Tuning Electrons Migration of Dual S Defects Mediated MoS2-x/ZnIn2S4-x Toward Highly Efficient Photocatalytic Hydrogen Production.

Photocatalytic hydrogen production is a prevalent method for hydrogen synthesis. However, high recombination rate of photogenerated carriers and high activation energy barrier of H remain persistent challenge. Here, the two-step hydrothermal method is utilized to prepare dual S-defect mediated catalyst molybdenum sulfide/zinc indium sulfide (MSv/ZISv), which has high hydrogen production rate of 8.83 mmol g-1h-1 under simulated sunlight. The achieved rate is 21.91 times higher than pure ZnIn2S4 substrate. Defects in ZIS within MSv/ZISv modify the primitive electronic structure by creating defect state that retaining good reducing power, leading to the rapid separation of electron-hole pairs and the generation of additional photogenerated carriers. The internal electric field further enhances the migration toward to cocatalyst. Simultaneously, the defects introduced on the MoS2 cause electron rearrangement, leading to electron clustering on both S vacancies and edge S. Thereby MSv/ZISv exhibits the lowest activation energy barrier and |ΔGH*|. This work explores the division of synergies between different types of S defects, providing new insights into the coupling of defect engineering.

Hierarchical Anion Exchange and Reverse Electron Transfer in Layered Double Hydroxides/Peroxymonosulfate System for Roxarsone Elimination.

Roxarsone (ROX) is the main form of arsenic pollution in the world, and developing effective methods for its elimination is beneficial to human health and the ecological environment. Herein, we report glutaraldehyde cross-linked chitosan-encapsulated CoCe-LDH (layered double hydroxides) as an outstanding catalyst for the advanced oxidation of ROX and the efficient adsorption of inorganic arsenic. 100% of ROX and more than 98.5% of As(III)/As(V) were eliminated, and over 99.3% of remaining inorganic arsenic was oxidized to low-toxicity As(V) in the peroxymonosulfate (PMS) activation system, and some specific properties of LDH are considered the main reasons. The hierarchical anion exchange has been confirmed to be beneficial for constructing a high-concentration PMS interlayer microenvironment. The unique reverse electron transfer process induced 100% selective production of singlet oxygen. This work not only develops an advanced ROX removal method but also provides a new understanding of the LDH-based advanced oxidation process.

Proton-Enriched Alginate-Graphene Hydrogel Microreactor for Enhanced Hydrogen Peroxide Photosynthesis.

Efficient synthesis of H2O2 via photocatalytic oxygen reduction without sacrificial agents is challenging due to inadequate proton supply from water and difficulty in maintaining O-O bond during O2 activation. Herein, we developed a straightforward strategy involving a proton-rich hydrogel cross-linked by metal ions [M(n)], which is designed to facilitate the selective production of H2O2 through proton relay and metal ion-assisted detachment of crucial intermediates. The hydrogel comprises CdS/graphene and alginate cross-linked by metal ions via O=C-O-M(n) bonds. Efficient O2 reduction and hydrogenation occurred, benefitting from the collaboration between proton-rich alginate and the photocatalytically active CdS/graphene. Meanwhile, the O=C-O-M(n) bonds enhance the electron density of α-carbon sites on graphene, crucial for O2 activation and *OOH intermediate detachment, preventing deeper O-O bond cleavage. The role of metal ions in promoting *OOH desorption was demonstrated through Lewis acidity-dependent activity, with Y(III) having the highest activity, followed by Lu(III), La(III), and Ca(II).

The Precision Defect Engineering with Nonmetallic Element Refilling Strategy in g-C3 N4 for Enhanced Photocatalytic Hydrogen Production.

Traditional defect engineering and doping strategies are considered effective means for improving H2 evolution, but the uncontrollability of the modification process does not always lead to efficient activity. A defect-induced heteroatom refilling strategy is used here to synthesize heteroatoms introduced carbon nitride by precisely controlling the "introduction" sites on efficient N1 sites. Density functional theory calculations show that the refilling of B, P, and S sites have stronger H2 O adsorption and dissociation capacity than traditional doping, which makes it an optimal H2 production path. The large internal electric field strength of heteroatom-refilled catalysts leads to fast electron transfer and the hydrogen production of the best sample is up to 20.9 mmol g-1  h-1 . This work provides a reliable and clear insight into controlled defect engineering of photocatalysts and a universal modification strategy for typical heteroatom and co-catalyst systems for H2 production.

