Hybrid nanostructures exhibiting both photocatalytic and antibacterial activity-a review.

The most vital issues of the modern world for a sustainable future are "health" and "the environment." Scientific endeavors to tackle these two major concerns for mankind need serious attention. The photocatalytic activity toward curbing environmental pollution and antibacterial performance toward a healthy society are two directions that have been emphasized for decades. Recently, materials engineering, in their nanodimension, has shown tremendous possibilities to integrate these functionalities within the same materials. In particular, hybrid nanostructures have shown magnificent prospects to combat both crucial challenges. Many researchers are separately engaged in this important field of research but the collective knowledge on this domain which can facilitate them to excel is badly missing. The present article integrates the development of different hybrid nanostructures which exhibit both photocatalytic degradations of environmental pollutants and antibacterial efficiency. Various synthesis techniques of those hybrid nanomaterials have been discussed. Hybrid nanosystems based on several successful materials have been categorically discussed for better insight into the research advancement in this direction. In particular, Ag-based, metal oxides-based, layered carbon material-based, and Mexene- and self-cleaning-based materials have been chosen for detailing their performance as anti-pollutant and antibacterial materials. Those hybrid systems along with some miscellaneous booming nanostructured materials have been discussed comprehensively with their success and limitations toward their bifunctionality as antipollutant and antibacterial agents.

Photoinduced bidirectional switching in lipid membranes containing azobenzene glycolipids.

Following the reaction of biological membranes to external stimuli reveals fundamental insights into cellular function. Here, self-assembled lipid monolayers act as model membranes containing photoswitchable azobenzene glycolipids for investigating structural response during isomerization by combining Langmuir isotherms with X-ray scattering. Controlled in-situ trans/cis photoswitching of the azobenzene N = N double bond alters the DPPC monolayer structure, causing reproducible changes in surface pressure and layer thickness, indicating monolayer reorientation. Interestingly, for monolayers containing azobenzene glycolipids, along with the expected DPPC phase transitions an additional discontinuity is observed. The associated reorintation represents a crossover point, with the surface pressure and layer thickness changing in opposite directions above and below. This is evidence that the azobenzene glycolipids themselves change orientation within the monolayer. Such behaviour suggests that azobenzene glycolipids can act as a bidirectional switch in DPPC monolayers providing a tool to investigate membrane structure-function relationships in depth.

Real-time observation of photoionization-induced water migration dynamics in 4-methylformanilide-water by picosecond time-resolved infrared spectroscopy and ab initio molecular dynamics simulations.

A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the trans-4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics. Time constants for the initial to the intermediate and hot product and to the final product are obtained. The acceleration of the dynamics by methyl substitution and the strong contribution of intracluster vibrational energy redistribution in the termination of the solvation dynamics is suggested. This picture is well confirmed by the ab initio on-the-fly molecular dynamics simulations. Vibrational assignments of 4MetFA and 4MetFA-W in the neutral (S0 and S1) and ionic (D0) electronic states measured by ns IR dip and electron-impact IR photodissociation spectroscopy are also discussed prior to the results of time-resolved spectroscopy.

Vibrational Spectroscopy of Benzonitrile-(Water)1-2 Clusters in Helium Droplets.

Polycyclic aromatic hydrocarbons are considered as primary carriers of the unidentified interstellar bands. The recent discovery of the first interstellar aromatic molecule, benzonitrile (C6H5CN), suggests a repository of aromatic hydrocarbons in the outer earth environment. Herein, we report an infrared (IR) study of benzonitrile-(D2O)n clusters using mass-selective detection in helium nanodroplets. In this work, we use isotopically substituted water, D2O, instead of H2O because of our restricted IR frequency range (2565-3100 cm-1). A comparison of the experimental and predicted spectra computed at the MP2/6-311++G(d,p) level of benzonitrile-(water)1-2 clusters reveals the formation of a unique local minimum structure, which was not detected in previous gas-phase molecular beam experiments. Here, the solvent water forms a nearly linear hydrogen bond (H-bond) with the nitrile nitrogen of benzonitrile, while the previously reported most stable cyclic H-bonded isomer is not observed. This can be rationalized by the stepwise aggregation process of precooled monomers. The addition of a second water molecule results in the formation of two different isomers. In one of the observed isomers, a H-bonded water chain binds linearly to the nitrile nitrogen similar to the monohydrated benzonitrile-water complex. In the other observed isomer, the water dimer forms a ring-type structure, where a H-bonded water dimer simultaneously interacts with the nitrile nitrogen and the adjacent ortho CH group. Finally, we compare the water-binding motif in the neutral benzonitrile-water complex with the corresponding positively and negatively charged benzonitrile-water monohydrates to comprehend the charge-induced alteration of the solvent binding motif.

