while best integrating green analytical chemistry principles. The choice of ionophore used in this approach was guided by computation and the data obtained was compared with traditional analytical techniques. DB, for which there are no previously reported stability-indicating methods and for which four novel such methods are proposed here, was selected as a model drug for this work. At-line UV-spectrophotometry DB assay was obtained by measuring the difference between the spectra of the degradation product and the same concentration of intact drug. The degradation kinetics were studied by this method through tracking the decrease of DB absorbance and/or the increase of a generated degradation product signal over time. Off-line separation based HPLC and TLC stability-indicating methods for DB were also presented. All methods employed in this work were validated for accuracy, precision, specificity, repeatability, linearity, range, detection and quantification limits according to the ICH guidelines and were applied to the analysis of laboratory prepared mixtures as well as commercial products. While all methods proposed were shown to be highly reliable, the smartphone integrated selective sensor is highlighted as a portable analyzer with potential high cloud connectivity and was shown to combine a wide linear dynamic range, the fastest response time with the lowest limits of detection and quantitation while best integrating green analytical chemistry principles., (© 2023. The Author(s).)

The potentiality of the β 12 borophene ( β 12 ) and pristine graphene (GN) nanosheets to adsorb tetrahalomethanes (CX 4 ; X = F, Cl, and Br) were investigated using density functional theory (DFT) methods. To provide a thorough understanding of the adsorption process, tetrel (XC-X 3 ∙∙∙ β 12 /GN)- and halogen (X 3 C-X∙∙∙ β 12 /GN)-oriented configurations were characterized at various adsorption sites. According to the energetic manifestations, the adsorption process of the CX 4 ∙∙∙ β and T@GN complexes within tetrel-/halogen-oriented configurations were -12.33/-8.91 and -10.03/-6.00 kcal/mol, respectively. Frontier molecular orbital (FMO) results exhibited changes in the 12 /GN complexes within the tetrel-oriented configuration led to more desirable negative adsorption energy ( E ads ) values than that within the halogen-oriented analogs. Numerically, E ads values of the CBr 4 ∙∙∙Br1@ β 12 and T@GN complexes within tetrel-/halogen-oriented configurations were -12.33/-8.91 and -10.03/-6.00 kcal/mol, respectively. Frontier molecular orbital (FMO) results exhibited changes in the E HOMO , E LUMO , and E gap values of the pure β 12 and GN nanosheets following the adsorption of CX 4 molecules. Bader charge transfer findings outlined the electron-donating property for the CX 4 molecules after adsorbing on the β 12 and GN nanosheets within the two modeled configurations, except the adsorbed CBr 4 molecule on the GN sheet within the tetrel-oriented configuration. Following the adsorption process, new bands and peaks were observed in the band structure and density of state (DOS) plots, respectively, with a larger number in the case of the tetrel-oriented configuration than in the halogen-oriented one. According to the solvent effect affirmations, adsorption energies of the CX 4 ∙∙∙ β 12 /GN complexes increased in the presence of a water medium. The results of this study will serve as a focal point for experimentalists to better comprehend the adsorption behavior of β 12 and GN nanosheets toward small toxic molecules.

Multidrug resistance (MDR) is one of the most problematic issues in chemotherapeutic carcinoma therapy. The ABCB1 transporter, a drug efflux pump overexpressed in cancer cells, has been thoroughly investigated for its association with MDR. Thus, discovering ABCB1 inhibitors can reverse the MDR in cancer cells. In the current work, a molecular docking technique was utilized for hunting the most prospective ABCB1 inhibitors from the Toxin and Toxin-Target Database (T3DB). Based on the docking computations, the most promising T3DB compounds complexed with the ABCB1 transporter were subjected to molecular dynamics (MD) simulations over 100 ns. Utilizing the MM-GBSA approach, the corresponding binding affinities were computed. Compared to ZQU (calc. -49.8 kcal/mol), Emamectin B1a (T3D1043), Emamectin B1b (T3D1044), Vincristine (T3D4016), Vinblastine (T3D4017), and Vindesine (T3D2479) complexed with ABCB1 transporter demonstrated outstanding binding affinities with Δ G binding values of -93.0, -92.6, -93.8, -92.2, and -90.8 kcal/mol, respectively. The structural and energetic investigations confirmed the constancy of the identified T3DB compounds complexed with the ABCB1 transporter during the 100 ns MD course. To mimic the physiological conditions, MD simulations were conducted for those identified inhibitors complexed with ABCB1 transporter in the presence of a POPC membrane. These findings revealed that Emamectin B1a, Emamectin B1b, Vincristine, Vinblastine, and Vindesine are promising ABCB1 inhibitors that can reverse the MDR. Therefore, subjecting those compounds to further in-vitro and in-vivo investigations is worthwhile.

