Isonitriles as Alkyl Radical Precursors in Visible Light Mediated Hydro- and Deuterodeamination Reactions.

Herein, we report the use of isonitriles as alkyl radical precursors in light-mediated hydro- and deuterodeamination reactions. The reaction is scalable, shows broad functional group compatibility and potential to be used in late-stage functionalization. Importantly, the method is general for Cα -primary, Cα -secondary and Cα -tertiary alkyl isonitriles. For most examples, high yields were obtained through direct visible-light irradiation of the isonitrile in the presence of a silyl radical precursor. Interestingly, in the presence of an organic photocatalyst (4CzIPN) a dramatic acceleration was observed. In-depth mechanistic studies using UV/Vis absorption, steady-state and time-resolved photoluminescence, and transient absorption spectroscopy suggest that the excited state of 4CzIPN can engage in a single-electron transfer with the isonitrile.

One-Metal/Two-Ligand for Dual Activation Tandem Catalysis: Photoinduced Cu-Catalyzed Anti-hydroboration of Alkynes.

A dual catalyst system based on ligand exchange of two diphosphine ligands possessing different properties in a copper complex has been devised to merge metal- and photocatalytic activation modes. This strategy has been applied to the formal anti-hydroboration of activated internal alkynes via a tandem sequence in which Cu/Xantphos catalyzes the B2pin2-syn-hydroboration of the alkyne whereas Cu/BINAP serves as a photocatalyst for visible light-mediated isomerization of the resulting alkenyl boronic ester. Photochemical studies by means of UV-vis absorption, steady-state and time-resolved fluorescence, and transient absorption spectroscopy have allowed characterizing the photoactive Cu/BINAP species in the isomerization reaction and its interaction with the intermediate syn-alkenyl boronic ester through energy transfer from the triplet excited state of the copper catalyst. In addition, mechanistic studies shed light into catalyst speciation and the interplay between the two catalytic cycles as critical success factors.

Topology and Excited State Multiplicity as Controlling Factors in the Carbazole-Photosensitized CPD Formation and Repair.

Photosensitized thymine<>thymine (Thy<>Thy) formation and repair can be mediated by carbazole (Cbz). The former occurs from the Cbz triplet excited state via energy transfer, while the latter takes place from the singlet excited state via electron transfer. Here, fundamental insight is provided into the role of the topology and excited state multiplicity, as factors governing the balance between both processes. This has been achieved upon designing and synthesizing different isomers of trifunctional systems containing one Cbz and two Thy units covalently linked to the rigid skeleton of the natural deoxycholic acid. The results shown here prove that the Cbz photosensitized dimerization is not counterbalanced by repair when the latter, instead of operating through-space, has to proceed through-bond.

Fundamental Insights into Photoelectrocatalytic Hydrogen Production with a Hole-Transport Bismuth Metal-Organic Framework.

Solar fuels production is a cornerstone in the development of emerging sustainable energy conversion and storage technologies. Light-induced H2 production from water represents one of the most crucial challenges to produce renewable fuel. Metal-organic frameworks (MOFs) are being investigated in this process, due to the ability to assemble new structures with the use of suitable photoactive building blocks. However, the identification of the reaction intermediates remains elusive, having negative impacts in the design of more efficient materials. Here, we report the synthesis and characterization of a new MOF prepared with the use of bismuth and dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acid (DTTDC), an electron-rich linker with hole transport ability. By combining theoretical studies and time-resolved spectroscopies, such as core hole clock and laser flash photolysis measurements, we have completed a comprehensive study at different time scales (fs to ms) to determine the effect of competitive reactions on the overall H2 production. We detect the formation of an intermediate radical anion upon reaction of photogenerated holes with an electron donor, which plays a key role in the photoelectrocatalytic processes. These results shed new light on the use of MOFs for solar fuel production.

Generation of the Thymine Triplet State by Through-Bond Energy Transfer.

Benzophenone (BP) and drugs containing the BP chromophore, such as the non-steroidal anti-inflammatory drug ketoprofen, have been widely reported as DNA photosensitizers through triplet-triplet energy transfer (TTET). In the present work, a direct spectroscopic fingerprint for the formation of the thymine triplet (3 Thy*) by through-bond (TB) TTET from 3 BP* has been uncovered. This has been achieved in two new systems that have been designed and synthesized with one BP and one thymine (Thy) covalently linked to the two ends of the rigid skeleton of the natural bile acids cholic and lithocholic acid. The results shown here prove that it is possible to achieve triplet energy transfer to a Thy unit even when the photosensitizer is at a long (nonbonding) distance.

"Snorkelling" vs. "diving" in mixed micelles probed by means of a molecular bathymeter.