Ga-Doped and Pt-Loaded Porous TiO2-SiO2 for Photocatalytic Nonoxidative Coupling of Methane.

Photodriven nonoxidative coupling of CH4 (NOCM) is a potential alternative approach to clean hydrogen and hydrocarbon production. Herein, a Mott-Schottky photocatalyst for NOCM is fabricated by loading Pt nanoclusters on a Ga-doped hierarchical porous TiO2-SiO2 microarray with an anatase framework, which exhibits a CH4 conversion rate of 3.48 µmol g-1 h-1 with 90% selectivity toward C2H6. This activity is 13 times higher than those from microarrays without Pt and Ga. Moreover, a continuous H2 production (36 µmol g-1) with a high CH4 conversion rate of ∼28% can be achieved through a longtime irradiation (32 h). The influence of Ga on the chemical state of a surface oxygen vacancy (Vo) and deposited Pt is investigated through a combination of experimental analysis and first-principles density functional theory calculations. Ga substitutes for the five-coordinated Ti next to Vo, which tends to stabilize the single-electron trapped Vo and reduce the electron transfer from Vo to the adsorbed Pt, resulting in the formation of a higher amount of cationic Pt. The cationic Pt and electron-enriched metallic Pt form a cationic-anionic active pair, which is more efficient for the dissociation of C-H bonds. However, the presence of too much cationic Pt results in more C2+ product with a decrease in the CH4 conversion rate due to the reduced charge-carrier separation efficiency. This study provides deep insight into the effect of the doping/loading strategy on the photocatalytic NOCM reaction and is expected to shed substantial light on future structural design and modulation.

Z-scheme inverse opal CN/BiOBr photocatalysts for highly efficient degradation of antibiotics.

Optimizing the heterojunction structure of semiconductor photocatalysts is vital for utilizing their abilities in organic matter degradation. Herein, a novel fabrication of a Z-scheme system with inverse opal g-C3N4 and BiOBr via a reflux process is developed. On the one hand, the unique inverse opal construction, formed by using silica (SiO2) photonic crystals as the template, not only provides a larger surface area for adsorption of antibiotics but also improves the separation and transfer efficiency of photogenerated electrons and holes as well as visible light absorption ability. On the other hand, by imitating natural photosynthesis, the artificial Z-scheme system with an inverse opal g-C3N4-BiOBr nanojunction further promotes the separation of photogenerated electrons and holes. The obtained IO CN/BiOBr catalyst exhibits superior photocatalytic performance for antibiotics degradation under visible light irradiation. In a typical test, almost complete degradation of levofloxacin (LVX) (10 mg L-1) could be achieved within 50 min due to the proper bandgap match between inverse opal g-C3N4 and BiOBr as well as enhanced surface area and light absorption. The present work provides an alternative strategy for construction of novel visible-light-driven Z-scheme photocatalysts and offers some new insights into the methods of waste water treatment.

Adsorptive removal of bisphenol A, chloroxylenol, and carbamazepine from water using a novel ß-cyclodextrin polymer.

The emerging organic micro-pollutants, such as bisphenol A (BPA), chloroxylenol (PCMX) and carbamazepine (CBZ), have raised concerns owing to their adverse impact on human health and ecological security. In this study, a novel cyclodextrin polymer (ß-CDP) has been successfully prepared by nucleophilic substitution of ß-cyclodextrin with tetrafluoroterephthalonitrile (TFP). The removal of three emerging organic micro-pollutants (BPA, CBZ and PCMX) by ß-CDP under a single or mixture adsorption system was examined, and the adsorption behavior was investigated by adsorption kinetics and isotherm study. The maximum adsorption capacity of ß-CDP for BPA, PCMX and CBZ according to Langmuir isotherm in single system was 164.4, 144.1 and 136.4 mg/g, respectively. Compared with single system, the competitive adsorption of each pollutant on ß-CDP in mixture system was only slightly inhibited. Changing the pH, raising the presence of fulvic acid (FA) or ionic strength had no significant influence on the adsorption of BPA, PCMX and CBZ onto ß-CDP. The removal of these three organic micro-pollutants was related to the value of logKow of the contaminants. These results demonstrated remarkable advantages of ß-CDP material relevant to organic micro-pollutants removal in wastewater treatment.

