UV emitting glass: A promising strategy for biofilm inhibition on transparent surfaces.

Marine biofouling causes serious environmental problems and has adverse impacts on the maritime industry. Biofouling on windows and optical equipment reduces surface transparency, limiting their application for on-site monitoring or continuous measurement. This work illustrates that UV emitting glasses (UEGs) can prevent the establishment and growth of biofilm on the illuminated surfaces. Specifically, this paper describes how UEGs are enabled by innovatively modifying the surfaces of the glass with light scattering particles. Modification of glass surface with silica nanoparticles at a concentration 26.5 µg/cm2 resulted in over ten-fold increase in UV irradiance, while maintaining satisfactory visible and IR transparency metrics of over 99 %. The UEG reduced visible biological growth by 98 % and resulted in a decrease of 1.79 log in detected colony forming units when compared to the control during a 20 day submersion at Port Canaveral, Florida, United States. These findings serve as strong evidence that UV emitting glass should be explored as a promising approach for biofilm inhibition on transparent surfaces.

Manipulation of the Thermochromic Transition Temperature in a Classic Metal-Organic Complex by Selective Anion Doping.

The origin of thermochromism displayed by the hybrid material [Ni(dieten)2](BF4)2 (dieten = N,N-diethylethylenediamine) is explored by anion substitution of the tetrafluoroborate anions (BF4-) with varying percentages (0-25%) of bromide (Br-). Differential scanning calorimetry and variable-temperature diffuse reflectance spectroscopy indicate that the yellow-orange to orange-red thermochromic transition inherent to undoped [Ni(dieten)2](BF4)2 shifts from 100 to 90 °C as the doping concentration increases from 0 to 25%. Similarly, a 15 nm line broadening of the Kubelka-Munk transformed diffuse reflectance signal (proportional to the absorbance of the complex) and a broadening of the endothermic transition are observed with increasing Br- doping. The structure of the undoped [Ni(dieten)2](BF4)2, determined by single-crystal X-ray diffraction, is presented, and powder X-ray diffraction was used to confirm that the crystal structure and crystallinity of each doped sample remains unchanged from the BF4- phase. We provide evidence for an underlying mechanism of thermochromism that is linked to hydrogen bonding within the crystal structure and which can be manipulated via targeted modulation of lattice anions. The mechanism proposed here is likely applicable to other materials within the family of dieten complexes ([M(dieten)2](X)2, where M = Ni2+, Cu2+ and X = BF4-, ClO4-, NO3-).

Surface- and Structural-Dependent Reactivity of Titanium Oxide Nanostructures with 2-Chloroethyl Ethyl Sulfide under Ambient Conditions.

Robust materials capable of heterogeneous reactivity are valuable for addressing toxic chemical clean up. Synthetic manipulations for generating titanium oxide nanomaterials have been utilized to alter both photochemical (1000 nm > λ > 400 nm) and chemical heterogeneous reactivity with 2-chloroethyl ethyl sulfide (2-CEES). Synthesizing TiO2 nanomaterials in the presence of long-chain alkylphosphonic acids enhanced the visible light-driven oxidation of the thioether sulfur of 2-CEES. Photooxidation reaction rates of 99 and 168 µmol/g/h (quantum yields of 5.07 × 10-4 and 8.58 × 10-4 molecules/photon, respectively) were observed for samples made with two different alkylphosphonic acids (C14H29PO3H2 and C9H19PO3H2, respectively). These observations are correlated with (i) generation of new surface defects/states (i.e., oxygen vacancies) as a result of TiO2 grafting by alkylphosphonic acid that may serve as reaction active sites, (ii) better light absorption by assemblies of nanorods and nanowires in comparison to individual nanorods, (iii) surface area differences, and (iv) the exclusion of OH groups due to the surface functionalization with alkylphosphonic acids via Ti-O-P bonds on the TiO2. Alternatively, nanowire-form H2Ti2O5·H2O was produced and found to be capable of highly efficient hydrolysis of the carbon-chlorine (C-Cl) bond of 2-CEES in the dark with a reaction rate of 279.2 µmol/g/h due to the high surface area and chemical nature of the titanate structure.