Unravelling the microhydration frameworks of prototype PAH by infrared spectroscopy: naphthalene-(water)1-3.

Hydration of aromatic molecules is a fundamental chemical process. Herein, microhydration framework of the prototypical neutral polycyclic aromatic hydrocarbon (PAH), naphthalene (naphthalene-(water)n≤3), is investigated by infrared spectroscopy inside helium nanodroplets. The measured data are analyzed by quantum chemical calculations at the MP2/6-311++G(d,p) level. This combined experimental and theoretical approach demonstrates that water binds to the naphthalene ring via π hydrogen bond (H-bond) for n = 1 case. Further addition of the solvent molecules occurs via the formation of a H-bonded water network facilitated by the nonadditive cooperative force. No isomers are observed in which the solvent molecules separately bind to the aromatic ring. For n = 3 case, we observe the formation of a cyclic H-bonded water moiety. Comparison with corresponding cationic and anionic naphthalene±-(water)n clusters demonstrates the charge-induced modification of the hydration motif. Our results are further compared with the prototypical benzene-(water)n complexes to comprehend the effect of an additional phenyl ring on the solvation network.

Stepwise Microhydration of Isoxazole: Infrared Spectroscopy of Isoxazole-(Water)n≤2 Clusters in Helium Nanodroplets.

Hydration of heterocyclic molecules plays a crucial role in biological and chemical recognition. Here, we present an infrared (IR) spectroscopic investigation of microhydrated, heterocyclic isoxazole molecule. The IR spectra of isoxazole-(water)n≤2 clusters are recorded using helium nanodroplet spectroscopy and are analyzed by quantum chemical calculations at the MP2/6-311++g(d,p) level. In the most abundant isoxazole-water dimer, the solvent water participates in a N···HO hydrogen bonding (H-bond) interaction, while in another observed structure, water simultaneously interacts with ring nitrogen and the neighboring CH group via N···HO and CH···O H-bonds. The addition of another water molecule to the monohydrated cluster results in the formation of a single isomer that features a seven-membered ring, in which the water dimer simultaneously interacts with skeletal nitrogen and the adjacent CH group through N···HO and CH···O bonds.

Directly Exfoliated Ultrathin Silicon Nanosheets for Enhanced Photocatalytic Hydrogen Production.

Here we present direct exfoliation of ultrathin silicon nanosheets from commercial silicon powders through an improved liquid phase exfoliation procedure. The feasibility of exfoliation was ascribed to the intrinsic anisotropic lattice structure, which allowed the oriented propagations of cryo-mediation-induced quenching cracks with the assistance of sonication. It was also revealed that the solid-solvent interface played a critical role in determining the morphology of exfoliated pieces as well as the exfoliation efficiency. Moreover, due to its superior morphology, enlarged surface area, and improved photon absorption, the resulting ultrathin silicon nanosheets presented enhanced and visible light responsive photocatalytic hydrogen generation performance, even without applying any co-catalyst.

Spectroscopic identification of fragment ions of DNA/RNA building blocks: the case of pyrimidine.

Pyrimidine (Pym, 1,3-diazine, 1,3-diazabenzene) is an important N-heterocyclic building block of nucleobases. Understanding the structures of its fragment and precursor ions provides insight into its prebiotic and abiotic synthetic route. The long-standing controversial debate about the structures of the primary fragment ions of the Pym+ cation (C4H4N2+, m/z 80) resulting from loss of HCN, C3H3N+ (m/z 53), is closed herein with the aid of a combined approach utilizing infrared photodissociation (IRPD) spectroscopy in the CH and NH stretch ranges (νCH/NH) and density functional theory (DFT) calculations. IRPD spectra of cold Ar/N2-tagged fragment ions reveal that the C3H3N+ population is dominated by cis-/trans-HCCHNCH+ ions (∼90%) along with a minor contribution of the most stable H2CCCNH+ and cis-/trans-HCCHCNH+ isomers (∼10%). We also spectroscopically confirm that the secondary fragment resulting from further loss of HCN, C2H2+ (m/z 26), is the acetylene cation (HCCH+). The spectroscopic characterization of the identified C3H3N+ isomers and their hydrogen-bonded dimers with Ar and N2 provides insight into the acidity of their CH and NH groups. Finally, the vibrational properties of Pym+ in the 3 µm range are probed by IRPD of Pym+-(N2)1-2 clusters, which shows a high π-binding affinity of Pym+ toward a nonpolar hydrophobic ligand. Its νCH spectrum confirms the different acidity of the three nonequivalent CH groups.

