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Designing the donor–acceptor polymers‐based modifiers with good charge mobility and abundant surface functional groups to bind on perovskite material is highly demanded to boost interfacial charge extraction and transport while yet realized. Here, two [WS4Cu4Br]+ and [WS4Cu5Br2]+ cluster units are bridged by triphenylamine ligands to yield an unprecedented a heteronuclear W/Cu/S clusters‐based donor–acceptor polymer. Due to the effect of Rydberg orbital components in different clusters mainly contributed by Cu ions, Cu‐rich units have negative potential, whereas Cu‐deficient groups display positive potential. This facilitates the formation of a circuit network with ligands acting as "wires" to realize efficient charge transport. Mobility tests reveal that the hole mobility of polymer film is 3.81 × 10−5 cm2 V−1 s−1. Such a polymer can efficiently extract and transport the holes from perovskite film, and thus improving the cell performance and stability. This work opens the opportunities for designing donor–acceptor polymers based on heteronuclear W/Cu/S clusters. [ABSTRACT FROM AUTHOR]

Apatite minerals can have various anions and cations in their crystal structure in addition to phosphate ion (PO₄³⁻) and calcium ion (Ca2+). The aim of this study is to investigate effects of the borate, fluoride and strontium ions on biomimetic nucleation of calcium phosphate. Nano-crystalline hydroxyapatite (H-Ap) was obtained from a supersaturated buffered solution containing 4.12 mM HPO 4 2- and 5.88 mM Ca2+ (H-Ap). Four additives were used in solid solution methods: (i) 0.588 mM F- (F-Ap), (ii) 5.88 mM Sr2+ (Sr-Ap), (iii) 4.12 mM BO 3 3- (BO3-Ap), and (iv) a surface pre-reacted glass ionomer (S-PRG) filler eluate that contained 0.17 mM Sr2+, 0.588 mM F-, 11.1 mM BO 3 3-- (SPRG-Ap). Apatite crystallization was investigated using a solid-state magic-angle spinning NMR spectroscopy and X-ray diffraction (XRD) with the Rietveld analysis. A 2D 1H–31P heteronuclear-correlation NMR showed F- ion incorporation in the apatite structure of the F-Ap and SPRG-Ap. The peaks on the 31P axis of the F-Ap, Sr-Ap, and BO 3 -Ap were different from that of the H-Ap, and the full width at half maximum increased in the following order: H-Ap∼F-Ap∼BO 3 -Ap< SPRG-Ap< Sr-Ap, suggesting the incorporation of the F-, Sr2+ and BO 3 3-. The incorporation of F and BO 3 was further confirmed by 19F and 11B NMR. The XRD revealed that Sr2+ was preferentially incorporated into the CaII site. The F-, Sr2+ and BO 3 3-ions might be involved in modifying the crystallization of apatite precipitation, producing a variety of apatite. S-PRG filler that release these ions may have an effect on remineralization, i.e., the reformation of apatite lost due to caries. • F-, Sr2+ and probably BO 3 3- from surface S-PRG filler are incorporated in hydroxyapatite crystal lattice. • Sr2+ incorporation is indicated by the increase in the axis lengths. • The ions from S-PRG filler are involved in modifying the crystallization of apatite precipitation. [ABSTRACT FROM AUTHOR]

We analyze schemes of high-fidelity multi-qubit CNOT N and C 2 NOT 2 gates for alkali metal neutral atoms used as qubits. These schemes are based on the electromagnetically induced transparency and Rydberg blockade. The fidelity of homonuclear multi-qubit CNOT N gate based on Rydberg blockade was limited by the undesirable interaction between the target atoms and by the coupling laser intensity. We propose overcoming these limits by using strong heteronuclear dipole–dipole interactions via Förster resonances for control and target atoms, while the target atoms are coupled by a weaker van der Waals interaction. We optimized the gate performance in order to achieve higher fidelity, while keeping the coupling laser intensity as small as possible in order to improve the experimental feasibility of the gate schemes. We also considered the optimization of the schemes of the C 2 NOT 2 gates, where the fidelity is affected by the relation between the control–control, control–target and target–target interaction energies. Our numeric simulations confirm that the fidelity of the CNOT 4 gate (single control and four target atoms) can be up to 99.3% and the fidelity of the C 2 NOT 2 (two control and two target atoms) is up to 99.7% for the conditions which are experimentally feasible. [ABSTRACT FROM AUTHOR]

• Two heteronuclear 3d-4f complexes (Ln = Tb, Gd) were synthesized using the compartmental Schiff base ligand and secondary sulfonate co-ligands. • These compounds represent rare instances of dinuclear Co(III)-Ln(III) SMMs. • These findings demonstrate the practicality of creating sulfonate-based Co(III)-Ln(III) coordination complexes, despite sulfonate's generally weak bonding with metal ions. • This research not only broaden the structural diversity of 3d-4f complexes but also provide a valuable experimental basis for further exploration of their magnetic properties. In this research, our team synthesized and characterized two heteronuclear 3d-4f complexes, [CoIIICl(μ -valen)(μ -4-HBS)LnIII(NO 3)(H 2 O)(4-HBS)], with Ln representing Tb (1) and Gd (2). Achievement of this was through the utilization of a compartmental Schiff base ligand H 2 valen, alongside secondary co-ligands Na(4-HBS) [H 2 valen=6,6′-((1E,1′E)-(ethane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))bis(2-methoxyphenol); Na(4-HBS)=sodium 4-hydroxybenzenesulfonate]. X-ray crystallography revealed that both complexes feature a similar [Co(III)-Ln(III)] core, connected by the phenoxo-O atoms from the compartmental Schiff base ligand and the sulfonate-O atoms from the co-ligand. In this context, Co(III) displays a distorted octahedral geometry within a CoN 2 O 3 Cl coordination sphere, while Ln(III) exhibits a muffin (MFF)-like distorted geometry in a LnO 9 coordination sphere. Magnetic analysis shows that the two complexes display unique magnetic properties. Complex 1 exhibits pronounced SMM behavior, with a notable energy barrier of 14.8 K for magnetization reversal. However, complex 2 presents a minor energy barrier of 4.8 K. Additionally, complexes 1 and 2 represent uncommon examples of dinuclear Co(III)-Ln(III) SMMs. [Display omitted] [ABSTRACT FROM AUTHOR]

We analyze schemes of high-fidelity multi-qubit CNOTN and C2NOT2 gates for alkali metal neutral atoms used as qubits. These schemes are based on the electromagnetically induced transparency and Rydberg blockade. The fidelity of homonuclear multi-qubit CNOTN gate based on Rydberg blockade was limited by the undesirable interaction between the target atoms and by the coupling laser intensity. We propose overcoming these limits by using strong heteronuclear dipole–dipole interactions via Förster resonances for control and target atoms, while the target atoms are coupled by a weaker van der Waals interaction. We optimized the gate performance in order to achieve higher fidelity, while keeping the coupling laser intensity as small as possible in order to improve the experimental feasibility of the gate schemes. We also considered the optimization of the schemes of the C2NOT2 gates, where the fidelity is affected by the relation between the control–control, control–target and target–target interaction energies. Our numeric simulations confirm that the fidelity of the CNOT4 gate (single control and four target atoms) can be up to 99.3% and the fidelity of the C2NOT2 (two control and two target atoms) is up to 99.7% for the conditions which are experimentally feasible.