Structural aspects of molnupiravir complexed with the RNA of the SARS-CoV-2 virus have been recently resolved inside the RNA-dependent RNA polymerase (RdRp), demonstrating the interactions of molnupiravir with purine nucleosides. However, the preference of molnupiravir to interact with one purine nucleoside over another has not been clearly investigated. Herein, the complexation of molnupiravir in its active form with guanosine and adenosine was compared, using sundry density functional theory calculations. The plausible tautomeric structures of the molnupiravir drug in complex with guanosine/adenosine were minutely scrutinized. The relative energy findings outlined the favorability of amino-molnupiravir···keto-amino-guanosine and imino-molnupiravir···amino-adenosine optimized complexes. According to the interaction ( E int ) and binding ( E bind ) energy values, higher preferential base-pairing of molnupiravir with guanosine over the adenosine one was recognized with E int / E bind values of -31.16/-21.81 and -13.93/-12.83 kcal/mol, respectively. This could be interpreted by the presence of three and two hydrogen bonds within the former and latter complexes, respectively. Observable changes in the electronic properties and global indices of reactivity of the studied complexes also confirmed the preferential binding within the studied complexes. The findings from the quantum theory of atoms in molecules and the noncovalent interaction index also support the partially covalent nature of the investigated interactions. For both complexes, changes in thermodynamic parameters outlined the spontaneous, exothermic, and nonrandom states of the inspected interactions. Inspecting the solvent effect on the studied interactions outlined more observable amelioration within the water medium compared with the gas one. These results would be a durable ground for the forthcoming studies concerned with the interactions of the molnupiravir drug with purine nucleosides., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The efficiency of pristine graphene (GN) in the delivery process of the Favipiravir (FPV) anti-COVID-19 drug was herein revealed within the FPV⋯GN complexes in perpendicular and parallel configurations in terms of the density functional theory (DFT) method. Adsorption energy findings unveiled that the parallel configuration of FPV⋯GN complexes showed higher desirability than the perpendicular one, giving adsorption energy up to -15.95 kcal mol -1 . This favorability could be interpreted as a consequence of the contribution of π-π stacking to the overall strength of the adsorption process in the parallel configuration. Frontier molecular orbitals (FMO) findings demonstrated the ability of the GN nanosheet to adsorb the FPV drug by the alteration in the E HOMO , E LUMO ) values. The FPV(R)⋯T@GN complex showed the most desirable E gap values before and after the adsorption process. Based on Bader charge results, the FPV drug and GN sheet exhibited electron-donating and -accepting characters, respectively, which was confirmed by the negative sign of the computed charge transfer ( Q t ) values. The FPV(R)⋯T@GN complex showed the most desirable Q t value of -0.0377 e , which was in synoptic with the adsorption energy pattern. Electronic properties of GN were also altered after the adsorption of the FPV drug in both configurations, with more observable changes in the parallel one. Interestingly, the Dirac point of the GN sheet coincided with the Fermi level after the adsorption process, indicating that the adsorption process unaffected the presence of the Dirac point. The occurrence of the adsorption process was also noticed by the existence of new bands and peaks in the band structure and DOS plots, respectively. Short recovery time rendered the GN nanosheet an efficient FPV drug delivery system. The obtained findings provide new insight into the biomedical applications of the GN sheet as a promising drug delivery system., Competing Interests: The authors declare that they have no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Graphene (GN) nanosheets have been widely exploited in biomedical applications as potential nanocarriers for various drugs due to their distinct physical and chemical properties. In this regard, the adsorption behavior of cisplatin ( cis PtCl 2 ) and some of its analogs on a GN nanosheet was investigated in perpendicular and parallel configurations by using density functional theory (DFT). According to the findings, the most significant negative adsorption energies ( E ads ) within