Microhydration of protonated biomolecular building blocks: protonated pyrimidine.

Protonation and hydration of biomolecules govern their structure, conformation, and function. Herein, we explore the microhydration structure in mass-selected protonated pyrimidine-water clusters (H+Pym-Wn, n = 1-4) by a combination of infrared photodissociation spectroscopy (IRPD) between 2450 and 3900 cm-1 and density functional theory (DFT) calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. We further present the IR spectrum of H+Pym-N2 to evaluate the effect of solvent polarity on the intrinsic molecular parameters of H+Pym. Our combined spectroscopic and computational approach unequivocally shows that protonation of Pym occurs at one of the two equivalent basic ring N atoms and that the ligands in H+Pym-L (L = N2 or W) preferentially form linear H-bonds to the resulting acidic NH group. Successive addition of water ligands results in the formation of a H-bonded solvent network which increasingly weakens the NH group. Despite substantial activation of the N-H bond upon microhydration, no intracluster proton transfer occurs up to n = 4 because of the balance of relative proton affinities of Pym and Wn and the involved solvation energies. Comparison to neutral Pym-Wn clusters reveals the drastic effects of protonation on microhydration with respect to both structure and interaction strength.

Protonation of Naphthalene-(Water)n Nanoclusters: Intracluster Proton Transfer to Hydration Shell Revealed by Infrared Photodissociation Spectroscopy.

Solvation-dependent intracluster proton transfer (ICPT) within bare and Ar-tagged protonated naphthalene-(water)n clusters, H+(Np-Wn) with n ≤ 3, is characterized by infrared photodissociation (IRPD) spectroscopy in a supersonic plasma expansion. IRPD spectra of size-selected clusters recorded in the CH and OH stretch range (2750-3800 cm-1) are analyzed with dispersion-corrected density functional theory (DFT) calculations (B3LYP-D3/aug-cc-pVTZ) to determine both the protonation site and the structure of the hydration network. Ar tagging of H+(Np-Wn) leads to colder spectra with higher spectral resolution. The position of the excess proton is controlled by a subtle balance between the difference in proton affinity (PA) of Np and Wn and the involved solvation energies. For n = 1, the excess proton is localized on the Np ring, leading to a H+Np-W structure with a bifurcated CH···O ionic H-bond, because of the large difference in PA of Np and W. For n = 2, ICPT occurs, and the cluster has a structure in which a symmetric Zundel ion is connected to Np via two strong OH···π ionic H-bonds. Because of the similar PA values of W2 and Np, the energetics of the ICPT is largely decided by the higher solvation energy in favor of Np-H+W2 as compared to H+Np-W2. For n ≥ 3, the PA of Wn substantially exceeds the one of Np, leading to ICPT. Attachment of the bulky planar Np ring to H+Wn causes an increasing perturbation of the bare H+Wn cluster with size by symmetry reduction and the strong OH···π H-bonds. Comparison of H+(Np-Wn) with the related H+(Bz-Wn) clusters (Bz = benzene) indicates the implications of extending the aromatic π-electron system on both the critical threshold size for ICPT (nc = 1 for Bz and nc = 2 for Np) and the structure of the hydration network.

Defect-Engineered MoS2 Nanostructures for Reactive Oxygen Species Generation in the Dark: Antipollutant and Antifungal Performances.

Meticulous surface engineering of layered structures toward new functionalities is a demanding challenge to the scientific community. Here, we introduce defects on varied MoS2 surfaces by suitable doping of nitrogen atoms in a sulfur-rich reaction environment, resulting in stable and scalable phase conversion. The experimental characterizations along with the theoretical calculations within the framework of density functional theory establish the impact of nitrogen doping on stabilization of defects and reconstruction of the 2H to 1T phase. The as-synthesized MoS2 samples exhibit excellent dye removal capacity in the dark, facilitated by a synergistic effect of reactive oxygen species (ROS) generation and adsorption. Positron annihilation spectroscopy and electron paramagnetic resonance studies substantiate the role of defects and associated sulfur vacancies toward ROS generation in the dark. Further, on the basis of its ample ROS generation in the dark and in the light, the commendable antimicrobial activity of the prepared MoS2 samples against fungal pathogen Alternaria alternata has been demonstrated. Thus, the present study opens up a futuristic avenue to develop newer functional materials through defect engineering by suitable dopants toward superior performances in environment issues.