Cyclodextrin modified filter paper for removal of cationic dyes/Cu ions from aqueous solutions.

A filter paper was functionalized with ß-cyclodextrin and citric acid via esterification reaction for the removal of dyes and Cu ions from aqueous solutions. The adsorption capacity and removal performance of the modified filter paper (MFP) was investigated using static and dynamic adsorption experiments. The static adsorption data fit well the Langmuir and pseudo-second-order models, and the adsorption capacity of Methylene Blue (MB), Brilliant Green (BG), Rhodamine-B (RB) and Cu(II) over the MFP were 124.6 mg/g, 130.4 mg/g, 99.7 mg/g and 39.1 mg/g, respectively, which are much higher than the unmodified filter paper (below 2 mg/g). Even better, the decolorization performance and Cu(II) removal of MFP are remarkable in dynamic adsorption. The effluent can reach the National Standard for dyeing and finishing of textile industry of China after three cycles in a continuous filtration-adsorption system. This method provides a new pathway to achieve high efficiency removal of dyes and metal ions from wastewater.

Cation-Dependent Gold Recovery with α-Cyclodextrin Facilitated by Second-Sphere Coordination.

Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly α-cyclodextrin (α-CD). Upon mixing eight salts composed of Na(+), K(+), Rb(+), or Cs(+) cations and [AuX4](-) (X = Cl/Br) anions with α-, ß-, or γ-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing α-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of α-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H···X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between α-CD and KAuBr4, a [K(OH2)6](+) cation is encapsulated inside the cavity between the secondary faces of two α-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous α-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb(+) and Cs(+) cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two α-CDs, facilitates the co-precipitation of the two adducts formed between α-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of α-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of α-CD to KAuBr4.

Carbon-Dot-Sensitized, Nitrogen-Doped TiO2 in Mesoporous Silica for Water Decontamination through Nonhydrophobic Enrichment-Degradation Mode.

Mesoporous silica synthesized from the cocondensation of tetraethoxysilane and silylated carbon dots containing an amide group has been adopted as the carrier for the in situ growth of TiO2 through an impregnation-hydrothermal crystallization process. Benefitting from initial complexation between the titania precursor and carbon dot, highly dispersed anatase TiO2 nanoparticles can be formed inside the mesoporous channel. The hybrid material possesses an ordered hexagonal mesostructure with p6mm symmetry, a high specific surface area (446.27 m(2) g(-1) ), large pore volume (0.57 cm(3) g(-1) ), uniform pore size (5.11 nm), and a wide absorption band between λ=300 and 550 nm. TiO2 nanocrystals are anchored to the carbon dot through TiON and TiOC bonds, as revealed by X-ray photoelectron spectroscopy. Moreover, the nitrogen doping of TiO2 is also verified by the formation of the TiN bond. This composite shows excellent adsorption capabilities for 2,4-dichlorophenol and acid orange 7, with an electron-deficient aromatic ring, through electron donor-acceptor interactions between the carbon dot and organic compounds instead of the hydrophobic effect, as analyzed by the contact angle analysis. The composite can be photocatalytically recycled through visible-light irradiation after adsorption. The narrowed band gap, as a result of nitrogen doping, and the photosensitization effect of carbon dots are revealed to be coresponsible for the visible-light activity of TiO2 . The adsorption capacity does not suffer any clear losses after being recycled three times.

In situ growth of TiO2 nanocrystals on g-C3N4 for enhanced photocatalytic performance.

Well dispersed TiO2 nanocrystals with (001) facets were successfully grown in situ on g-C3N4 through a facial solvothermal method. The resultant TiO2/g-C3N4 composites exhibit remarkably higher efficiency for photocatalytic degradation of phenol as compared to pure catalysts (g-C3N4 or TiO2) or mechanically mixed TiO2/g-C3N4. The optimal composite with 11.2 wt% TiO2 showed the highest degradation rate constant, which is 2.8 times that of pure g-C3N4, 2.2 times that of pure TiO2, and 1.4 times that of mechanically mixed TiO2/g-C3N4. The enhanced photocatalytic activity is mainly attributed to the effective charge separation derived from two aspects: (1) well matched energy levels between TiO2 and g-C3N4 and (2) a uniform and close contact between TiO2 and g-C3N4 that resulted from the in situ growth of highly dispersed TiO2 nanocrystals. The TiO2/g-C3N4 hybrid material prepared in this study is expected to provide a good foundation for the further design and synthesis of advanced TiO2/g-C3N4-based functional materials, and the in situ growth method developed is hopeful to provide a new strategy for the synthesis of other semiconductor-modified g-C3N4 materials.