A photoactive bathymeter based on a carboxylic acid moiety covalently linked to a signalling methoxynaphthalene (MNP) fluorophore has been designed to prove the concept of "snorkelling" vs. "diving" in mixed micelles (MM). The carboxylic acid "floats" on the MM surface, while the MNP unit sinks deep in MM. The rate constants of MNP fluorescence quenching by iodide, which remains basically in water, consistently decrease with increasing spacer length, revealing different regions. This is associated with the distance MNP should "dive" in MM to achieve protection from aqueous reactants. Unequivocal proof of the exergonic photoinduced electron transfer was obtained from the UV-visible spectral signature of I3- upon steady-state photolysis. The applicability of the bathymeter was examined upon testing a family of MNP derivatives. The obtained results were validated by comparison with different lipophilicity tests: (i) a modified version of the Kow partition coefficient and (ii) the retention factor on thin layer chromatography. This concept could potentially be extended to test drugs or pharmacophores exhibiting any photoactive moiety.

Photoactive bile salts with critical micellar concentration in the micromolar range.

The aggregation behavior of bile salts is strongly dependent on the number of hydroxyl groups. Thus, cholic acid (CA), with three hydroxyls, starts forming aggregates at 15 mM, while deoxycholic, chenodeoxycholic or ursodeoxycholic acids, with two hydroxyls, start aggregating at 5-10 mM; for lithocholic acid, with only one hydroxyl group, aggregation is observed at lower concentration (2-3 mM). Here, the singular self-assembling properties of dansyl and naproxen derivatives of CA (3ß-Dns-CA and 3ß-NPX-CA, respectively) have been demonstrated on the basis of their photoactive properties. Thus, the emission spectra of 3ß-Dns-CA registered at increasing concentrations (25-140 µM) showed a remarkable non-linear enhancement in the emission intensity accompanied by a hypsochromic shift of the maximum and up to a three-fold increase in the singlet lifetime. The inflection point at around 50-70 µM pointed to the formation of unprecedented assemblies at such low concentrations. In the case of 3ß-NPX-CA, when the NPX relative triplet lifetime was plotted against concentration, a marked increase (up to two-fold) was observed at 40-70 µM, indicating the formation of new 3ß-NPX-CA assemblies at ca. 50 µM. Additional evidence supporting the formation of new 3ß-Dns-CA or 3ß-NPX-CA assemblies at 40-70 µM was obtained from singlet excited state quenching experiments using iodide. Moreover, to address the potential formation of hybrid assemblies, 1 : 1 mixtures of 3ß-Dns-CA and 3ß-NPX-CA (2-60 µM, total concentration) were subjected to steady-state fluorescence experiments, and their behavior was compared to that of the pure photoactive derivatives. A lower increase in the emission was observed for 3ß-NPX-CA in the mixture, while a huge increase was experienced by 3ß-Dns-CA in the same concentration range (up to 60 µM total). A partial intermolecular energy transfer from NPX to Dns, consistent with their reported singlet energies, was revealed, pointing to the formation of extremely fluorescent hybrid assemblies at 5-10 µM (total concentration). The morphology of the entities was investigated by means of confocal microscopy. At 90 µM, 3ß-Dns-CA showed disperse assemblies in the µm range.

Correction to "Iterative Dual-Metal and Energy Transfer Catalysis Enables Stereodivergence in Alkyne Difunctionalization: Carboboration as Case Study".

[This corrects the article DOI: 10.1021/acscatal.3c03570.].

An anthraquinone-based bismuth-iron metal-organic framework as an efficient photoanode in photoelectrochemical cells.

Metal-organic frameworks (MOFs) are appealing candidate materials to design new photoelectrodes for use in solar energy conversion because of their modular nature and chemical versatility. However, to date there are few examples of MOFs that can be directly used as photoelectrodes, for which they must be able to afford charge separation upon light absorption, and promote the catalytic dissociation of water molecules, while maintaining structural integrity. Here, we have explored the use of the organic linker anthraquinone-2, 6-disulfonate (2, 6-AQDS) for the preparation of MOFs to be used as photoanodes. Thus, the reaction of 2, 6-AQDS with Bi(iii) or a combination of Bi(iii) and Fe(iii) resulted in two new MOFs, BiPF-10 and BiFePF-15, respectively. They display similar structural features, where the metal elements are disposed in inorganic-layer building units, which are pillared by the organic linkers by coordination bonds through the sulfonic acid groups. We show that the introduction of iron in the structure plays a crucial role for the practical use of the MOFs as a robust photoelectrode in a photoelectrochemical cell, producing as much as 1.23 mmol H2 cm-2 with the use of BiFePF-15 as photoanode. By means of time-resolved and electrochemical impedance spectroscopic studies we have been able to unravel the charge transfer mechanism, which involves the formation of a radical intermediate species, exhibiting a longer-lived lifetime by the presence of the iron-oxo clusters in BiFePF-15 to reduce the charge transfer resistance.