the cis PtX 2 ⋯GN complexes (where X = Cl, Br, and I) were observed for the parallel configuration, with values up to -25.67 kcal/mol at the H@GN site. Within the perpendicular configuration of the cis PtX 2 ⋯GN complexes, three orientations were investigated for the adsorption process, namely, X/X, X/NH 3 , and NH 3 /NH 3 . The negative E ads values of the cis PtX 2 ⋯GN complexes increased with the increasing atomic weight of the halogen atom. The Br@GN site showed the largest negative E ads values for the cis PtX 2 ⋯GN complexes in the perpendicular configuration. The Bader charge transfer outcomes highlighted the electron-accepting properties of cis PtI 2 within the cis PtI 2 ⋯GN complexes in both configurations. The electron-donating character of the GN nanosheet increased as the electronegativity of the halogen atom increased. The band structure and density of state plots revealed the occurrence of the physical adsorption of the cis PtX 2 on the GN nanosheet, which was indicated by the appearance of new bands and peaks. Based on the solvent effect outlines, the negative E ads values generally decreased after the adsorption process in a water medium. The recovery time results were in line with the E ads findings, where the cis PtI 2 in the parallel configuration took the longest time to be desorbed from the GN nanosheet with values of 61.6 × 10 8 ms at 298.15 K. The findings of this study provide better insights into the utilization of GN nanosheets in drug delivery applications.

There is an increasing need to find cost-effective and sustainable solutions for treating wastewater from contaminants of emerging concern (CECs). In this regard, cape gooseberry husk-typically an agri-food waste-is investigated for the first time as a potential biosorbent for the removal of model pharmaceutical contaminants of caffeine (CA) and salicylic acid (SA) from water. Three different preparations of husks were investigated and characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller analysis, zeta potential, and point of zero charge measurements. The activation of the husk led to an increase in the surface area, pore volume, average pore size, and adsorption favorability. The single-component adsorption of SA and CA onto the three husks was investigated at different initial concentrations and pH values to determine the optimal operating conditions. The maximal removal efficiencies of SA and CA reached up to 85 and 63%, respectively, for the optimal husk which also offers a less energy-intensive option in its activation. This husk also exhibited high rates of adsorption that exceeded other husk preparations by up to four times. It was proposed that CA interacts electrostatically with the husk, while SA binds through weak physical interactions (e.g., van der Waals and H-bonding). In binary systems, CA adsorption was highly favored over SA adsorption, owing to its electrostatic interactions. The selectivity coefficients α SA CA varied with initial concentration and ranged between 61 and 627. The regeneration of husk was also successful resulting in its re-use for up to four full consecutive cycles, further demonstrating the efficiency of cape gooseberry husk use in wastewater treatment., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The dramatic rise in cancer incidence, alongside treatment deficiencies, has elevated cancer to the second-leading cause of death globally. The increasing morbidity and mortality of this disease can be traced back to a number of causes, including treatment-related side effects, drug resistance, inadequate curative treatment and tumor relapse. Recently, anti-cancer bioactive peptides (ACPs) have emerged as a potential therapeutic choice within the pharmaceutical arsenal due to their high penetration, specificity and fewer side effects. In this contribution, we present a general overview of the literature concerning the conformational structures, modes of action and membrane interaction mechanisms of ACPs, as well as provide recent examples of their successful employment as targeting ligands in cancer treatment. The use of ACPs as a diagnostic tool is summarized, and their advantages in these applications are highlighted. This review expounds on the main approaches for peptide synthesis along with their reconstruction and modification needed to enhance their therapeutic effect. Computational approaches that could predict therapeutic efficacy and suggest ACP candidates for experimental studies are discussed. Future research prospects in this rapidly expanding area are also offered.