Dental research often uses bovine teeth as a substitute for human teeth. The aim of this study was to evaluate differences in the crystalline nanostructures of enamel and dentin between bovine and human teeth, using X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (NMR). The crystallite size (crystallinity) and microstrains were analyzed using XRD with the Rietveld refinement technique and the Halder–Wagner method. The 31P and 1H NMR chemical environments were analyzed by two-dimensional (2D) 1H-31P heteronuclear-correlation (HETCOR) magic-angle spinning (MAS) NMR spectroscopy. Enamel had a greater crystallite size and fewer microstrains than dentin for both bovine and human teeth. When compared between the species, the bovine apatite had a smaller crystallite size with more microstrains than the human apatite for both dentin and enamel. The 2D HETCOR spectra demonstrated that a water-rich layer and inorganic HPO42− ions were abundant in dentin; meanwhile, the hydroxyl group in the lattice site was more dominant in enamel. A greater intensity of the hydroxyl group was detected in human than in bovine for both dentin and enamel. For 31P projections, bovine dentin and bovine enamel have wider linewidths than human dentin and human enamel, respectively. There are differences in the crystallite profile between human and bovine. The results of dental research should be interpreted with caution when bovine teeth are substituted for human teeth. [ABSTRACT FROM AUTHOR]

Two heteroctanuclear Au4Ag4 cluster complexes of 4,5-diethynylacridin-9-one (H2L) were prepared through the self-assembly reactions of [Au(tht)2](CF3SO3), Ag(tht)(CF3SO3), H2L and PPh3 or PPh2Py (2-(diphenylphosphino)pyridine). The Au4Ag4 cluster consists of a [Au4L4]4− and four [Ag(PPh3)]+ or [Ag(PPh2Py)]+ units with Au4L4 framework exhibiting a twisted paper clip structure. In CH2Cl2 solutions at ambient temperature, both compounds show ligand fluorescence at ca. 463 nm as well as phosphorescence at 650 nm for 1 and 630 nm for 2 resulting from admixture of 3IL (intraligand) of L ligand, 3LMCT (from L ligand to Au4Ag4) and 3MC (metal-cluster) triplet states. Crystals or crystalline powders manifest bright yellow-green phosphorescence with vibronic-structured emission bands at 530 (568sh) nm for complex 1 and 536 (576sh) nm for complex 2. Upon mechanical grinding, yellow-green emission in the crystalline state is dramatically converted to red luminescence centered at ca. 610 nm with a drastic redshift of the emission after crystal packing is destroyed. [ABSTRACT FROM AUTHOR]

Dental research often uses bovine teeth as a substitute for human teeth. The aim of this study was to evaluate differences in the crystalline nanostructures of enamel and dentin between bovine and human teeth, using X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (NMR). The crystallite size (crystallinity) and microstrains were analyzed using XRD with the Rietveld refinement technique and the Halder–Wagner method. The 31P and 1H NMR chemical environments were analyzed by two-dimensional (2D) 1H-31P heteronuclear-correlation (HETCOR) magic-angle spinning (MAS) NMR spectroscopy. Enamel had a greater crystallite size and fewer microstrains than dentin for both bovine and human teeth. When compared between the species, the bovine apatite had a smaller crystallite size with more microstrains than the human apatite for both dentin and enamel. The 2D HETCOR spectra demonstrated that a water-rich layer and inorganic HPO42− ions were abundant in dentin; meanwhile, the hydroxyl group in the lattice site was more dominant in enamel. A greater intensity of the hydroxyl group was detected in human than in bovine for both dentin and enamel. For 31P projections, bovine dentin and bovine enamel have wider linewidths than human dentin and human enamel, respectively. There are differences in the crystallite profile between human and bovine. The results of dental research should be interpreted with caution when bovine teeth are substituted for human teeth.

Two heteroctanuclear Au4Ag4 cluster complexes of 4,5-diethynylacridin-9-one (H2L) were prepared through the self-assembly reactions of [Au(tht)2](CF3SO3), Ag(tht)(CF3SO3), H2L and PPh3 or PPh2Py (2-(diphenylphosphino)pyridine). The Au4Ag4 cluster consists of a [Au4L4]4− and four [Ag(PPh3)]+ or [Ag(PPh2Py)]+ units with Au4L4 framework exhibiting a twisted paper clip structure. In CH2Cl2 solutions at ambient temperature, both compounds show ligand fluorescence at ca. 463 nm as well as phosphorescence at 650 nm for 1 and 630 nm for 2 resulting from admixture of 3IL (intraligand) of L ligand, 3LMCT (from L ligand to Au4Ag4) and 3MC (metal-cluster) triplet states. Crystals or crystalline powders manifest bright yellow-green phosphorescence with vibronic-structured emission bands at 530 (568sh) nm for complex 1 and 536 (576sh) nm for complex 2. Upon mechanical grinding, yellow-green emission in the crystalline state is dramatically converted to red luminescence centered at ca. 610 nm with a drastic redshift of the emission after crystal packing is destroyed.

