A chemiresistive methane sensor.

A chemiresistive sensor is described for the detection of methane (CH4), a potent greenhouse gas that also poses an explosion hazard in air. The chemiresistor allows for the low-power, low-cost, and distributed sensing of CH4 at room temperature in air with environmental implications for gas leak detection in homes, production facilities, and pipelines. Specifically, the chemiresistors are based on single-walled carbon nanotubes (SWCNTs) noncovalently functionalized with poly(4-vinylpyridine) (P4VP) that enables the incorporation of a platinum-polyoxometalate (Pt-POM) CH4 oxidation precatalyst into the sensor by P4VP coordination. The resulting SWCNT-P4VP-Pt-POM composite showed ppm-level sensitivity to CH4 and good stability to air as well as time, wherein the generation of a high-valent platinum intermediate during CH4 oxidation is proposed as the origin of the observed chemiresistive response. The chemiresistor was found to exhibit selectivity for CH4 over heavier hydrocarbons such as n-hexane, benzene, toluene, and o-xylene, as well as gases, including carbon dioxide and hydrogen. The utility of the sensor in detecting CH4 using a simple handheld multimeter was also demonstrated.

Triphenylphosphine Oxide: A Versatile Covalent Functionality for Carbon Nanotubes.

Broadening the scope of functionalities that can be covalently bound to single-walled carbon nanotubes (SWCNTs) is crucial for enhancing the versatility of this promising nanomaterial class in applied settings. Here we report the covalent linkage of triphenylphosphine oxide [Ph3P(O)] to SWCNTs, a hitherto overlooked surface functionality. We detail the synthesis and structural characterization of a new family of phosphine oxide-functionalized diaryliodonium salts that can facilitate direct Ph3P(O) transfer and afford novel SWCNTs with tunable Ph3P(O) content (SWCNT-P). The molecularly-distributed and robust nature of the covalent Ph3P(O) attachment in SWCNT-P was supported by a combination of characterization methods including Raman, infrared, UV/Vis-NIR and X-ray photoelectron spectroscopies coupled with thermogravimetric analysis. Electron microscopy further revealed the effectiveness of the Ph3P(O) moiety for de-bundling SWCNTs to yield SWCNT-P with superior dispersibility and processability. Finally, electrochemical studies established that SWCNT-P is sensitive to the presence of Li+, Na+ and K+ wherein the Gutmann-Beckett Lewis acidity parameters of the ions were quantitatively transduced by Ph3P(O) to electrochemical responses. This work hence presents a synthetic, structural, spectroscopic and electrochemical foundation for a new phosphorus-enriched responsive nanomaterial platform featuring the Ph3P(O) functionality.

Phosphine Oxide-Functionalized Terthiophene Redox Systems.

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e- reductions at potentials below -2 V vs Fc/Fc+ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e- galvanostatic charge-discharge cycling and enabled characterization of a 2 e- redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.

Wireless Lateral Flow Device for Biosensing.

Many biosensing methods rely on signals produced by enzyme-catalyzed reactions and efficient methods to detect and record this activity. Herein, we report a wireless lateral flow device and demonstrate the conversion of oxidase reactions to changes in the resonance of radio frequency identification (RFID) circuits. The detection is triggered by polyoxometalate-catalyzed oxidative doping of polypyrrole (pPy) when exposed to oxidase-generated H2O2. We have integrated this transduction and RFID capability into a lateral flow device to create a low-cost, rapid, and portable method for quantitative biological signal detection. We further report a new method for creating functional coatings from pPy core-shell colloidal particles bioconjugated for streptavidin-biotin recognition with glucose oxidase or pyruvate oxidase. The biofunctionalized pPy particles coalesce on the nitrocellulose membrane to produce a chemiresistive band. Glucose or pyruvate solutions result in formation of H2O2 at the pPy bands, functionalized with the respective oxidase, to produce conductivity enhancements exceeding 7·105%. Placing the pPy band in the RFID circuit converts the resistivity response to a change of RF resonance. The enzymatic response of glucose oxidase is recorded within 30 min with as low as 0.6 mM of glucose using this lateral flow device. Pyruvate is also shown to produce large responses. The oxidase enzymes/pPy transduction establishes a resistivity-based platform for the construction of a new family of lateral flow devices capable of detecting and quantifying biological targets.