Thermosensitive liposomes (TSL) have been used for localized temperature-responsive release of chemotherapeutics into solid cancers, with a minimum of one invention currently in clinical trials (phase III). In this study, TSL was designed using a lipid blend comprising 1,2-dipalmitoyl- sn -glycero-3-phosphocholine (DPPC), 1,2-distearoyl- sn -glycero-3-phosphocholine (DSPC), cholesterol, and 1,2-distearoyl- sn -glycero-3-phosphoethanolamine- N -[maleimide(polyethylene glycol)-2000] (DSPE-PEG-2000) (molar ratio of 88:9:2.8:0.2). Either nedaplatin (ND) or p -sulfonatocalix[4]arene-nedaplatin was encapsulated in the aqueous inner layer of TSL to form (ND-TSL) or p -SC4-ND-TSL, respectively. The hydrophobic platinum-based drug picoplatin (P) was loaded into the external lipid bilayer of the TSL to develop P-TSL. The three nanosystems were studied in terms of size, PDI, surface charge, and on-shelf stability. Moreover, the entrapment efficiency (EE%) and release % at 37 and 40 °C were evaluated. In a 30 min in vitro release study, the maximum release of ND, p -SC4-ND, and picoplatin at 40 °C reached 74, 79, and 75%, respectively, compared to approximately 10% at 37 °C. This demonstrated temperature-triggered drug release from the TSL in all three developed systems. The designed TSL exhibited significant in vitro anticancer activity at 40 °C when tested on human mammary gland/breast adenocarcinoma cells (MDA-MB-231). The cytotoxicity of ND-TSL, p -SC4-ND-TSL, and P-TSL at 40 °C was approximately twice those observed at 37 °C. This study suggests that TSL is a promising nanoplatform for the temperature-triggered release of platinum-based drugs into cancer cells., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Cyclophosphamide is a well-known anticancer agent acting by means of DNA alkylation. Associated with its tumor selectivity, it also possesses a wide spectrum of toxicities. As the requirement of metabolic activation before cyclophosphamide exerts either its therapeutic or toxic effects is well recognized, research aiming at elucidating the pathways that lead to the activation of this drug is of key importance. This has created the necessity for developing an effective analytical method for detecting cyclophosphamide and its breakdown products. In this paper, an Acquity TQ tandem quadrupole mass spectrometer equipped with electrospray ionization in positive-ion mode was employed for detecting cyclophosphamide in its protonated form. The full-scan mass spectrum of cyclophosphamide shows two ion clusters displaying the characteristic isotopic pattern of two chlorine atoms and assigned as sodiated cyclophosphamide, [CP + Na] + , and protonated cyclophosphamide, [CP + H] + or PCP. With the aid of quantum mechanical DFT calculation, free energy differences in the gas phase among PCP protomers were computed with respect to the most stable protomer being protonated on the 2-oxide oxygen of the 1,3,2-oxazaphosphorine-2-oxide ring. In addition, the interconversion mechanisms among the different protomers were also proposed by intercepting the corresponding transition states in the gas phase. Collision-induced dissociation (CID) of PCP generated six characteristic product ions. Fragmentation mechanisms were proposed and supported by computation. The calculated energy barriers for all of the located transition states were found to be accessible under the reported experimental conditions.