Light-Driven Nitrogen Fixation to Ammonia over Aqueous-Dispersed Mo-Doped TiO2 Colloidal Nanocrystals.

Photocatalytic nitrogen fixation to ammonia and nitrates holds great promise as a sustainable route powered by solar energy and fed with renewable energy resources (N2 and H2O). This technology is currently under deep investigation to overcome the limited efficiency of the process. The rational design of efficient and robust photocatalysts is crucial to boost the photocatalytic performance. Widely used bulk materials generally suffer from charge recombination due to poor interfacial charge transfer and difficult surface diffusion. To overcome this limitation, this work explores the use of aqueous-dispersed colloidal semiconductor nanocrystals (NCs) with precise morphological control, better carrier mobility, and stronger redox ability. Here, the TiO2 framework has been modified via aliovalent molybdenum doping, and resulting Mo-TiO2 NCs have been functionalized with charged terminating hydroxyl groups (OH-) for the simultaneous production of ammonia, nitrites, and nitrates via photocatalytic nitrogen reduction in water, which has not been previously found in the literature. Our results demonstrate the positive effect of Mo-doping and nanostructuration on the overall N2 fixation performance. Ammonia production rates are found to be dependent on the Mo-doping loading. 5Mo-TiO2 delivers the highest NH4+ yield rate (ca. 105.3 µmol g-1 L-1 h-1) with an outstanding 90% selectivity, which is almost four times higher than that obtained over bare TiO2. The wide range of advance characterization techniques used in this work reveals that Mo-doping enhances charge-transfer processes and carriers lifetime as a consequence of the creation of new intra band gap states in Mo-doped TiO2 NCs.

Iterative Dual-Metal and Energy Transfer Catalysis Enables Stereodivergence in Alkyne Difunctionalization: Carboboration as Case Study.

Stereochemically defined tetrasubstituted olefins are widespread structural elements of organic molecules and key intermediates in organic synthesis. However, flexible methods enabling stereodivergent access to E and Z isomers of fully substituted alkenes from a common precursor represent a significant challenge and are actively sought after in catalysis, especially those amenable to complex multifunctional molecules. Herein, we demonstrate that iterative dual-metal and energy transfer catalysis constitutes a unique platform for achieving stereodivergence in the difunctionalization of internal alkynes. The utility of this approach is showcased by the stereodivergent synthesis of both stereoisomers of tetrasubstituted ß-boryl acrylates from internal alkynoates with excellent stereocontrol via sequential carboboration and photoisomerization. The reluctance of electron-deficient internal alkynes to undergo catalytic carboboration has been overcome through cooperative Cu/Pd-catalysis, whereas an Ir complex was identified as a versatile sensitizer that is able to photoisomerize the resulting sterically crowded alkenes. Mechanistic studies by means of quantum-chemical calculations, quenching experiments, and transient absorption spectroscopy have been applied to unveil the mechanism of both steps.

Degradation of Benzotriazole UV-stabilizers in the presence of organic photosensitizers and visible light: A time-resolved mechanistic study.

Benzotriazole UV-stabilizers (BUVSs) are commonly used in industry as solar filters, due to their strong UV light absorption. Because of their extended usage, environmental contamination of waters due to BUVSs constitutes a growing concern. Direct photodegradation of BUVSs is not efficient due to their intrinsic thermal pathways to release the absorbed light. Nevertheless, their abatement in natural environments could be assisted by chromophoric dissolved organic matter. Among the BUVSs, three representative candidates were selected, UV-326, UV-327 and UV-328, to demonstrate the potential of Riboflavin (RF) as a natural visible-light absorbing photocatalyst for the abatement of these recalcitrant pollutants under reductive conditions. The use of visible light and DABCO, as a model sacrificial electron donor, generates the radical anion RFTA.-. This key species reacts with the solar filters, achieving their reductive abatement from the medium. Moreover, the participation of every potential reactive species has been investigated by photophysical techniques, together with determination of the quenching rate constant for every reaction pathway. Consequently, evidence supported the main role of the reductive photodegradation pathway, being RFTA.- the key species in the abatement of BUVSs.

Laser-Reduced BiVO4 for Enhanced Photoelectrochemical Water Splitting.