Nanosecond transient absorption studies of the pH-dependent hydrated electron quenching by HSO3.

The large standard reduction potential of an aqueous solvated electron (eaq-, E° = -2.9 V) makes it an attractive candidate for reductive treatment of wastewater contaminants. Using transient absorption spectroscopy, the nanosecond to microsecond dynamics of eaq- generated from 10 mM solutions of Na2SO3 at pH 4 to 11 in H2O and D2O are characterized, resulting in the determination that between pH 4 and 9 it is the HSO3-, and not H+ as previously postulated by others, that effectively quenches eaq-. The observed bimolecular quenching rate constant (k = 1.2 × 108 M-1 s-1) for eaq- deactivation by HSO3- is found to be consistent with a Brønsted acid catalysis mechanism resulting in formation of H˙ and SO32-. A large solvent isotope effect is observed from the lifetimes of the eaq- in H2O compared to D2O (kH2O/kD2O = 4.4). In addition, the bimolecular rate constant for eaq- deactivation by DSO3- (k = 2.7 × 107 M-1 s-1) is found to be an order of magnitude lower than by HSO3-. These results highlight the role of acids, such as HSO3-, in competition with organic contaminant targets for eaq- and, by extension, that knowledge of the pKa of eaq- sources can be a predictive measure of the effective pH range for the treatment of wastewater contaminants.

Proton-Coupled Electron Transport in Anthraquinone-Based Zirconium Metal-Organic Frameworks.

The ditopic ligands 2,6-dicarboxy-9,10-anthraquinone and 1,4-dicarboxy-9,10-anthraquinone were used to synthesize two new UiO-type metal-organic frameworks (MOFs; namely, 2,6-Zr-AQ-MOF and 1,4-Zr-AQ-MOF, respectively). The Pourbaix diagrams (E vs pH) of the MOFs and their ligands were constructed using cyclic voltammetry in aqueous buffered media. The MOFs exhibit chemical stability and undergo diverse electrochemical processes, where the number of electrons and protons transferred was tailored in a Nernstian manner by the pH of the media. Both the 2,6-Zr-AQ-MOF and its ligand reveal a similar electrochemical pKa value (7.56 and 7.35, respectively) for the transition between a two-electron, two-proton transfer (at pH < pKa) and a two-electron, one-proton transfer (at pH > pKa). In contrast, the position of the quinone moiety with respect to the zirconium node, the effect of hydrogen bonding, and the amount of defects in 1,4-Zr-AQ-MOF lead to the transition from a two-electron, three-proton transfer to a two-electron, one-proton transfer. The pKa of this framework (5.18) is analogous to one of the three electrochemical pKa values displayed by its ligand (3.91, 5.46, and 8.80), which also showed intramolecular hydrogen bonding. The ability of the MOFs to tailor discrete numbers of protons and electrons suggests their application as charge carriers in electronic devices.

Study of Electrocatalytic Properties of Metal-Organic Framework PCN-223 for the Oxygen Reduction Reaction.

A highly robust metal-organic framework (MOF) constructed from Zr6 oxo clusters and Fe(III) porphyrin linkers, PCN-223-Fe was investigated as a heterogeneous catalyst for oxygen reduction reaction (ORR). Films of the framework were grown on a conductive FTO substrate and showed a high catalytic current upon application of cathodic potentials and achieved high H2O/H2O2 selectivity. In addition, the effect of the proton source on the catalytic performance was also investigated.

Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film.

Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal-organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2 ]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH∼7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.

Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex.