In this study, two environmentally-friendly macroscopically formal (PVF) composited sponges (PL and PLS) functionalized with lignin and lignosulfonate, respectively, were fabricated by a one-step mechanical foaming method. PLS, obtained with the fed mass ratio of 0.3:1 lignosulfonate to PVF in the preparation process, possessed a large specific surface area of approximately 22.396 m 2 /g, a three-dimensional skeleton structure with a skeletal density of 3.236 g/cm 3 , and 0.338 mmol/g of acidic oxygen-containing groups. Thus, it showed a high adsorption capacity of 0.16-0.24 mmol/g in removing seven antibiotics, of the popular fluoroquinolones (FQs) family from water. The contributions of hydrogen bonding, electrostatic attraction (EA) and π-π electron donor-acceptor interaction to the adsorption of FQs onto the PL and PLS sponges were analyzed systematically by investigating the pH dependence of the adsorption capacity, and the changes in adsorption of two sub structural analogs of FQs as molecular probes, and by performing theoretical calculations. The EA between the acidic oxygen-containing groups on the sponges and the amino groups of FQs played a dominant role in adsorption in near neutral conditions, leading to a superior adsorption performance for PLS. Overall, the composited sponges have the advantages of simple production, environmental-friendliness, convenient recycle, and low cost, which renders them potentially viable in treating real wastewater containing FQs., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Marine algae are a rich source of biologically active compounds that can be utilized in various food and pharmaceutical applications. In this study, ultrasound-assisted extraction (UAE) was optimized to maximize yield and total carbohydrate content extracted from the red algae, Pterocladia capillacea . The extract was shown to possess potent antioxidant activity of up to ~70%, and was successfully used as a reducing and capping agent in the green synthesis of copper nanoparticles, which were characterized by UV-spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and dynamic light scattering (DLS). Primarily, CuO nanoparticles with an average size of 62 nm were produced. FTIR spectra for the extract and algal-mediated CuO nanoparticles showed characteristic polysaccharide peaks. The synthesized CuO nanoparticles were subsequently loaded with nedaplatin where UV data suggested a complex formation. Nedaplatin release profiles showed a sustained release that reached a maximum at 120 h. The formulation was shown to have greater cytotoxicity relative to nedaplatin on hepatocellular carcinoma, breast cancer and ovarian cancer cell lines with IC 50 values of 0.40 ± 0.08, 1.50 ± 0.12, and 0.70 ± 0.09 µg/mL, respectively. Loading nedaplatin onto CuO nanoparticles synthesized using red algae extract, greatly enhances its anticancer effect.

Historical records document medieval immigration from North Africa to Iberia to create Islamic al-Andalus. Here, we present a low-coverage genome of an eleventh century CE man buried in an Islamic necropolis in Segorbe, near Valencia, Spain. Uniparental lineages indicate North African ancestry, but at the autosomal level he displays a mosaic of North African and European-like ancestries, distinct from any present-day population. Altogether, the genome-wide evidence, stable isotope results and the age of the burial indicate that his ancestry was ultimately a result of admixture between recently arrived Amazigh people (Berbers) and the population inhabiting the Peninsula prior to the Islamic conquest. We detect differences between our sample and a previously published group of contemporary individuals from Valencia, exemplifying how detailed, small-scale aDNA studies can illuminate fine-grained regional and temporal differences. His genome demonstrates how ancient DNA studies can capture portraits of past genetic variation that have been erased by later demographic shifts-in this case, most likely the seventeenth century CE expulsion of formerly Islamic communities as tolerance dissipated following the Reconquista by the Catholic kingdoms of the north., (© 2021. The Author(s).)

Choline (Ch + ), is a vitamin-like essential water-soluble organic micronutrient. The US-FDA requires that infant formula not made from cow's milk must be supplemented with Ch + . Direct determination of Ch + in milk powders and infant formulas is a challenging task due to the lack of a detectable chromophore, its existence in free and complexed forms as well as the presence of multi-analytes in these complex matrices. Here, an enzyme-free potentiometric ion selective electrode (ISE) with high selectivity for Ch + , a linear range from 0.03 μM up to 1 mM, a 0.061 μM detection limit (LOD) and a typical response time less than 5 and no greater than 60 s is developed for monitoring of Ch + in infant formula and milk powders. To achieve these ISE parameters we relied on the ability of calixarenes and its derivatives to form host-guest complexes with the positively charged quaternary ammonium moiety of Ch + . We employed a lipophilic (membrane-compatible) calixarene as an ionophore in the sensing membrane phase to provide a molecular receptor for Ch + capable of selective binding; while utilizing, hydrophilic (water-soluble) p-sulfonated calixarene as a buffering agent to optimize the inner filling solution to reduce transmembrane Ch + fluxes. All the calixarene structures and their complexes with Ch + were optimized at the density functional theory (DFT) level and the Gibbs free energies for the inclusion of Ch + into the calixarenes were calculated. The prepared sensor was shown to selectively respond only to Ch + in the presence of all other interferents in the tested matrices with results that are not statistically significantly different for either accuracy or precision relative to the much more laborious official AOAC 1999 coupled enzymatic-spectrophotometric method. The proposed method is