Abstract. With the attempt to synthesize Nb‐enclosed germanium Zintl cluster ion in ethylenediamine (en) / toluene solution, the reaction of K4Ge9/Na4Ge9 with Nb(mes)2 (mes = mesitylene) gives unexpected 18‐crown‐6 cleavage product of [K14Na2(NbO2)2(C8H16O5)8](Ge5) (en)·solv in the form of very air‐sensitive, light‐brown, plate‐like crystals. This unique compound crystallizes in monoclinic Pn (No. 7) space group, the cleavage of crown linked the 14 potassium, 2 sodium, and 2 niobium atoms into the bulky 2+ charged cation, which balances the [Ge5]2– anion. This compound represents the rare example of heteronuclear metal alkoxide / Zintl ion hybrid. [ABSTRACT FROM AUTHOR]

A new heteronuclear complex [LCuCo(NO3)2] (1) (H2L = N,N'-ethylenebis [3-methoxysalicylaldimine]) was synthesized and structurally characterized. The complex consists of a dimer skeleton which composed of a slightly distorted square-planar copper and pentacoordinated cobalt ions. The magnetic properties reveal the presence of antiferromagnetic interactions between the metal centers linked by double phenoxo-bridging. [ABSTRACT FROM AUTHOR]

• The heteronuclear DACs (MoX@NC) possesses higher catalytic ability than the homonuclear DACs (2X@NC). • Compared to the homonuclear DACs, the Bader charge indicates that the electronic interaction between Mo atom and other transition metals is enhanced for the heteronuclear DACs. • The synergistic effect of the heteronuclear DACs originates from the enhancement of the intermetallic interaction between Mo atom and other transition metals in dimer. In order to identify the synergistic effect in the heteronuclear double-atom catalysts (DACs) on CO activation, the homonuclear and heteronuclear DACs have been designed based on graphene supporter. And the three CO dissociation pathways have been considered using the density functional theory (DFT) calculation. It reveals that the heteronuclear DACs (MoX@NC) possesses higher catalytic ability than the homonuclear DACs (2X@NC) for CO activation. And the unpaired d -orbital electron plays a significant role on CO activation, which can change the magnetic moment of the DACs. The coordination atoms offer similar local coordination environment for the homonuclear and heteronuclear DACs. However, the Bader charge displays that there is a strong electronic interaction between Mo atom and other transition metals of dimer for the heteronuclear DACs. The synergistic effect of the heteronuclear DACs originates from the enhancement of the intermetallic interaction between the Mo atom and other transition metals. The work offers rational guideline for the synthesis of DACs with excellent catalytic performances, and has great potential for application in various catalytic fields. [Display omitted] [ABSTRACT FROM AUTHOR]

Polychlorinated biphenyls are a class of persistent environmental contaminants, and micellar solubilization can be applied to remediate them. The intermolecular aggregates of biphenyl (BP) analogs and cetyltrimethyl ammonium bromide (CTAB) were studied by chemical shift perturbation, nuclear magnetic resonance (NMR) diffusometry, quantitative proton NMR, and nuclear Overhauser effect (NOE) spectroscopy to understand the structural determinants of their solubilization. The micelles of CTAB solubilized BPs readily, but its capacity depended strongly on the nature of the functional group (BPCH2OH > > BPCHO > BPCOOH ≈ BPCl ≈ BP). Upon internalization, the BPs diffused much slower, introduced significant low‐frequency 1H chemical shift changes for CTAB, and displayed strong intermolecular NOEs. The semiquantitative analysis of NOEs revealed further that the BPs are located in the palisade layer closer to the N+(CH3)3 head group, away from the hydrophobic core. 1H NMR offers a simple high‐throughput screening assay for evaluating and quantitating the solubilization of organics in micelles. The intermolecular NOEs and site‐specific perturbation of chemical shifts add further insights on the location of solubilizates in micelles, which may be important for designing surfactants specific for environmental pollutants. [ABSTRACT FROM AUTHOR]

A new hetero trinuclear manganese(III)-iron(II) complex, [Mn(salen)(H2O)]2[Fe(CN)6], in which salen is the dianionic form of N,N’-bis(5-methylsalicylidene)-1,2-diaminoethane, has been prepared and characterized by elemental analyses, IR, and single crystal X-ray crystallographic determination. The crystal of the complex is monoclinic: space group P21/c, a = 10.768(2), b = 14.248(3), c = 15.222(3) Å, β = 95.394(2)º, V = 2325.0(8) Å3, Z = 2, R1 = 0.0754, wR2 = 0.2366. The bis-Schiff base ligand coordinates to the Mn atom through phenolate O and imine N atoms. Each Mn atom in the complex is in octahedral coordination, with the equatorial donor atoms come from the Schiff base ligand, and with the axial donor atoms come from a water O atom and a cyanide N atom. The effects of the complex on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were studied. DOI: http://dx.doi.org/10.4314/bcse.v29i3.8

A series of novel homonuclear and heteronuclear bis-isatin derivatives tethered through ethylene were designed, synthesized and evaluated for their in vitro anti-mycobacterial activities against MTB H37Rv and MDR-TB. All hybrids exhibited potential anti-mycobacterial activities against MTB H37Rv and MDR-TB with MIC ranging from 16 to 256 μg/mL. In particular, the heteronuclear bis-isatin 4i (MIC: 25 and 16 μg/mL) was most active against MTB H37Rv and MDR-TB strains, and could act as a lead for further optimization. [ABSTRACT FROM AUTHOR]

The metallostibine Os 2 (CO) 8 ( μ -SbPh), 2 , acts as a good two-electron donor ligand, reacting readily with Group 8 metal carbonyls to give heterometallic clusters. Specifically, it undergoes ligand substitution reaction with Fe 2 (CO) 9 , Os 3 (CO) 11 (CH 3 CN), or Os 3 (CO) 10 (CH 3 CN) 2 to afford Os 2 Fe(CO) 12 ( μ 3 -SbPh), 3 , Os 5 (CO) 19 ( μ 3 -SbPh), 4 , or Os 7 (CO) 26 ( μ 3 -SbPh) 2 , 5 , respectively, in moderate to high yields. An analogous reaction with Ru 3 (CO) 11 (CH 3 CN) afforded another spirocyclic cluster Os 3 Ru(CO) 14 ( μ -PhCO)( μ 4 -Sb), 9 . UV irradiation of 4 afforded the spirocyclic clusters Os 5 (CO) 18 ( μ , η 2 -PhCO)( μ 4 -Sb), 6 , and Os 5 (CO) 18 ( μ , η 2 -C 6 H 4 )( μ -H)( μ 4 -Sb), 7 , while the raft-like cluster Os 5 (CO) 19 ( μ 3 -SbPh), 8 , was obtained when a methanolic solution was exposed to natural light; cluster 5 failed to react under similar conditions. All the new clusters have been characterized spectroscopically and crystallographically, and possible pathways for the formation of 6 - 9 proposed. [ABSTRACT FROM AUTHOR]