Developing a consensus definition of psychosocial complexity in cancer patients using Delphi methods.

OBJECTIVE: Cancer is one of the biggest health challenges of our times, affecting all the personal areas of a patient. The interrelationships between these areas and the need for multidisciplinary care require the assessment of psychosocial complexity in cancer patients. The main aim of this study was to reach a consensus on the general definition of psychosocial complexity in cancer and its main elements according to the experts in the field. METHOD: A Delphi study was performed, which first involved a comprehensive review of the literature to create a questionnaire that was validated by two expert panels. The first panel consisted of intra-institutional experts, while the second included extra-institutional experts in the field. The study included three more rounds: (1) validation of the questionnaire by the internal panel, (2) discussion of the results and resolving discrepancies, and (3) validation of the questionnaire by the external panel. RESULTS: After the four-round Delphi process, we obtained a consensus definition of psychosocial complexity in cancer patients, as well as of its main factors: medical-physical, social-family, psychological, and spiritual. A 21-indicators list and its 8-indicators brief version were also proposed as indicators of psychosocial complexity. SIGNIFICANCE OF RESULTS: We present a definition of psychosocial complexity in cancer patients that has been agreed by experts, also establishing its four factors: medical-physical, social-family, psychological, and spiritual. This has led to the development of a list of indicators (and its brief version) that, after a validation process, could help health professionals to identify patients with high psychosocial complexity to provide them an optimal care.

Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters.

A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole, and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, [(η5-C5Me5)Rh(N-C)H] (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of [(η5-C5Me5)Rh(bq)H] induced C(sp2)-H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2, both of the [(η5-C5Me5)Rh(N-C)H] precursors and [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, [(η5-C5Me5)4Rh5H7], the structure of which was established by NMR spectroscopy, X-ray diffraction, and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of [(η5-C5Me5)4Rh5H7] serving as a deactivation pathway.

Ni(I)-X Complexes Bearing a Bulky α-Diimine Ligand: Synthesis, Structure, and Superior Catalytic Performance in the Hydrogen Isotope Exchange in Pharmaceuticals.

The synthesis and spectroscopic characterization of a family of Ni-X (X = Cl, Br, I, H) complexes supported by the bulky α-diimine chelate N, N'-bis(1 R,2 R,3 R,5 S)-(-)-isopinocampheyl-2,3-butanediimine (ipcADI) are described. Diimine-supported, three-coordinate nickel(I)-X complexes have been proposed as key intermediates in a host of catalytic transformations such as C-C and C-heteroatom cross-coupling and C-H functionalization but have until now remained synthetically elusive. A combination of structural, spectroscopic, electrochemical, and computational studies were used to establish the electronic structure of each monomeric [(ipcADI)NiX] (X = Cl, Br, I) complex as a nickel(I) derivative supported by a redox-neutral α-diimine chelate. The dimeric nickel hydride, [(ipcADI)Ni(µ2-H)]2, was prepared and characterized by X-ray diffraction; however, magnetic measurements and 1H NMR spectroscopy support monomer formation at ambient temperature in THF solution. This nickel hydride was used as a precatalyst for the hydrogen isotope exchange (HIE) of C-H bonds in arenes and pharmaceuticals. By virtue of the multisite reactivity and high efficiency, the new nickel precatalyst provided unprecedented high specific activities (50-99 Ci/mmol) in radiolabeling, meeting the threshold required for radioligand binding assays. Use of air-stable and readily synthesized nickel precursor, [(ipcADI)NiBr2], broad functional group tolerance, and compatibility with polar protic solvents are additional assets of the nickel-catalyzed HIE method.

Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a ß-Agostic Ethyl: Structure, Dynamics and Mechanism.