A method is described here by which to dope ruthenium(II) bis(2,2'-bipyridine) (2,2'-bipyridyl-5,5'-dicarboxylic acid), RuDCBPY, into a UiO-67 metal-organic framework (MOF) derivative in which 2,2'-bipyridyl-5,5'-dicarboxylic acid, UiO-67-DCBPY, is used in place of 4,4'-biphenyldicarboxylic acid. Emission lifetime measurements of the RuDCBPY triplet metal-to-ligand charge transfer, (3)MLCT, excited state as a function of RuDCBPY doping concentration in UiO-67-DCBPY are discussed in light of previous results for RuDCBPY-UiO-67 doped powders in which quenching of the (3)MLCT was said to be due to dipole-dipole homogeneous resonance energy transfer, RET. The bulk distribution of RuDCBPY centers within MOF crystallites are also estimated with the use of confocal fluorescence microscopy. In the present case, it is assumed that the rate of RET between RuDCBPY centers has an r(-6) separation distance dependence characteristic of Förster RET. The results suggest (1) the dimensionality in which RET occurs is dependent on the RuDCBPY concentration ranging from one-dimensional at very low concentrations up to three-dimensional at high concentration, (2) the occupancy of RuDCBPY within UiO-67-DCBPY is not uniform throughout the crystallites such that RuDCBPY densely populates the outer layers of the MOF at low concentrations, and (3) the average separation distance between RuDCBPY centers is ∼21 Å.

Spectroscopic investigation of the noncovalent association of the nerve agent simulant diisopropyl methylphosphonate (DIMP) with zinc(II) porphyrins.

Organophosphonates pose a significant threat as chemical warfare agents, as well as environmental toxins in the form of pesticides. Thus, methodologies to sense and decontaminate these agents are of significant interest. Porphyrins and metalloporphyrins offer an excellent platform to develop chemical threat sensors and photochemical degradation systems. These highly conjugated planar molecules exhibit relatively long-lived singlet and triplet states with high quantum yields and also form self-associated complexes with a wide variety of molecules. A significant aspect of porphyrins is the ability to functionalize the peripheral ring system either directly to the pyrrole rings or to the bridging methine carbons. In this report, steady-state absorption and fluorescence are utilized to probe binding affinities of a series of symmetric and asymmetric zinc(II) metalloporphyrins for the nerve agent simulant diisopropyl methylphosphonate (DIMP) in hexane. The red shifts in the absorption and emission spectra observed for all of the metalloporphyrins probed are discussed in the frame of Gouterman's four orbital model and a common binding motif involving coordination between the metalloporphyrin and DIMP via interaction between the zinc metal center of the porphyrin and phosphoryl oxygen of DIMP (Zn-O═P) is proposed.

Fluorescent properties and resonance energy transfer of 3,4-bis(2,4-difluorophenyl)-maleimide.

A fluorescent compound 3,4-bis(2,4-difluorophenyl)-maleimide from the 3,4-diaryl-substituted maleimides was synthesized and determined to have a Stokes shift of 140 nm (λ(abs) 341 nm, λ(em) 481 nm), a high fluorescent quantum yield (Φ(fl) 0.61) and an extinction coefficient ε((340)) of 48 400 M(-1) cm(-1) in dichloromethane. For the first time we demonstrated the successful implementation of a 3,4-diaryl-substituted maleimide molecule as a donor component in FRET experiments.

Understanding ion sensing in Zn(II) porphyrins: spectroscopic and computational studies of nitrite/nitrate binding.

The development of effective sensor elements relies on the ability of a chromophore to bind an analyte selectively and then study the binding through changes in spectroscopic signals. In this report the ability of Zn(II) Tetraphenyl Porphyrin (ZnTPP) to selectively bind nitrite over nitrate ions is examined. The results of Benesi-Hildebrand analysis reveals that ZnTPP binds NO(2)(-) and NO(3)(-) ions with association constants of 739 ± 70 M(-1) and 134 ± 15 M(-1), respectively. Interestingly, addition of a pyridine ligand to the fifth coordination site of the Zn(II) center enhances ion binding with the association constants increasing to 71,300 ± 8,000 M(-1) and 18,900 ± 3,000 M(-1) for nitrite and nitrate, respectively. Density functional theory calculations suggest a binding mechanism through which Zn(II)-porphyrin interactions are disrupted by ligand and base coordination to Zn(II), with Zn(II) having more favorable overlap with nitrite orbitals, which are less delocalized than nitrate orbitals. Overall, these provide new insights into the ability to tune the affinity and selectivity of porphyrin based sensors utilizing electronic factors associated with the central Zn(II) ion.