Abstract: Two compartmental Schiff bases, H2L1 [N,N′‐bis(3‐ethoxysalicylidene)propane‐1,3‐diamine] and H2L2 [N,N′‐bis(3‐ethoxysalicylidene)‐2,2‐dimethylpropane‐1,3‐diamine], have been utilized to prepare two new hetero‐dinuclear nickel(II)/zinc(II) complexes, [(DMSO)2NiL1Zn(NCS)2] (1) and [NiL2Zn(NCS)2] (2) respectively. Both complexes have been characterized by elemental and spectral analysis and single crystal X‐ray diffraction. Nickel(II) is located in the inner compartment while zinc(II) is positioned in the outer compartment in both complexes. Supramolecular interactions have been explored for both complexes. Hirshfeld surface analysis has been used for visually analyzing intermolecular C−H⋅⋅⋅O (hydrogen bonding), π‐π stacking, conventional C−H⋅⋅⋅π(arene) and unconventional C−H⋅⋅⋅π(SCN) interactions in the crystal structures. Theoretical studies on the formation of C−H⋅⋅⋅O (hydrogen bonding), π‐π stacking, conventional C−H⋅⋅⋅π(arene) and unconventional C−H⋅⋅⋅π(SCN) interactions in the solid state X‐ray structures of both complexes have been performed using the Gaussian‐09 and M06‐2X/6‐31+G* level of theory. [ABSTRACT FROM AUTHOR]

Leveraging the demonstrated accuracy of the group contribution statistical associating fluid theory for potentials of variable range (GC-SAFT-VR) equation of state to predict the phase equilibrium and thermodynamic properties of fluids, we use this approach to study organic sulfur molecules and their mixtures. Knowledge of the phase equilibria and thermodynamic properties of sulfur containing compounds, while of interest in a number of fields, is important to the development of petroleum products with lower sulfur content. In this work the CH (thiophene) and –S- functional groups are characterized by fitting to experimental data for pure thiophene and cross interactions determined in order to extend the GC-SAFT-VR equation of state to the study of organic sulfur molecules. Theoretical predictions are compared with experimental results for the phase behavior of 3-methylthiophene, 2-methylthiophene, and benzothiophene, as well as their binary mixtures with alkanes, alkenes, aromatics, carbon dioxide, and alcohols. As far as we are aware, this work is the first SAFT-based study of mixtures containing thiophene molecules with aromatics, alcohols, and hydrocarbon molecules. The GC-SAFT-VR approach is found to accurately predict the phase behavior of the sulfur organic compounds studied, providing a method to determine the phase behavior of these compounds without heavy reliance on experimental data. [ABSTRACT FROM AUTHOR]

Fluorinated molecules such as perfluoroalkanes (PFA), perfluoroalkylalkanes (PFAA), fluoroalkanes, and hydrofluoroethers (HFE) possess attractive physical properties that have resulted in their use in a wide range of applications. However, while there is an abundance of thermophysical data for hydrocarbons in the literature, only limited studies have been performed that report the properties of the corresponding fluorinated species. Predictive approaches are therefore needed to accurately and reliably determine the physical properties of these molecules. The statistical associating fluid theory (SAFT) is a commonly used molecular-based equation of state that in its various forms has been applied to study a wide range of fluid systems. In recent work, several group contribution (GC) SAFT equations of state have been proposed, such as the GC-SAFT-VR equation that combines the SAFT equation for potentials of variable range (VR) with a group contribution approach that uniquely allows for the description of hetero-segmented chains. The GC-SAFT-VR equation has been shown to provide an excellent description of the phase behavior of pure associating and non-associating fluids and their mixtures, with a minimal reliance on fitting the model parameters to experimental data. Specifically, parameters for key functional groups (such as CH 3 , CH 2 , CH, CH 2 =CH, C=O, C 6 H 5 , ether and ester, OH, NH 2 , CH=O, COOH) have been obtained by fitting to experimental vapor pressure and saturated liquid density data for selected low molecular weight fluids and then used to predict the phase behavior of pure fluids and their mixtures without further adjusting the group parameters. To expand upon this effort, here we report parameters for the CF 3 , CF 2 , CF, CH 2 F, CHF 2 , and CHF functional groups and their cross interactions. The theoretical predictions are compared with experimental data for pure PFAs, PFAAs, and HFEs, as well as binary mixtures of alkanes, alkenes, PFAs, PFAAs, and CO 2 in order to test the transferability of the new group parameters. The GC-SAFT-VR approach is found to accurately predict the phase behavior of the systems studied. [ABSTRACT FROM AUTHOR]

Three new heteronuclear [FeW 9 O 34 ]-based sandwich-type complexes [Fe III 2 Mn II 2 (H 2 O) 2 (FeW 9 O 34 ) 2 ] 12− ( 1 ), [Fe III 2 Mn III 2 (H 2 O) 2 (FeW 9 O 34 ) 2 ] 10− ( 2 ) and [Fe III 2 Ni II 2 (H 2 O) 2 (FeW 9 O 34 ) 2 ] 12− ( 3 ) have been synthesized by an innovative method of pH-controllable degradation in aqueous solution, in which the [FeW 12 O 40 ] 5− precursor could be predominantly degraded into the trivacant [FeW 9 O 34 ] 11− anion. The active ligand of trivacant [FeW 9 O 34 ] 11− anion can catch in situ the mixed transition metal ions to conduce a directed coordination assembly reaction. These three heteronuclear complexes have been characterized by elemental analysis, single-crystal and powder X-ray diffraction analyses, IR spectra, UV–vis spectra, and thermal gravimetric analysis, cyclic voltammetry, magnetic properties, and thermal gravimetric analysis. Complexes 1 and 3 exhibit obvious catalytic activities for electrocatalytic reduction of nitrate. Compared with 1 , the magnetic property of 2 shows a remarkable change by only a conversion of Mn(II) into Mn(III), so that a strong ferromagnetic interaction occurs in 2 . [ABSTRACT FROM AUTHOR]

A novel method, Spin-State-Selective (S 3 ) HMBC hetero , for accurate measurement of heteronuclear coupling constants is introduced. The method extends the S 3 HMBC technique for measurement of homonuclear coupling constants by appending a pulse sequence element that interchanges the polarization in 13 C- 1 H methine pairs. This amounts to converting the spin-state selectivity from 1 H spin states to 13 C spin states in the spectra of long-range coupled 1 H spins, allowing convenient measurement of heteronuclear coupling constants similar to other S 3 or E.COSY-type methods. As usual in this type of techniques, the accuracy of coupling constant measurement is independent of the size of the coupling constant of interest. The merits of the new method are demonstrated by application to vinyl acetate, the alkaloid strychnine, and the carbohydrate methyl β -maltoside. [ABSTRACT FROM AUTHOR]