A square-planar tetracoordinate oxygen-containing Ti4O17 cluster stabilized by two 1,1'-ferrocenedicarboxylato ligands.

By introducing steric constraints into molecular compounds, it is possible to achieve atypical coordination geometries for the elements. Herein, we demonstrate that a titanium-oxo cluster [{Ti4(µ4-O)(µ2-O)2}(OPr(i))6(fdc)2], which possesses a unique edge-sharing Ti4O17 octahedron tetramer core, is stabilized by the constraints produced by two orthogonal 1,1'-ferrocenedicarboxylato (fdc) ligands. As a result, a square-planar tetracoordinate oxygen (ptO) can be generated. The bonding pattern of this unusual anti-van't Hoff/Le Bel oxygen, which has been probed by theoretical calculations, can be described by two horizontally σ-bonded 2p(x) and 2p(y) orbitals along with one perpendicular nonbonded 2p(z) orbital. While the two ferrocene units are separated spatially by the ptO with an Fe⋅⋅⋅Fe separation of 10.4 Å, electronic communication between them still takes place as revealed by the cluster's two distinct one-electron electrochemical oxidation processes.

Boosting Peroxymonosulfate Activation via CoS/MXene Nanocomposite for Rhodamine B Degradation under Simulated Sunlight Irradiation.

Cobalt-based heterogeneous catalysts have been demonstrated as an effective PMS activator for pollutant degradation. However, the limited active sites on their surface lead to an unsatisfactory catalytic efficiency. Immobilizing the catalysts on the support material can be a promising modification strategy to solve this problem. MXene has been considered as an ideal support material due to its unique morphology and physicochemical properties. Therefore, in this work, the CoS-loaded Ti3 C2 MXene (CoS/Ti3 C2 MXene) catalyst for peroxymonosulfate (PMS) activation was successfully synthesized through a solvothermal method. Under the simulated sunlight irradiation, the CoS/Ti3 C2 MXene+PMS system achieved an impressive efficiency in removing the organic pollutant rhodamine B (97.2 % in 10 min). Among the tested catalysts, 30 %-CoS-TC stood out, exhibited a broad pH tolerance from 5 to 9 and maintained robust degradation performance over cycles. Upon detailed analysis, the degradation mechanism revealed the collaborative action dominated by singlet oxygen, and supplemented by photogenerated holes and superoxide radicals in the process. Notably, the sandwich-like structure of MXene played a pivotal role, not only dispersing the CoS particles evenly on the surface of catalysts, but also providing ample space for the active sites, thus accelerating the PMS activation for the degradation of rhodamine B. Overall, this study developed an innovative MXene-based catalyst for the application of environmental remediation.

A binary dumbbell visible light driven photocatalyst for simultaneous hydrogen production with the selective oxidation of benzyl alcohol to benzaldehyde.

Photocatalytic H2 production with selective oxidation of organic moieties in an aqueous medium is a fascinating research area. However, the rational design of photocatalysts and their photocatalytic performance are still inadequate. In this work, we efficiently synthesized the MoS2 tipped CdS nanowires (NWs) photocatalyst using soft templates via the two-step hydrothermal method for efficient H2 production with selective oxidation of benzyl alcohol (BO) under visible light illumination. The optimized MoS2 tipped CdS NWs (20 % MoS2) photocatalyst exhibits the highest photocatalytic H2 production efficiency of 13.55 mmol g-1 h-1 with 99 % selective oxidation of BO, which was 42.34 and 2.21 times greater photocatalytic performance than that of pristine CdS NWs and MoS2/CdS NWs, respectively. The directional loading of MoS2 at the tips of CdS NWs (as compared to nondirectional MoS2 at CdS NWs) is the key factor towards superior H2 production with 99 % selective oxidation of BO and has an inhibitory effect on the photo corrosion of pristine CdS NWs. Therefore, the amazing enhancement in the photocatalytic performance and selectivity of optimized MoS2 tipped CdS NWs (20 % MoS2) photocatalyst is due to the spatial separation of their photoexcited charge carriers through the Schottky junction. Moreover, the unique structure of the MoS2 flower at the tip of 1D CdS NWs offers separate active sites for adsorption and surface reactions such as H2 production at the MoS2 flower (confirmed by Pt photo deposition) and subsequently the selective oxidation of BO at the stem of CdS NWs. This rational design of a photocatalyst could be an inspiring work for the further development of an efficient photocatalytic system for H2 production with selective oxidation of BO (a strategy of mashing two potatoes with one fork).