Intracluster proton transfer in protonated benzonitrile-(H2O)n≤6 nanoclusters: hydrated hydronium core for n≥ 2.

Protonation and hydration of aromatic hydrocarbon molecules and their derivatives play a key role in many biological and chemical processes. The recent detection of benzonitrile (BN, cyanobenzene, C6H5CN) in the interstellar medium suggests the existence of its protonated form (H+BN) in both the gas phase and in or on ice grains. Herein, we analyze the vibrational signatures of size-selected protonated clusters composed of BN and water (W, H2O), H+(BN-Wn=1-6), in the XH stretch range (X = C, N, O) with the aid of dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). The size-dependent frequency shifts provide detailed insight about the site of protonation and the structure of the hydration shell. For n = 1, the proton is attached to the N atom of the CN group in BN, and W acts as a proton acceptor in an NHO ionic hydrogen bond (H-bond) of a H+BN-W type structure with cation-dipole configuration. For n≥ 2, the proton is transferred to the H-bonded hydration network, consistent with thermochemical arguments arising from both the relative proton affinities of BN and Wn and the solvation energies. In these proton-transferred BN-H+Wn structures, the excess proton is more or less localized at a H3O+ hydronium core solvated by neutral W and BN ligands. At least for the considered cluster size (n≤ 6), the BN impurity molecule is located in the first solvation shell of the H3O+ ion, consistent with the larger electric dipole moment and proton affinity of BN as compared to W. However, the energy gap between these structures and surface isomers with BN solvated further away from the charge decreases with cluster size, suggesting that BN is located at the surface in large BN-H+Wn clusters. While for smaller clusters (n≤ 4) the hydration network prefers branched structures at T = 0 K, in larger clusters (n≥ 5) cyclic configurations with four- or five-membered H+Wn rings are most stable because they feature more H-bonds than the branched structures. Comparison with bare H+Wn clusters reveals the substantial effects of the perturbation by the BN impurity on the structure of the hydration network.

Microhydration Structures of Protonated Oxazole.

The initial microhydration structures of the protonated pharmaceutical building block oxazole (Ox), H+Ox-Wn≤4, are determined by infrared photodissociation (IRPD) spectroscopy combined with quantum chemical dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). Protonation of Ox, achieved by chemical ionization in a H2-containing plasma, occurs at the most basic N atom. The analysis of systematic shifts of the NH and OH stretch vibrations as a function of the cluster size provides a clear picture for the preferred cluster growth in H+Ox-Wn. For n = 1-3, the IRPD spectra are dominated by a single isomer, and microhydration of H+Ox with hydrophilic protic W ligands occurs by attachment of a hydrogen-bonded (H-bonded) Wn solvent cluster to the acidic NH group via an NH···O H-bond. Such H-bonded networks are stabilized by strong cooperativity effects. This is in contrast to previously studied hydrophobic ligands, which prefer interior ion solvation. The strength of the NH···O ionic H-bond increases with the degree of hydration because of the increasing proton affinity (PA) of the Wn cluster. At n = 4, proton-transferred structures of the type Ox-H+Wn become energetically competitive with H+Ox-Wn structures, because differences in solvation energies can compensate for the differences in the PAs, and barrierless proton transfer from H+Ox to the Wn solvent subcluster becomes feasible. Indeed, the IRPD spectrum of the n = 4 cluster is more complex suggesting the presence of more than one isomer, although it lacks unequivocal evidence for the predicted intracluster proton transfer.

Ionization-Induced π → H Site Switching in Resorcinol-Arn (n = 1 and 2) Clusters Probed by Infrared Spectroscopy.