Two Pd(II) complexes, (HLCSS)Pd ( 1) and (KLCSS)Pd ( 2), were synthesized by stirring 2-(1-piperazinyl)ethanol (HLH)/ l-lysine (HL2H) monohydrate in methanol with KOH, CS and PdCl. Homobimetallic (Sn, Sn) products, PhSnLSn(Cl)Bu ( 3) and PhSnLSnBu ( 4) were produced by refluxing sodium but-2-ynedioate (NaL) with PhSnCl and BuSnCl or PhSnCl and BuSnCl in methanol. A heteronuclear (Sn,Pd) product, [(BuSn)LCSS]Pd ( 5) was synthesized by the reaction of 5-aminoisophthalic acid (HLH), KOH, CS, PdCl with BuSnCl. The products were characterized by elemental analysis, FT-IR, UV-Vis, H NMR and EIMS. A square planar geometry of Pd(II) and a penta-coordinated environment around Sn(IV) were verified in solid state. The complexes maintain their solid state geometries around Pd(II) even in solutions. Pd(II) complexes 1 and 2 exhibited a significant intercalating mode of binding with salmon sperm DNA. ALPs were inhibited in a concentration dependent manner. Sn(IV) complexes ( 3 and 4) were inactive against ALPs. Pd(II) complexes ( 1 and 2) were potent ALPs inhibitors, while the heteronuclear complex 5 was comparatively less active. Organotin(IV) products demonstrated significant antibacterial/ antifungal potential while Pd(II) products were inactive. The heteronuclear (Sn,Pd) product demonstrated moderate inhibition. Among all products, Pd(II) derivative 1 exhibited the highest hemolytic effect. [ABSTRACT FROM AUTHOR]

Two unique heteronuclear Schiff base complexes of Cu(II), [{Cu(L)Na(ClO 4 )} 2 (μ-H 2 L)] ( 1 ) and Ni(II), [{Ni(L)Na(BF 4 )} 2 (μ-H 2 L)] ( 2 ) were synthesized and characterized by different spectroscopic methods as well as X-ray crystallography. The Schiff base ligand (H 2 L) was synthesized from the condensation meso-1,2-diphenyl-1,2-ethylenediamine with 3-methoxysalicylaldehyde. The 3d metal ions in these complexes have been accommodated by the inner N 2 O 2 compartment of the Schiff base ligand, while the O 2 O′ 2 outer compartment has accommodated the Na(I) ion (O and O′ denote the phenolic and methoxy oxygen atoms, respectively). Besides, a Schiff base ligand has doubly bridged the M(II)/Na(I) moieties via the (OO′) 2 coordination mode. This mode of bidentate action of a potentially tetradentate Schiff base ligand is very rare and has been observed for the first time in such 3d-ns complexes. The in vitro antibacterial activity of the Schiff base ligand and the complexes ( 1 ) and ( 2 ) were tested against human pathogenic bacteria such as Bacillus subtilis (Gram positive); Staphylococcus aureus (Gram positive); Salmonella typhi (Gram negative); and Escherichia coli (Gram negative). The results showed that these new hetero-polynuclear complexes had moderate antibacterial activity against both Gram type bacteria. [ABSTRACT FROM AUTHOR]

Two new heteronuclear Nickel(II)/Sodium(I) complexes of a side-off compartmental Schiff base ligand were synthesized and characterized by spectroscopic methods. Crystal structures of both of the complexes were also obtained. The Schiff base ligand was synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-3-methoxybenzaldehyde. In both of the complexes the Ni(II) ion is coordinated to the inner N 2 O 2 coordination sphere with square-planar geometry and the Na(I) ion is coordinated to the outer O 2 O 2 ′ coordination sphere. In Complex ( 1 ) with general formula [Ni(L)Na(CH 3 OH)(ClO 4 )] the sodium ion is seven coordinated while in ( 2 ) with general formula [{Ni(L)Na(OH 2 )} 2 (μ-Ni(CN) 4 )] the sodium ion is six coordinated. Intermolecular interactions in two studied complexes were analyzed using 3D Hirshfeld surfaces and corresponding 2D fingerprint plots. This analysis showed that the H … H and C … H/H … C contacts for both structures (altogether 67.5% of total Hirshfeld surface area for ( 1 ) and 77.6% for ( 2 )) and the O … H/H … O (24.2%) for ( 1 ) and the N … H/H … N (8.1%) contacts for ( 2 ) were the characteristic intermolecular contacts in the related crystal structures. [ABSTRACT FROM AUTHOR]

Biodiesel fuels, which consist of a blend of long chain fatty acid methyl esters, have attracted increased interest in recent years as possible alternates to fuels derived from petroleum. An understanding of the thermophysical properties and phase behavior of these molecules are therefore important to the investigation and design of biodiesel processes; however, such data is limited, making the development of molecular based modeling approaches that can accurately and reliably determine the thermophysical properties of fatty acid methyl esters an important research area. Here we apply the group contribution based statistical associating fluid theory for potential of variable range (GC-SAFT-VR) equation of state to the study of long chain fatty acid methyl esters that comprise biodiesel fuels. With minimal reliance on experimental data, the GC-SAFT-VR equation of state offers a predictive approach that allows for the description of hetero-segmented chains that can correlate and predict the phase behavior of pure associating and non-associating fluids and their mixtures. Model parameters for the C O, CH 3 , CH 2 , CH CH 2 , OCH 2 , and OCH 3 functional groups and their cross interactions were taken from earlier work and used here in a transferable fashion to predict the thermophysical properties and phase behavior of pure fatty acid methyl esters and their mixtures with other fatty acid methyl esters, alcohols, and carbon dioxide. It is shown that the GC-SAFT-VR approach can be used as a purely predictive tool without fitting any new model parameters) to accurately predict the phase behavior of the fatty acid methyl ester fluids and their mixtures studied. [ABSTRACT FROM AUTHOR]

A new hetero trinuclear manganese(III)-iron(II) complex, [Mn(salen)(H2O)] 2[Fe(CN)6], in which salen is the dianionic form of N,N'-bis(5-methylsalicylidene)-1,2-diaminoethane, has been prepared and characterized by elemental analyses, IR, and single crystal X-ray crystallographic determination. The crystal of the complex is monoclinic: space group P21/c, a = 10.768(2), b = 14.248(3), c = 15.222(3) Å, β = 95.394(2)º, V = 2325.0(8) ų, Z = 2, R1 = 0.0754, wR2 = 0.2366. The bis-Schiff base ligand coordinates to the Mn atom through phenolate O and imine N atoms. Each Mn atom in the complex is in octahedral coordination, with the equatorial donor atoms come from the Schiff base ligand, and with the axial donor atoms come from a water O atom and a cyanide N atom. The effects of the complex on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were studied. [ABSTRACT FROM AUTHOR]