Constructing a non-noble metal WC/CaIn2S4 Schottky heterojunction photocatalyst for enhanced photocatalytic H2 production.

To take the pronounced issue of recombination among photogenerated electrons and holes in the photocatalytic reaction, we report a WC/CaIn2S4 Schottky heterojunction photocatalyst using a straightforward one-step hydrothermal method and applied it for the enhanced hydrogen evolution reaction in photocatalysis. A stable Schottky energy barrier can be formed by closely connecting the metal-like WC with the n-type semiconductor CaIn2S4, accelerating the migration of photogenerated carriers. Meanwhile, WC can lower the overpotential for hydrogen evolution, leading to a notable enhancement in the photocatalytic hydrogen evolution rate. The hydrogen evolution rate of the optimal WC/CaIn2S4 Schottky heterojunction photocatalyst WCIS1:1 was approximately 2.3 times higher than that of Pt-loaded photocatalyst CIS+Pt. This study delves into the application significance of the Schottky heterojunction principle in the photocatalytic hydrogen production reaction. Furthermore, this study provides a novel approach to replacing noble metal Pt with metal-like WC in the field of photocatalytic hydrogen evolution.

Contamination characteristics and dietary intake risk of brominated flame retardants in fishes around a typical e-waste dismantling site in Southern China.

Polybrominated diphenyl ethers (PBDEs) and their substitutes, novel brominated flame retardants (NBFRs), are ubiquitously present in the aquatic environment of electronic waste (e-waste) dismantling region, leading to their inevitable absorption and accumulation by aquatic organisms, which can be transferred to human via directly aquatic product consumption or through food chain, thereby posing potential health risks. This study focused on fish samples from Guiyu and its surrounding areas, and found the total PBDEs concentrations were 24-7400 ng/g lw (mean: 1800 ng/g lw) and the total NBFRs concentrations were 14 to 2300 ng/g lw (mean: 310 ng/g lw). Significant positive correlations were found among PBDE congeners, among different NBFRs, and between NBFRs and commercial PBDEs that they replace. ΣPBDEs and ΣNBFRs in the intestine were 620-350,000 and 91-81,000 ng/g lw (mean: 83000 and 12,000 ng/g lw, respectively), significantly exceeding those in the gills, where ΣPBDEs and ΣNBFRs were 14-37,000 and 39-45,000 ng/g lw (mean: 9200 and 2400 ng/g lw, respectively). The ΣPBDEs and ΣNBFRs showed no non-carcinogenic risks to the target population through dietary intake. Despite the significantly higher daily intake of decabromodiphenyl ethane (DBDPE) compared to decabromodiphenyl ether (BDE209), the non-carcinogenic risk associated with BDE209 remained higher than that of DBDPE. Our findings can assist researchers in understanding the presence of BFRs in aquatic organisms, inhabiting e-waste dismantling areas, and in evaluating the associated health risks posed to humans through dietary exposure.

Insight on photocatalytic synchronous oxidation and reduction for pollutant removal: Chemical energy conversion between macromolecular organic pollutants and heavy metal.