The interconversion of molybdenum ethylene and ethyl complexes by proton-coupled electron transfer (PCET) is described, an unusual transformation in organometallic chemistry. The cationic molybdenum ethylene complex [(PhTpy)(PPh2Me)2Mo(C2H4)][BArF24] ([1-C2H4]+; PhTpy = 4'-Ph-2,2',6',2″-terpyridine, ArF24 = [C6H3-3,5-(CF3)2]4) was synthesized, structurally characterized, and its electronic structure established by a combination of spectroscopic and computational methods. The overall electronic structure is best described as a molybdenum(III) complex with a metallacyclopropane and a redox neutral terpyridine ligand. Addition of the nonclassical ammine complex [(PhTpy)(PPh2Me)2Mo(NH3)][BArF24] ([1-NH3]+) to [1-C2H4]+ resulted in a net C-H bond-forming PCET reaction to yield the molybdenum ethyl [(PhTpy)(PPh2Me)2Mo(CH2CH3)][BArF24] ([1-CH2CH3]+) and amido [(PhTpy)(PPh2Me)2Mo(NH2)][BArF24] ([1-NH2]+) compounds. The reaction was reversed by addition of 2,4,6-tri tert-butylphenoxyl radical to [1-CH2CH3]+. The solid-state structure of [1-CH2CH3]+ established a ß-agostic ethyl ligand that is maintained in solution as judged by variable temperature 1H and 13C NMR experiments. A combination of variable-temperature NMR experiments and isotopic labeling studies were used to probe the dynamics of [1-CH2CH3]+ and established restricted ß-agostic -CH3 rotation at low temperature (Δ G‡ = 9.8 kcal mol-1 at -86 °C) as well as ethyl isomerization by ß-hydride elimination-olefin rotation-reinsertion (Δ H‡ = 19.3 ± 0.6 kcal mol-1; Δ S‡ = 3.4 ± 1.7 cal mol-1 K-1). The ß-(C-H) bond-dissociation free energy (BDFE) in [1-CH2CH3]+ was determined experimentally as 57 kcal mol-1 (THF) supported by a DFT-computed value of 52 kcal/mol-1 (gas phase). Comparison of p Ka and electrochemical data for the complexes [1-C2H4]+ and [1-NH3]+ in combination with a deuterium kinetic isotope effect ( kH/ kD) of 3.5(2) at 23 °C support a PCET process involving initial electron transfer followed by protonation leading to the formation of [1-CH2CH3]+ and [1-NH2]+ or a concerted pathway. The data presented herein provides a structural, thermochemical and mechanistic foundation for understanding the PCET reactivity of organometallic complexes with alkene and alkyl ligands.

Selective [1,4]-Hydrovinylation of 1,3-Dienes with Unactivated Olefins Enabled by Iron Diimine Catalysts.

The selective, intermolecular [1,4]-hydrovinylation of conjugated dienes with unactivated α-olefins catalyzed by α-diimine iron complexes is described. Value-added "skipped" diene products were obtained with exclusive [1,4]-selectivity, and the formation of branched, ( Z)-olefin products was observed with no evidence for alkene isomerization. Mechanistic studies conducted with the well-defined, single-component iron precatalyst (MesDI)Fe(COD) (MesDI = [2,4,6-Me3-C6H2-N═CMe]2); COD = 1,5-cyclooctadiene) provided insights into the origin of the high selectivity. An iron diene complex was identified as the catalyst resting state, and one such isoprene complex, (iPrDI)Fe(η4-C5H8), was isolated and characterized. A combination of single crystal X-ray diffraction, Mößbauer spectroscopy, magnetic measurements, and DFT calculations established that the complex is best described as a high-spin Fe(I) center ( SFe = 3/2) engaged in antiferromagnetic coupling to an α-diimine radical anion ( SDI = -1/2), giving rise to the observed S = 1 ground state. Deuterium-labeling experiments and kinetic analyses of the catalytic reaction provided support for a pathway involving oxidative cyclization of an alkene with the diene complex to generate an iron metallacycle. The observed selectivity can be understood in terms of competing steric interactions in the transition states for oxidative cyclization and subsequent ß-hydrogen elimination.

Ultrafast Photophysics of a Dinitrogen-Bridged Molybdenum Complex.