The 2-(benzo[d]thiazole-2′-yl)- N-alkylanilines have previously revealed the presence of a strong intramolecular hydrogen bond. This in turn gives rise to a more complicated multiplet for the protons attached to the carbon adjacent to the amino group. This intramolecular hydrogen bond was investigated by a deuterium exchange experiment using heteronuclear NMR spectroscopy (1H, 13C, 15 N and 2H). We observed changes in the multiplet structure and chemical shifts providing further evidence that the deuterium replaces the hydrogen in the intramolecular hydrogen bond. A time course study of the D2O exchange confirmed the presence of a strong hydrogen bond. The comparison of the structures obtained by X-ray crystallography showed a very small difference in planarity between the two-substituted and four-substituted amino compounds. In both the cases, the phenyl ring is not absolutely coplanar with the thiazole unit. The existence of this intramolecular hydrogen bond in 2-(benzo[d]thiazole-2′-yl)- N-alkylanilines was further confirmed by single crystal X-ray crystallography. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Two lanthanide complexes are achieved by utilizing H 2 salen/acac ligands (H 2 salen = N , N′ -ethylenebis(salicylideneimine), acac = acetylacetonate). They are homonuclear [Nd 4 ( μ 3 -OH) 2 (salen) 2 (acac) 6 (CH 3 OH) 2 ]·CH 3 OH ( 1 ) and heteronuclear [NdYb(salen) 2 (acac) 2 ] ( 2 ). The structures of the two complexes were determined by X-ray crystallographic studies and their photophysical properties were investigated. The homonuclear Nd 4 complex exhibits characteristic metal-centered NIR emission. The heteronuclear NdYb shows ‘dual emission’ from both neodymium(III) and ytterbium(III) ions. [ABSTRACT FROM AUTHOR]

Reaction of a carbosilane congener of ferroquine 1 with the half-sandwich [Ru(η- p-PrCHMe)(µ-Cl)Cl] dimer yields an unexpected neutral heteronuclear Ru(II) silicon-containing ferroquine derivative complex 3 upon crystallisation. The complex crystallises in a monoclinic system with P2/c space group, with unit cell parameters a = 14.3000(10) Å, b = 17.7457(13) Å, c = 21.5727(15) Å, β = 102.908(2), Z = 4. Compound 1 acts as a monodentate ligand that coordinates to ruthenium via the quinoline nitrogen of the aminoquinoline scaffold, and the amine adjacent to the organosilicon entity. Each ruthenium center is surrounded by four ligands and is restricted within a slightly distorted tetrahedral environment. Graphical Abstract: A carbosilane congener of ferroquine 1 was reacted with [Ru(η- p-PrCHMe)(µ-Cl)Cl] to produce an unexpected trimetallic heteronuclear silicon-containing ferroquine derivative upon crystallisation. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Acylation of 5,7-di( tert-butyl)-2-(5,8-dimethyl-4-piperidinoquinolin-2-yl)-3-(3,5-dimethylphenylamino)tropone leads to the corresponding 3-( N-acetyl- N-arylamino)tropone. Heteronuclear, two-dimensional, and dynamic NMR spectroscopy were used to determine structures of conformers of N-acetyl-3-arylaminotropone. The structure of 3-[ N-acetyl- N(3,5-dimethylphenyl)amino]-5,7-di( tert-butyl)-2-(5,8-dimethyl-4-piperidinoquinolin-2-yl)tropone was established by X-ray diffraction studies. [ABSTRACT FROM AUTHOR]

Highlights: [•] Recent advances in lanthanide luminescence of heteronuclear arrays are reviewed. [•] Metal-organic chromphores act as light-harvesting sensitizers. [•] Lanthanide luminescence is sensitized through intercomponent energy transfer. [•] Heteronuclear assemblies exhibit various colored visible or NIR luminescence. [•] Bright white light can be achieved due to dual emission of heteronuclear systems. [Copyright &y& Elsevier]

Highlights: [•] Nine new heterometallic complexes containing copper(II) and silver(I). [•] The second examples of 3d–silver(I) compounds from acyclic Schiff base ligands. [•] Two compounds are coordination polymers due to Ag–π (arene; η1-/η2-/η3-) bonds.. [•] Six dimer-of-dinuclear systems due to silver(I)⋯silver(I) interaction. [•] CSD survey reveals some definitely significant aspects. [Copyright &y& Elsevier]

[Display omitted] • Cancer making it the second most leading cause of death after cardiovascular diseases. • Though many platinum-based drugs are currently being used widely in anticancer therapy, the therapeutic value of these complexes comes with severe side effects. • Thus, a tremendous amount of research is being carried out on the anticancer activity of other metal complexes to explore their anticancer activity. • Herein, we discuss the study of cellular uptake, localisation, mechanism of action and cytotoxicity profiles of several mononuclear and multinuclear ruthenium, iridium and rhenium complexes as potential chemotherapeutic agents. More than 10 million death tolls in 2020 were reported as a result of heinous impact of cancer, making it second most prime cause of death after cardiovascular diseases. In annihilation of cancer, many platinum-based drugs are currently being applied in anticancer therapy but the therapeutic value of these complexes comes with severe side effects. Hence, a profound research is needed to develop more selective and target specific chemotherapeutics so as to diminish the side effects. In this scenario, the anticancer activity of ruthenium, iridium and rhenium-based complexes have shown a light of hope for being explored as anticancer metallotherapeutics. This present review article, therefore, delineates the study of cellular uptake, localisation, mechanism of action and cytotoxicity profiles of several mononuclear and multinuclear ruthenium, iridium and rhenium complexes as target specific potential chemotherapeutic agents. [ABSTRACT FROM AUTHOR]

Highlights: [•] A T box riboswitch Specifier domain–tRNA anticodon arm complex was prepared. [•] The complex mirrors ribosomal codon–anticodon pairing with three base pairs. [•] Specifier bases rotate towards the minor groove to engage the tRNA anticodon. [•] The structure of the anticodon loop evolves to adopt a U-turn motif in the complex. [•] Loss of the U-turn reduces affinity but does not prevent complex formation. [ABSTRACT FROM AUTHOR]

Highlights: [•] A T box riboswitch Specifier domain–tRNA anticodon arm complex was prepared. [•] The complex mirrors ribosomal codon–anticodon pairing with three base pairs. [•] Specifier bases rotate towards the minor groove to engage the tRNA anticodon. [•] The structure of the anticodon loop evolves to adopt a U-turn motif in the complex. [•] Loss of the U-turn reduces affinity but does not prevent complex formation. [ABSTRACT FROM AUTHOR]