Infrared (IR) spectra of resorcinol (Rs)-Arn clusters (n = 1 and 2) have been measured in the neutral and cationic ground states (S0 and D0) by IR dip and resonance-enhanced multiphoton ionization (REMPI)-IR spectroscopy. The OH stretching vibrations in S0 keep their frequency regardless of the number of Ar atoms and the conformation of the OH groups in Rs (rotamers RsI and RsII), demonstrating that the Ar atoms are attached to the aromatic π-ring (π-bound structure) in S0. In the D0 state, the IR spectra of Rs+-Arn reflect the difference in the Rs conformations (RsI+ and RsII+). For n = 1, the IR spectra of both rotamers are almost the same as those of the corresponding monomer cations, indicating that Ar ligands essentially remain π-bonded after ionization. In contrast, the IR spectra of Rs+-Ar2 show hydrogen-bonded and free OH stretching vibrations, demonstrating that for a significant fraction of the clusters, the Ar atoms migrate from the π-bound site to the OH groups. The ionization-induced π → H migration yields are not unity for both rotamers RsI+-Ar2 and RsII+-Ar2. This result is in sharp contrast to phenol+-Ar2, in which one of the Ar atoms migrates to the OH site with 100% yield. The mechanism leading to the nonunity yield in Rs+-Ar2 is discussed in terms of the number of OH binding sites and Franck-Condon factors. The ionization excess energy dependence of the IR spectra of Rs+-Ar2 and its Rs+-Ar fragments is discussed in terms of the Ar binding energies estimated from the photoionization and photodissociation efficiency spectra.

Unraveling the protonation site of oxazole and solvation with hydrophobic ligands by infrared photodissociation spectroscopy.

Protonation and solvation of heterocyclic aromatic building blocks control the structure and function of many biological macromolecules. Herein the infrared photodissociation (IRPD) spectra of protonated oxazole (H+Ox) microsolvated by nonpolar and quadrupolar ligands, H+Ox-Ln with L = Ar (n = 1-2) and L = N2 (n = 1-4), are analyzed by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level to determine the preferred protonation and ligand binding sites. Cold H+Ox-Ln clusters are generated in an electron impact cluster ion source. Protonation of Ox occurs exclusively at the N atom of the heterocyclic ring, in agreement with the thermochemical predictions. The analysis of the systematic shifts of the NH stretch frequency in the IRPD spectra of H+Ox-Ln provides a clear picture of the sequential cluster growth and the type and strength of various competing ligand binding motifs. The most stable structures observed for the H+Ox-L dimers (n = 1) exhibit a linear NHL hydrogen bond (H-bond), while π-bonded isomers with L attached to the aromatic ring are local minima on the potential and thus occur at a lower abundance. From the spectra of the H+Ox-L(π) isomers, the free NH frequency of bare H+Ox is extrapolated as νNH = 3444 ± 3 cm-1. The observed H+Ox-L2 clusters with L = N2 feature both bifurcated NHL2 (2H isomer) and linear NHL H-bonding motifs (H/π isomer), while for L = Ar only the linear H-bond is observed. No H+Ox-L2(2π) isomers are detected, confirming that H-bonding to the NH group is more stable than π-bonding to the ring. The most stable H+Ox-(N2)n clusters with n = 3-4 have 2H/(n - 2)π structures, in which the stable 2H core ion is further solvated by (n - 2) π-bonded ligands. Upon N-protonation, the aromatic C-H bonds of the Ox ring get slightly stronger, as revealed by higher CH stretch frequencies and strongly increased IR intensities.

The antibacterial and anticancer properties of zinc oxide coated iron oxide nanotextured composites.

Core-shell α-Fe2O3-ZnO structures of different nanotextured morphology were synthesized through wet chemical routes using different solvents like ethanol, ethanolamine, water and acetaldehyde. Morphological tuning using different solvents resulted in the formation of different shapes, such as disc, spindle, rod and sphere (abbreviated as FZ-ND, FZ-NSP, FZ-NR and FZ-NS, respectively). Structural, morphological and compositional characterization of these nanoparticles (NPs) has been carried out. Antibacterial efficacy of the synthesized NPs was checked against Gram negative V. cholerae N16961 (VcN16961) and Gram positive S. aureus bacteria by recording optical density (OD) at different time points. Among the NPs tested, FZ-NSP was found to be the most effective against VcN16961, while FZ-NR showed maximum efficacy against S. aureus, implying the importance of nanotextured surface as well as the morphology in the manifestation of antibacterial activity. The kinetics of growth for both the bacteria has been modelled using logistic approach. Cytotoxicity was evaluated through MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide) assay against human breast adenocarcinoma cell line (MCF-7), human hepatocarcinoma cell line (HepG2) and against normal human embryonic kidney cell line (HEK-293). The lesser toxicity of α-Fe2O3-ZnO towards HEK-293 and the potent anticancer activity against MCF-7 and HepG2 cells underline its applicability as anticancer agent. With continued improvement of nanotechnology, this study may pave the way for designing and construction of various morphologically diverse, nanotextured materials with desired functional attributes.