highly selective, non-enzymatic, requires no derivatization or incubation steps, offers a fast response time, and has the potential of portability for in situ analysis, while being relatively cost effective and non-laborious., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m 3 , respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a 'reference city' for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Following the discovery of cisplatin over 50 years ago, platinum-based drugs have been a widely used and effective form of cancer therapy, primarily causing cell death by inducing DNA damage and triggering apoptosis. However, the dose-limiting toxicity of these drugs has led to the development of second and third generation platinum-based drugs that maintain the cytotoxicity of cisplatin but have a more acceptable side-effect profile. In addition to the creation of new analogs, tumor delivery systems such as liposome encapsulated platinum drugs have been developed and are currently in clinical trials. In this study, we have created the first PEGylated liposomal form of nedaplatin using thin film hydration. Nedaplatin, the main focus of this study, has been exclusively used in Japan for the treatment of non-small cell lung cancer, head and neck, esophageal, bladder, ovarian and cervical cancer. Here, we investigate the cytotoxic and genotoxic effects of free and liposomal nedaplatin on the human non-small cell lung cancer cell line A549 and human osteosarcoma cell line U2OS. We use a variety of assays including ICP MS and the highly sensitive histone H2AX assay to assess drug internalization and to quantify DNA damage induction. Strikingly, we show that by encapsulating nedaplatin in PEGylated liposomes, the platinum uptake cytotoxicity and genotoxicity of nedaplatin was significantly enhanced in both cancer cell lines. Moreover, the enhanced platinum uptake as well as the cytotoxic/antiproliferative effect of liposomal nedaplatin appears to be selective to cancer cells as it was not observed on two noncancer cell lines. This is the first study to develop PEGylated liposomal nedaplatin and to demonstrate the superior cell delivery potential of this product.

Fava bean peels, Vicia faba (FBP) are investigated as biosorbents for the removal of Methylene Blue (MB) dye from aqueous solutions through a novel and efficient sorption process utilizing ultrasonic-assisted (US) shaking. Ultrasonication remarkably enhanced sorption rate relative to conventional (CV) shaking, while maintaining the same sorption capacity. Ultrasonic sorption rate amounted to four times higher than its conventional counterpart at 3.6 mg/L initial dye concentration, 5 g/L adsorbent dose, and pH 5.8. Under the same adsorbent dose and pH conditions, percent removal ranged between 70-80% at the low dye concentration range (3.6-25 mg/L) and reached about 90% at 50 mg/L of the initial dye concentration. According to the Langmuir model, maximum sorption capacity was estimated to be 140 mg/g. A multiple linear regression statistical model revealed that adsorption was significantly affected by initial concentration, adsorbent dose and time. FBP could be successfully utilized as a low-cost biosorbent for the removal of MB from wastewater via US biosorption as an alternative to CV sorption. US biosorption yields the same sorption capacities as CV biosorption, but with significant reduction in operational times.

The preoxidation effects of H 2 O 2 , NaClO, and KMnO 4 on the dewaterability of sewage sludge were compared by analyzing the changes in specific resistance to filtration (SRF), filter cake moisture content (FCMC), extracellular polymeric substance (EPS) fractions and components, and floc properties. The three oxidants varied in oxidation efficiency and exhibited distinctive mechanisms. NaClO not only destroyed sludge flocs and EPSs but also effectively caused cell lysis, resulting in release of a considerable amount of organic matters and subsequently significant deterioration of dewatering performance. The oxidation of H 2 O 2 and KMnO 4 was relatively mild and occurred mainly on the outer layers of the sludge flocs and cell-bound EPSs. By contrast, the SRF and FCMC of the sludge conditioned with a low dose of KMnO 4 were slightly improved, and a fraction of soluble EPS was compressed because of the coagulation effect of the oxidation product MnO 2 . The pH of the sludge conditioned with H 2 O 2 and KMnO 4 showed no considerable change. Meanwhile, NaClO evidently increased the alkalinity of the sludge because of the hydrolysis effect. After the pH of the NaClO-treated sludge was readjusted to 7.0, the partial protonation efficiency slightly alleviated the deterioration of sludge dewatering performance. The preoxidized sludge was then subjected to reflocculation treatment using FeCl 3 , polyacrylamide, and a cationic starch-based flocculant, respectively. The combined treatment of preoxidation and reflocculation showed a high dewatering efficiency owing to their synergistic effect., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Chemotherapeutic agents are considered one of the strategies in treating cancer. However, their use is faced by many challenges, such as poor water solubility leading to poor bioavailability and non-selective targeting of cancerous cells leading to diminished therapeutic actions and systemic adverse effects. Many approaches were adopted to overcome these drawbacks and to achieve the targeted delivery of the chemotherapeutic agents to the cancerous cells while minimizing adverse effects. Recently, supramolecular systems such as macrocycles have gained attention in the field of cancer therapy for being able to encapsulate different anticancer drugs via either host-guest complexation or self-assembly leading to a myriad of advantages. This review highlights the most recent studies concerned with the design of such novel systems for cancer therapy., Competing Interests: The authors declare no conflict of interest.