Among the many metal-dinitrogen complexes synthesized, the end-on bridging (µ2, η1, η1-N2) coordination mode is notoriously unreactive for nitrogen fixation. This is principally due to the large activation energy for ground-state nitrogen-element bond formation and motivates exploration of the photoexcited reactivity of this coordination mode. To provide the foundation for this concept, the photophysics of a dinitrogen-bridged molybdenum complex was explored by ultrafast electronic spectroscopies. The complex absorbs light from the UV to near-IR, and the transitions are predominantly of metal-to-ligand charge transfer (MLCT) character. Five excitation wavelengths (440, 520, 610, 730, and 1150 nm) were employed to access MLCT bands, and the dynamics were probed between 430 and 1600 nm. Despite the large energy space occupied by electronic states (ca. 1.2 eV), the dynamics were independent of the excitation wavelength. In the proposed kinetic model, photoexcitation from a Mo-N═N-Mo centered ground state populates the π*-state delocalized over two terpyridine ligands. Due to a large terpyridine-terpyridine spatial separation, electronic localization occurs within 100 fs, augmented by symmetry breaking. The subsequent interplay of internal conversion and intersystem crossing (ISC) populates the lowest 3MLCT state in 2-3 ps. Decay to the ground state occurs either directly or via a thermally activated metal-centered (3MC) trap state having two time constants (10-15 ps, 23-26 ps [298 K]; 103 ps, 612 ps [77 K]). ISC between 1MLCT and 3MLCT involves migration of energized electron density from the terpyridine π* orbitals to the Mo-N═N-Mo core. Implication of the observed dynamics for the potential N-H bond forming reactivity are discussed.

Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer.

Interconversion of the molybdenum amido [(Ph Tpy)(PPh2 Me)2 Mo(NHtBuAr)][BArF24 ] (Ph Tpy=4'-Ph-2,2',6',2"-terpyridine; tBuAr=4-tert-butyl-C6 H4 ; ArF24 =(C6 H3 -3,5-(CF3 )2 )4 ) and imido [(Ph Tpy)(PPh2 Me)2 Mo(NtBuAr)][BArF24 ] complexes has been accomplished by proton-coupled electron transfer. The 2,4,6-tri-tert-butylphenoxyl radical was used as an oxidant and the non-classical ammine complex [(Ph Tpy)(PPh2 Me)2 Mo(NH3 )][BArF24 ] as the reductant. The N-H bond dissociation free energy (BDFE) of the amido N-H bond formed and cleaved in the sequence was experimentally bracketed between 45.8 and 52.3 kcal mol-1 , in agreement with a DFT-computed value of 48 kcal mol-1 . The N-H BDFE in combination with electrochemical data eliminate proton transfer as the first step in the N-H bond-forming sequence and favor initial electron transfer or concerted pathways.

Cobalt-Catalyzed 1,1-Diboration of Terminal Alkynes: Scope, Mechanism, and Synthetic Applications.

A cobalt-catalyzed method for the 1,1-diboration of terminal alkynes with bis(pinacolato)diboron (B2Pin2) is described. The reaction proceeds efficiently at 23 °C with excellent 1,1-selectivity and broad functional group tolerance. With the unsymmetrical diboron reagent PinB-BDan (Dan = naphthalene-1,8-diaminato), stereoselective 1,1-diboration provided products with two boron substituents that exhibit differential reactivity. One example prepared by diboration of 1-octyne was crystallized, and its stereochemistry established by X-ray crystallography. The utility and versatility of the 1,1-diborylalkene products was demonstrated in a number of synthetic applications, including a concise synthesis of the epilepsy medication tiagabine. In addition, a synthesis of 1,1,1-triborylalkanes was accomplished through cobalt-catalyzed hydroboration of 1,1-diborylalkenes with HBPin. Deuterium-labeling and stoichiometric experiments support a mechanism involving selective insertion of an alkynylboronate to a Co-B bond of a cobalt boryl complex to form a vinylcobalt intermediate. The latter was isolated and characterized by NMR spectroscopy and X-ray crystallography. A competition experiment established that the reaction involves formation of free alkynylboronate and the two boryl substituents are not necessarily derived from the same diboron source.

C(sp2)-H Borylation of Fluorinated Arenes Using an Air-Stable Cobalt Precatalyst: Electronically Enhanced Site Selectivity Enables Synthetic Opportunities.