The work in this report presents the syntheses, characterization, crystal structures and electronic spectra of the six heteronuclear complexes [CuIIL1NaI(μ-BF4)2NaIL1CuII]·2CH3COCH3 (1), [CuIIL1NaI(NO3)(MeOH)] (2), [CuIIL1ZnII(H2O)2L1CuII](ClO4)2 (3), [CuII(MeOH)L1ZnIICl2] (4), [CuIIL1CdII(H2O)(MeOH)2](ClO4)2 (5) and [CuIIL1CdIICl2(MeOH)]·[CuII(MeOH)L1CdIICl2] (6), where H2L1 is N,N′-ethylenebis(3-methoxysalicylaldimine). The crystal systems and space groups are as follows: 1 and 2, triclinic, ; 3 and 6, monoclinic, P21/c; 4, orthorhombic, P212121; 5, monoclinic, C2/c. While the N(imine)2O(phenoxo)2 compartment accommodates the copper(II) center, the larger and open O(phenoxo)2O(methoxy)2 compartment interacts with the second metal ion. Compounds 2, 4 and 5 are diphenoxo-bridged dinuclear systems, compound 3 is a trinuclear system in which the two CuIIZnII pairs are monophenoxo-bridged, compound 1 is a tetranuclear system in which two diphenoxo-bridged CuIINaI units are interlinked by two tetrafluoroborate moieties, and compound 6 is a [2×1+2×1] co-crystal of two dinuclear CuIICdII units. The solid state electronic spectra of compounds 1–6 and also the mononuclear compound [CuIIL1(H2O)] have been recorded in the range 400–800nm. While correlating the d–d band position with the structural parameters and a previously proposed correlation, some inconsistency has been found, indicating that this area should be explored further. [ABSTRACT FROM AUTHOR]

Optimal control theory in combination with time-dependent quantum dynamics is employed to design laser pulses which can perform selective vibrational and rotational excitations in a heteronuclear diatomic system. We have applied the conjugate gradient method for the constrained optimization of a suitably designed functional incorporating the desired objectives and constraints. Laser pulses designed for several excitation processes of the HF molecule were able to achieve predefined dynamical goals with almost 100% yield. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: In Gram-positive bacteria, the RNA transcripts of many amino acid biosynthetic and aminoacyl tRNA synthetase genes contain 5′ untranslated regions, or leader RNAs, that function as riboswitches. These T-box riboswitches bind cognate tRNA molecules and regulate gene expression by a transcription attenuation mechanism. The Specifier Loop domain of the leader RNA contains nucleotides that pair with nucleotides in the tRNA anticodon loop and is flanked on one side by a kink-turn (K-turn), or GA, sequence motif. We have determined the solution NMR structure of the K-turn sequence element within the context of the Specifier Loop domain. The K-turn sequence motif has several noncanonical base pairs typical of K-turn structures but adopts an extended conformation. The Specifier Loop domain contains a loop E structural motif, and the single-strand Specifier nucleotides stack with their Watson–Crick edges displaced toward the minor groove. Mg2+ leads to a significant bending of the helix axis at the base of the Specifier Loop domain, but does not alter the K-turn. Isothermal titration calorimetry indicates that the K-turn sequence causes a small enhancement of the interaction between the tRNA anticodon arm and the Specifier Loop domain. One possibility is that the K-turn structure is formed and stabilized when tRNA binds the T-box riboswitch and interacts with Stem I and the antiterminator helix. This motif in turn anchors the orientation of Stem I relative to the 3′ half of the leader RNA, further stabilizing the tRNA–T box complex. [Copyright &y& Elsevier]

Abstract: Intermolecular multiple-quantum coherences (iMQCs) have some intrinsic properties different from conventional single-quantum coherences in solution NMR. In this paper, we extended our study to heteronuclear iMQCs in IS (I =1/2, S =3/2) spin systems. A sample of sodium chloride (NaCl) water solution was taken as an example. Heteronuclear COSY revamped by asymmetric Z-gradient echo detection (CRAZED) experiments were performed. One- and two-dimensional heteronuclear iMQC spectra were obtained. The quantum-mechanical treatment was used to deduce the signal expressions. Magic angle experiments validate that the signals are indeed from intermolecular dipolar interaction and insensitive to the imperfection of radio-frequency (RF) flip angles. Both experimental results and theoretical analysis indicate that heteronuclear CRAZED experiment allows coherence transfer from spin-3/2 nuclei to spin-1/2, and vice verse. Furthermore, the dependences of iMQC signal intensities on RF pulse flip angles follow the same rules as those for heteronuclear IS (I =1/2, S =1/2 or 1) spin systems. [Copyright &y& Elsevier]

Abstract: The hetero-segmented version of the statistical associating fluid theory for potentials of variable range (hetero-SAFT-VR) is used to develop a predictive molecular-based group-contribution SAFT-VR equation of state (GC-SAFT-VR). The hetero-SAFT-VR approach models molecules composed of segments of different size and/or energies of interaction enabling an accurate description of real molecules composed of different functional groups. The differences in interactions between functional groups are maintained throughout the theory in contrast to other approaches in which the parameters for functional groups are averaged in order to model a molecule as a homonuclear chain with “group-averaged” parameters. Through the GC-SAFT-VR approach we can study the effect of molecular functionality and topology on the thermodynamic properties of real fluid systems, since parameters are determined for each functional group and chain connectivity is explicitly specified. In this initial study GC-SAFT-VR parameters are developed for key organic functional groups (CH3, CH2, CH2 glyph name="dbnd" />O, C6H5, OCH3 and OCH2) by fitting to experimental vapor pressure and saturated liquid density data for a selected group of compounds that contain these functional groups. The transferability of the parameters obtained is tested by comparing theoretical predictions with experimental data for pure fluids not included in the fitting process and binary mixtures. Using the GC-SAFT-VR approach good agreement is obtained between experimental data and the theoretical predictions for pure substances, including isomers, and their mixtures. The GC-SAFT-VR approach is able to accurately predict the effect of molecular functionality on mixture phase behavior without fitting to any experimental data for the system being studied. [Copyright &y& Elsevier]