Aromatic Charge Resonance Interaction Probed by Infrared Spectroscopy.

Charge resonance is a strong attractive intermolecular force in aromatic dimer radical ions. Despite its importance, this fundamental interaction has not been characterized at high resolution by spectroscopy of isolated dimers. We employ vibrational infrared spectroscopy of cold aromatic pyrrole dimer cations to precisely probe the charge distribution by measuring the frequency of the isolated N-H stretch mode (νNH ). We observe a linear correlation between νNH and the partial charge q on the pyrrole molecule in different environments. Subtle effects of symmetry reduction, such as substitution of functional groups (here pyrrole replaced by N-methylpyrrole) or asymmetric solvation (here by an inert N2 ligand), shift the charge distribution toward the moiety with lower ionization energy. This general approach provides a precise experimental probe of the asymmetry of the charge distribution in such aromatic homo- and heterodimer cations.

Switching of binding site from nonpolar to polar ligands toward cationic benzonitrile revealed by infrared spectroscopy.

Noncovalent interactions of aromatic molecules in their various charge states with their surrounding environment are of fundamental importance in chemistry and biology. Herein, we analyze the infrared photodissociation spectra of mass-selected cationic clusters of benzonitrile (BN, cyanobenzene, C6H5CN) with L = Ar, N2, and H2O (W), in the CH and OH stretch range (2950-3800 cm-1) with the aid of density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level to probe the interaction of this fundamental aromatic cation in its 2B1 ground electronic state with nonpolar, quadrupolar, and dipolar solvent molecules. While Ar and N2 prefer π-stacking to the aromatic ring of BN+ strongly supported by dispersion forces, W forms a bifurcated CH⋯O ionic hydrogen bond to two adjacent CH groups stabilized by electrostatic forces. Comparison of the BN+-L dimers with related aromatic clusters reveals the effect of ionization, protonation, and substitution of functional groups on the type and strengths of the competing ligand binding motifs.

Photoswitchable Glycolipid Mimetics: Synthesis and Photochromic Properties of Glycoazobenzene Amphiphiles.

Glycolipids as constituents of cell membranes play an important role in cell membrane functioning. To enable the structural modification of membranes on demand, embedding of photosensitive glycolipid mimetics was envisioned and novel amphiphilic glycolipid mimetics comprising a photoswitchable azobenzene unit were synthesized. In this study, the photochromic properties of these glycolipid mimetics were analyzed by means of UV/Vis spectroscopy and reversible photoswitching. The glycolipids were based on a racemic glycerolipid derivative to be comparable in DPPC (dipalmitoylphosphatidylcholine) phospholipid membrane monolayers. Carbohydrate head groups were altered between a ß-glucoside and a ß-lactosyl unit, as well as acyl chain lengths between C12 and C16, resulting in altered photoswitching. Langmuir isotherms showed that photoswitching of Langmuir films comprising the synthetic photosensitive glycoamphiphiles was successful.

MoS2 -Carbon Nanotube Porous 3 D Network for Enhanced Oxygen Reduction Reaction.

Future generation power requirement triggers the increasing search for electrocatalysts towards oxygen reduction, which is the pivotal part to enhance the activity of metal-air batteries and fuel cells. The present article reports a novel 3 D composite structure weaving 1 D carbon nanotubes (CNT) and 2 D MoS2 nanosheets. The MoS2 -CNT composite exhibits excellent electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline environment. Measurements show better methanol immunity and higher durability than Pt/C, which is considered the state-of-the-art catalyst for ORR. Experimental results suggest that the hybridization of 1 D functionalized multiwalled CNTs (MWCNTs) and exfoliated 2 D MoS2 nanosheet results significant synergistic effect, which greatly promotes the ORR activity. This work presents a new avenue to rationally design a 3 D porous composite out of 1 D and 2 D interlaced components and demonstrate appreciable electrochemical performance of the materials towards ORR activity for fuel cells as well as metal-air batteries.