Cobalt catalysts with electronically enhanced site selectivity have been developed, as evidenced by the high ortho-to-fluorine selectivity observed in the C(sp2)-H borylation of fluorinated arenes. Both the air-sensitive cobalt(III) dihydride boryl 4-Me-(iPrPNP)Co(H)2BPin (1) and the air-stable cobalt(II) bis(pivalate) 4-Me-(iPrPNP)Co(O2CtBu)2 (2) compounds were effective and exhibited broad functional group tolerance across a wide range of fluoroarenes containing electronically diverse functional groups, regardless of the substitution pattern on the arene. The electronically enhanced ortho-to-fluorine selectivity observed with the cobalt catalysts was maintained in the presence of a benzylic dimethylamine and hydrosilanes, overriding the established directing-group effects observed with precious-metal catalysts. The synthetically useful selectivity observed with cobalt was applied to an efficient synthesis of the anti-inflammatory drug flurbiprofen.

Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand.

Treatment of the bis(imino)pyridine molybdenum η6-benzene complex (iPrPDI)Mo(η6-C6H6) (iPrPDI, 2,6-(2,6-iPr2C6H3N═CMe)2C5H3N) with NH3 resulted in coordination induced haptotropic rearrangement of the arene to form (iPrPDI)Mo(NH3)2(η2-C6H6). Analogous η2-ethylene and η2-cyclohexene complexes were also synthesized, and the latter was crystallographically characterized. All three compounds undergo loss of the η2-coordinated ligand followed by N-H bond activation, bis(imino)pyridine modification, and H2 loss. A dual ammonia activation approach has been discovered whereby reversible M-L cooperativity and coordination induced bond weakening likely contribute to dihydrogen formation. Significantly, the weakened N-H bonds in (iPrPDI)Mo(NH3)2(η2-C2H4) enabled hydrogen atom abstraction and synthesis of a terminal nitride from coordinated ammonia, a key step in NH3 oxidation.

Terpyridine Molybdenum Dinitrogen Chemistry: Synthesis of Dinitrogen Complexes That Vary by Five Oxidation States.

A bimetallic molybdenum complex bridged by an activated dinitrogen ligand and supported by phosphine and terpyridine ligands, [{((Ph)Tpy)(PPh2Me)2Mo}2(µ2-N2)][BArF(24)]2 [(Ph)Tpy = 4'-Ph-2,2',6',2″-terpyridine; ArF(24) = (C6H3-3,5-(CF3)2)4], was synthesized and structurally characterized, and its electronic structure was determined using a combination of experimental and density functional theory computational methods. Each molybdenum atom is best described as molybdenum(II) bridged by a modestly activated [N2](2-) ligand. The cyclic voltammogram of [{((Ph)Tpy)(PPh2Me)2Mo}2(µ2-N2)](2+) displays two reversible reductive and two reversible oxidative features, prompting the preparation and characterization of a series of molybdenum dinitrogen compounds spanning five oxidation states ([{((Ph)Tpy)(PPh2Me)2Mo}2(µ2-N2)][BArF(24)]n, where n = 4, 3, 2, 1, 0). Raman and (15)N NMR spectroscopic data establish that the bridging nitrogen ligand remains intact across the redox series. Electron paramagnetic resonance spectroscopy was used to probe the nature of the unpaired electron in the mixed-valent electronic oxidized and reduced products. The singly occupied molecular orbital is principally metal-based in [{((Ph)Tpy)(PPh2Me)2Mo}2(µ2-N2)](3+) and ligand-localized in [{((Ph)Tpy)(PPh2Me)2Mo}2(µ2-N2)](+).

Expanding Boundaries: N2 Cleavage and Functionalization beyond Early Transition Metals.

Early transition metals are well known to catalyze the cleavage and functionalization of N2 . In this Highlight, recent work showing that a rhenium catalyst is also capable of carrying out this difficult task is summarized, and a synthetic cycle for the stoichiometric incorporation of atmospheric N2 into acetonitrile is presented.

A Dye-Sensitized Sensor for Oxygen Detection under Visible Light.