Abstract: A new group contribution (GC) approach based on the statistical associating fluid theory (SAFT-) has recently been proposed [A. Lymperiadis, C. S. Adjiman, A. Galindo, G. Jackson, J. Chem. Phys. 127 (2007) 234903]. In this continuum equation of state GC approach, the molecules are formed from fused heteronuclear spherical segments each of which represents a distinct chemical functional group. The different segments are characterised by size and attractive energy (well-depth and range) parameters, and a shape-factor parameter which describes the contribution that each segment makes to the overall molecular properties. In addition a number of bonding sites are included on a given segment to deal with association interactions where appropriate; the association between sites introduces two additional energy and range parameters. Our heteronuclear molecular models are thus fundamentally different from the homonuclear models employed with other GC versions of SAFT in which the GC concept is introduced to obtain average molecular parameters. In the current work, we generalise the SAFT- equation of state to treat chemical groups which are represented by more than a single spherical segment. This allows for a good description of the properties of large functional groups such as carboxyl and carbonyl groups. The original parameter table for the CH3, CH2, CH3CH, ACH (where AC denotes an aromatic carbon), ACCH2, CH2 lyph name="dbnd" /> and OH groups is now extended to include the Cand NH2 groups by examining the vapour–liquid equilibria (VLE) of pure 2-ketones, carboxylic acids, and primary amines. It is demonstrated that the proposed theory provides an excellent description of the vapour–liquid equilibria for all of the chemical families considered, and that the new group parameters can be used in a predictive fashion to model the phase behaviour of larger compounds not included in the estimation database. One of the principal advantages of the SAFT- formalism is that the binary interaction parameters between groups of different types can be estimated from pure component data alone. This is particularly useful in describing the properties of fluid mixtures. The adequacy of the method in predicting the VLE is assessed for selected binary mixtures of associating and non-associating compounds. A strict test of any GC method is its ability to capture both vapour–liquid and liquid–liquid equilibria (LLE) with the same set of group parameters. It is very gratifying to find that with SAFT- one is able to reproduce the VLE and LLE behaviour for several mixtures simultaneously, for example, n- , and n- . [Copyright &y& Elsevier]

A carboxylate-bridged Cu(II)-Gd(III) complex, [GdCu(CH2CH(CH3COO)4(H2O)4]n(NO3)n, was prepared and characterized. Single crystal X-ray analysis reveals the complex as a carboxylate-bridged 1-D Cu(II)-Gd(III) coordination polymer. The magnetic measurement showed this complex exhibiting weak ferromagnetic behavior. [ABSTRACT FROM AUTHOR]

A carboxylate-bridged Co(II)-Gd(III) complex, [(bipy)CoL3Gd(NO3)L3Co(bipy)] (HL = α-methylacrylic acid, bipy = 2,2'-bipyridine), was prepared and characterized. Single crystal X-ray analysis reveals that the complex assumes a carboxylate-bridged CoGdCo unit. Magnetic measurements showed χmT decreases when the temperature is lowered. [ABSTRACT FROM AUTHOR]

Applications of conventional (X-band), High-Field and High-Frequency EPR to study the nature of exchange interactions between Cu(II) centres in different homo- and hetronuclear systems are reviewed. The fine structure EPR spectra have been observed and analyzed in terms of spin-Hamiltonian parameters corresponding to S ≥ 1 for different [Cu2(β-alanine)4Cl2]Cl2·H2O dimeric complexes present in one unit cell, Cu(II) dimers possessing different conformations, dimeric species formed between Cu(II) ions and polyfunctional ligand in solution, Cu–Zn–Cu–Zn and Cu–Co–Cu–Co tetrameric heterometallomacrocycles, Cu4O4 cubane-like tetramers and for the chain Cu(II) hexamer. [ABSTRACT FROM AUTHOR]

Abstract: Measurement of heteronuclear spin–lattice relaxation times is hampered by both low natural abundance and low detection sensitivity. Combined with typically long relaxation times, this results in extended acquisition times which often renders the experiment impractical. Recently a variant of dynamic nuclear polarisation has been demonstrated in which enhanced nuclear spin polarisation, generated in the cryo-solid state, is transferred to the liquid state for detection. Combining this approach with small flip angle pulse trains, similar to the FLASH-T 1 imaging sequence, allows the rapid determination of spin–lattice relaxation times. In this paper we explore this method and its application to the measurement of T 1 for both carbon-13 and nitrogen-15 at natural abundance. The effects of RF inhomogeneity and the influence of proton decoupling in the context of this experiment are also investigated. [Copyright &y& Elsevier]

An extension of the SAFT-VR equation of state, the so-called hetero-SAFT approach [Y. Peng, H. Zhao, and C. McCabe, Molec. Phys. 104, 571 (2006)], is used to examine the phase equilibria exhibited by a number of model binary mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants. Despite the increasing recent interest in semifluorinated alkanes (or perfluoroalkylalkane diblock molecules), the phase behaviour of mixtures involving these molecules with n-alkanes or perfluoroalkanes is practically unknown from the experimental point of view. In this work, we use simple molecular models for n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock molecules to predict, from a molecular perspective, the phase behaviour of selected model mixtures of perfluoroalkylalkanes with n-alkanes and perfluoroalkanes. In particular, we focus our interest on the understanding of the microscopic conditions that control the liquid-liquid separation and the stabilization of these mixtures. n-Alkanes and perfluoroalkanes are modelled as tangentially bonded monomer segments with molecular parameters taken from the literature. The perfluoroalkylalkane diblock molecules are modelled as heterosegmented diblock chains, with parameters for the alkyl and perfluoroalkyl segments developed in earlier work. This simple approach, which was proposed in previous work [P. Morgado, H. Zhao, F. J. Blas, C. McCabe, L. P. N. Rebelo, and E. J. M. Filipe, J. Phys. Chem. B, 111, 2856], is now extended to describe model n-alkane (or perfluoroalkane) + perfluroalkylalkane binary mixtures. We have obtained the phase behaviour of different mixtures and studied the effect of the molecular weight of n-alkanes and perfluoroalkanes on the type of phase behaviour observed in these mixtures. We have also analysed the effect of the number of alkyl and perfluoroalkyl chemical groups in the surfactant molecule on the phase behaviour. In addition to the usual vapour-liquid phase separation, liquid-liquid, positive azeotropes, and Bancroft points are found for different mixtures. This rich phase behaviour is a consequence of a delicate balance between the alkyl-alkyl, perfluoroalkyl-perfluoroalkyl, and alkyl-perfluoroalkyl interactions in different molecules. We used the SAFT-VR microscopic description of chain-like systems to analyse the conditions that n-alkane (or perfluoroalkane) + perfluoroalkyalkane mixtures should posses in order to exhibit complete liquid miscibility. Although the model proposed here is chosen to reproduce most of the quantitative features of the phase equilibria of some pure perfluoroalkylalkane diblock surfactants and their mixtures with n-alkanes, this is the first time the SAFT approach has been used to predict the phase behaviour of the mixtures considered here. The lack of experimental data for these systems does not allow us to test the accuracy of our theoretical predictions directly. However, since SAFT has proven to be an excellent approach for the prediction of the phase behaviour of complex mixtures, we expect that the theory will reproduce the most important qualitative trends exhibited by real mixtures. [ABSTRACT FROM AUTHOR]