Organophosphate esters (OPEs) are commonly used as flame retardants (FRs) and plasticizers. The usage of OPEs has increased recently due to the ban of several brominated flame retardants, but information on levels in the environment, including the indoor environment is still limited. We investigated the occurrence and distribution of 12 OPEs in urban house dust from Vancouver, Canada; Istanbul, Turkey; and Cairo, Egypt. The median ∑OPE concentration was 41.4 μg/g in the Vancouver samples while median levels in Istanbul and Cairo were significantly lower. The median composition profiles of OPEs in Vancouver and Cairo were dominated by tris (2-butoxyethyl) phosphate (TBOEP), accounting for 56 and 92% of total OPEs respectively while it showed a detection frequency of only 14% in Istanbul. Tris (2-chloropropyl) phosphate (TCPP) was the most abundant chlorinated OPE representing 20 and 36% of the total OPEs in Vancouver and Istanbul respectively, but was below the detection limit in the Cairo dust samples. Consistent with other studies, ΣOPE concentrations were ~1 to 2 orders of magnitude higher than PBDEs and currently used flame retardants in the same dust samples. The mean estimated daily intakes (EDI) of ΣOPE from dust were 115, 38 and 9 ng/kg/bw/day in Vancouver, Cairo and Istanbul respectively for toddlers where adults were ~10 times lower. The total toddler OPE intake ranged from 115 to 2900, 38 to 845 and from 9 to 240 ng/kg bw/day across the three cities. TBOEP had the largest contribution to the EDI in both toddler and adults, where toddler TBOEP exposures via dust represented 4% to 80%, 2% to 44% and 0.1% to 6% of the Reference Doses (RfD) in the mean and high intake scenarios for toddlers in Vancouver, Cairo and Istanbul respectively., (Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.)

The occurrence and concentrations of six common phthalates were investigated for the first time in bottled water locally produced in the Egyptian market. The compounds investigated were dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), n-butyl benzyl phthalate (BBP), diethyl hexyl phthalate (DEHP), and Di-n-octyl phthalate (D-n-OP). A set of 108 bottled water samples from six different commercial brands of water bottled in transparent polyethylene terephthalate (PET) plastic bottles with high density polyethylene (HDPE) plastic caps were investigated. Water samples were analyzed immediately after purchasing (~2weeks after production), after being stored at room temperature (25±5°C), in a refrigerator (4±1°C) and outdoor under sun exposure (daylight temperature of 40±5°C). Samples were stored up to six months depending on the tested condition. Among the target compounds, only DEHP and DBP were detected in the samples analyzed immediately after purchasing with a detection frequency of 50 and 58% and mean concentrations of 0.104 and 0.082μgl -1 respectively. Significant positive correlation was obtained between the storage time, temperature and the concentration of phthalate compounds detected in the bottled water, indicating possible migration from the PET plastic material as the source. The estimated contribution of bottled water consumption to the tolerable daily intake (TDI) levels of the two most abundant phthalates observed here for adults and toddlers did not exceed 0.16 and 0.72% for DBP while these values were 0.04 and 0.16% for DEHP respectively. These estimated daily intake values from PET bottled water consumption were far below their respective TDI values and therefore should constitute no adverse health effects., (Copyright © 2017 Elsevier B.V. All rights reserved.)