Sensors that can accurately assess oxygen (O2) concentrations in real time are crucial for a wide range of applications spanning personal health monitoring, environmental protection, and industrial process development. Here a high-performance chemiresistive sensor that allows for the rapid detection of O2 at room temperature under visible light illumination is described. Inspired by the operating principles of dye-sensitized solar cells, the chemiresistor is based on a single-walled carbon nanotube-titania hybrid (SWCNT-TiO2) bearing a molecular Re-based photosensitizer [(Pbpy)(CO)3ReBr] (Pbpy = 4,4'-[P(O)(OH)2]2-2,2'-bipyridine). The resulting SWCNT-TiO2-Re composite undergoes photoinduced charge transfer that is sensitive to ppb levels of O2, thereby yielding a rapid and reversible chemiresistive response. Owing to its unique mode of operation and robust components, the sensor shows a high degree of selectivity for O2 over a range of interferants, humidity tolerance, and multimonth benchtop stability. The approach presented herein demonstrates the translatability of concepts in light harvesting to the development of robust, rapid, and low-power sensing technologies.

Safety of thiopurines and anti-TNF-α drugs during pregnancy in patients with inflammatory bowel disease.

OBJECTIVES: The safety of thiopurines and anti-tumor necrosis factor-α (TNF-α) drugs during pregnancy remains controversial, as the experience with these drugs in this situation is limited. Our aim is to assess the safety of thiopurines and anti-TNF-α drugs for the treatment of inflammatory bowel disease (IBD) during pregnancy. METHODS: Retrospective, multicenter study in IBD patients. Pregnancies were classified according to the therapeutic regimens during pregnancy or during the 3 months before the conception: non-exposed group, pregnancies exposed to thiopurines alone (group A), and pregnancies exposed to anti-TNF-α drugs (group B). An unfavorable Global Pregnancy Outcome (GPO) was considered if pregnancy developed with obstetric complications in the mother and in the newborn. RESULTS: A total of 187 pregnancies in the group A, 66 pregnancies in the group B, and 318 pregnancies in the non-exposed group were included. The rate of unfavorable GPO was different among the three groups (31.8% in non-exposed group, 21.9% in group A, and 34.8% in group B), being lower in pregnancies under thiopurines than among non-exposed (P = 0.01). The rate of pregnancy complications was similar among the three groups (27.7% in non-exposed, 20.9% in group A, and 30.3% in group B). The rate of neonatal complications was different among the three groups (23.3% in non-exposed group, 13.9% in group A, and 21.2% in group B), being lower in pregnancies under thiopurines than among non-exposed (P = 0.01). In the multivariate analysis, the treatment with thiopurines (odds ratio = 0.6; 95% confidence interval = 0.4-0.9, P = 0.02) was the only predictor of favorable GPO, whereas maternal age >35 years at conception was the only predictor of unfavorable GPO. The treatment with anti-TNF-α drugs was not associated with an unfavorable GPO. CONCLUSION: The treatment with thiopurines and anti-TNF-α drugs does not seem to increase the risk of complications during pregnancy and does seem to be safe for the newborn.

Ruthenium(II) complexes bearing a naphthalimide fragment: a modular dye platform for the dye-sensitized solar cell.

Cycloruthenated complexes of the type [Ru(II)(N^N)2(C^N)](+) (N^N = substituted 2,2'-bipyridine; C^N = substituted 3-(2'-pyridyl)-1,8-naphthalimide ligand) are shown to generate high power conversion efficiencies (PCEs) in the dye-sensitized solar cell (DSSC). It is shown that substitution of the pyridine ring of the C^N ligand with conjugated groups can enhance molar absorption extinction coefficients, while the electron density imparted on the metal center is alleviated by the 1,8-naphthalimide fragment. This latter feature maintains a Ru(III)/Ru(II) redox couple more positive than 0.8 V versus NHE, thereby accommodating regeneration of the oxidized dye by an iodide-based redox mediator. This dye platform can consequently be modulated at various sites to enhance light absorption and suppress recombination between the redox mediator and the TiO2 surface without compromising dye regeneration, thereby maintaining device PCEs as high as 7%. We also introduce a new phosphine-based coadsorbent, bis(2-ethylhexyl)phosphinic acid (BEPA), which is significantly easier to synthesize than the widely used bis(3,3-dimethylbutyl)phosphinic acid (DINHOP) while also facilitating high dye loading.