Collaborative treatment of pollutants is a promising approach for wastewater treatment. In this work, a covalent organic framework material (COFs) with an imine structure was synthesised by the Schiff base reaction, and photochemical tests showed good photochemical effects. It was used to explore the photocatalytic treatment of co-existing pollutants (heavy metal ions and antibiotics) and the performance of treating co-existing wastewater was investigated. The degradation performance of levofloxacin (LVX) and Cr(VI) was improved in the coexisting pollutants system, with the LVX degradation being 4.2 times more effective than that of the LVX solitary system. Moreover, this phenomenon was also observed in LVX/Ag(I), LVX/Fe(III), sulfadiazine/Cr(VI), norfloxacin/Cr(VI) and tetracycline/Cr(VI) systems. The analysis of active species suggesting that the synergistic promotion of photocatalytic oxidation-reduction systems was not only promoting from the improvement of simple charge separation, but it was also found that high-valent metal species can act directly in the oxidative decomposition of antibiotics. The interaction of pollutants and intermediates were rationally exploited and confirmed by control experiments and theoretical calculation. This conclusion helps us to re-examine the underlying mechanisms of photocatalytic synchronous oxidation and reduction reactions, simultaneously beneficial for the development of mixed pollutant control processes.

Mechanical bond-induced radical stabilization.

A homologous series of [2]rotaxanes, in which cyclobis(paraquat-p-phenylene) (CBPQT(4+)) serves as the ring component, while the dumbbell components all contain single 4,4'-bipyridinium (BIPY(2+)) units centrally located in the midst of oligomethylene chains of varying lengths, have been synthesized by taking advantage of radical templation and copper-free azide-alkyne 1,3-dipolar cycloadditions in the formation of their stoppers. Cyclic voltammetry, UV/vis spectroscopy, and mass spectrometry reveal that the BIPY(•+) radical cations in this series of [2]rotaxanes are stabilized against oxidation, both electrochemically and by atmospheric oxygen. The enforced proximity between the BIPY(2+) units in the ring and dumbbell components gives rise to enhanced Coulombic repulsion, destabilizing the ground-state co-conformations of the fully oxidized forms of these [2]rotaxanes. The smallest [2]rotaxane, with only three methylene groups on each side of its dumbbell component, is found to exist under ambient conditions in a monoradical state, a situation which does not persist in acetonitrile solution, at least in the case of its longer analogues. (1)H NMR spectroscopy reveals that the activation energy barriers to the shuttling of the CBPQT(4+) rings over the BIPY(2+) units in the dumbbells increase linearly with increasing oligomethylene chain lengths across the series of [2]rotaxanes. These findings provide a new way of producing highly stabilized BIPY(•+) radical cations and open up more opportunities to use stable organic radicals as building blocks for the construction of paramagnetic materials and conductive molecular electronic devices.

Photoexpulsion of surface-grafted ruthenium complexes and subsequent release of cytotoxic cargos to cancer cells from mesoporous silica nanoparticles.

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions.

Relative unidirectional translation in an artificial molecular assembly fueled by light.

Motor molecules present in nature convert energy inputs, such as a chemical fuel or incident photons of light, into directed motion and force biochemical systems away from thermal equilibrium. The ability not only to control relative movements of components in molecules but also to drive their components preferentially in one direction relative to each other using versatile stimuli is one of the keys to future technological applications. Herein, we describe a wholly synthetic small-molecule system that, under the influence of chemical reagents, electrical potential, or visible light, undergoes unidirectional relative translational motion. Altering the redox state of a cyclobis(paraquat-p-phenylene) ring simultaneously (i) inverts the relative heights of kinetic barriers presented by the two termini--one a neutral 2-isopropylphenyl group and the other a positively charged 3,5-dimethylpyridinium unit--of a constitutionally asymmetric dumbbell, which can impair the threading/dethreading of a [2]pseudorotaxane, and (ii) controls the ring's affinity for a 1,5-dioxynaphthalene binding site located in the dumbbell's central core. The formation and subsequent dissociation of the [2]pseudorotaxane by passage of the ring over the neutral and positively charged termini of the dumbbell component in one, and only one, direction relatively defined has been demonstrated by (i) spectroscopic ((1)H NMR and UV/vis) means and cyclic voltammetry as well as with (ii) DFT calculations and by (iii) comparison with control compounds in the shape of constitutionally symmetrical [2]pseudorotaxanes, one with two positively charged ends and the other with two neutral ends. The operation of the system relies solely on reversible, yet stable, noncovalent bonding interactions. Moreover, in the presence of a photosensitizer, visible-light energy is the only fuel source that is needed to drive the unidirectional molecular translation, making it feasible to repeat the operation numerous times without the buildup of byproducts.