The present study proposes a laser irradiation method to superficially reduce BiVO4 photoelectrodes and boost their water oxidation reaction performance. The origin of this enhanced performance toward oxygen evolution reaction (OER) was studied using a combination of a suite of structural, chemical, and mechanistic advanced characterization techniques including X-ray photoelectron (XPS), X-ray absorption spectroscopy (XAS), electrochemical impedance spectroscopy (EIS), and transient absorption spectroscopy (TAS), among others. We found that the reduction of the material is localized at the surface of the sample and that this effect creates effective n-type doping and a shift to more favorable energy band positions toward water oxidation. This thermodynamic effect, together with the change in sample morphology to larger and denser domains, results in an extended lifetime of the photogenerated carriers and improved charge extraction. In addition, the stability of the reduced sample in water was also confirmed. All of these effects result in a two-fold increase in the photocurrent density of the laser-treated samples.

Controlled Synthesis of Up-Conversion NaYF4:Yb,Tm Nanoparticles for Drug Release under Near IR-Light Therapy.

Up-Conversion materials have received great attention in drug delivery applications in recent years. A specifically emerging field includes the development of strategies focusing on photon processes that promote the development of novel platforms for the efficient transport and the controlled release of drug molecules in the harsh microenvironment. Here, modified reaction time, thermal treatment, and pH conditions were controlled in the synthesis of NaYF4:Yb,Tm up-converted (UC) material to improve its photoluminescence properties. The best blue-emission performance was achieved for the UC3 sample prepared through 24 h-synthesis without thermal treatment at a pH of 5, which promotes the presence of the ß-phase and smaller particle size. NaYF4:Yb,Tm has resulted in a highly efficient blue emitter material for light-driven drug release under near-IR wavelength. Thus, NaYF4:Yb,Tm up-converted material promotes the N-O bond cleavage of the oxime ester of Ciprofloxacin (prodrug) as a highly efficient photosensitized drug delivery process. HPLC chromatography and transient absorption spectroscopy measurements were performed to evaluate the drug release conversion rate. UC3 has resulted in a very stable and easily recovered material that can be used in several reaction cycles. This straightforward methodology can be extended to other drugs containing photoactive chromophores and is present as an alternative for drug release systems.

Direct Oxidative Damage of Naked DNA Generated upon Absorption of UV Radiation by Nucleobases.

It has been shown that in addition to formation of pyrimidine dimers, UV irradiation of DNA in the absence of photosensitizer also induces formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine, but the mechanism of formation of that oxidized base has not been clearly established. In the present study, we provide an unambiguous demonstration that absorption of UVC and UVB radiation by the nucleobases induces DNA oxidation via a direct process (one-electron oxidation) and not singlet oxygen. Evidence arose from the fact that polyamine-guanine adducts that are specifically produced through the transient formation of guanine radical cation are generated following UV irradiation of DNA in the presence of a polyamine even in the absence of any photosensitizer.

New photoactive compounds to probe cholic acid and cholesterol inside mixed micelles.

New photoactive dyads have been synthesized by derivatization of cholic acid (CA) or cholesterol (Ch). These compounds have proven to be efficient tools to monitor incorporation of CA and Ch to mixed micelles (MM) and to probe the microenvironment experienced inside these entities. The outstanding capability of MM to solubilize Ch has been demonstrated.

Influence of drug encapsulation within mixed micelles on the excited state dynamics and accessibility to ionic quenchers.

Photophysical techniques, specifically time-resolved fluorescence and laser flash photolysis, have proven to be noninvasive, straightforward, and valuable tools to demonstrate how drug encapsulation into biomimetic mixed micelles (MM) influences the dynamics of excited states and their accessibility to ionic quenchers. This concept has been illustrated by choosing a set of currently administered drugs containing a common naphthalene chromophore, namely, (S)-naproxen and its methyl ester, (R)-cinacalcet and (S)-propranolol. A remarkable increase of their triplet lifetimes is noticed when experiments are performed in MM, indicating efficient entrapment of the drugs in these supramolecular entities. Furthermore, a decrease of 1 order of magnitude in the quenching rate constant of the singlet and triplet excited states (by iodide or nitrite, respectively) is observed upon encapsulation into MM. This approach can in principle be extended to other microenvironments capable of incorporating photoactive compounds.

Dansyl-labeled cholic acid as a tool to build speciation diagrams for the aggregation of bile acids.

Bile acids (BAs) are a family of natural steroids biosynthesized from cholesterol in the liver that tend to form aggregates in solution. A fluorescent derivative of cholic acid, namely 3α-Dns-ChA, was employed as a reporter to establish the speciation diagrams of the most abundant BAs that can be found mainly in three microenvironments, solution, and primary and secondary aggregates. The developed methodology is based on the analysis of the combined steady-state and time-resolved experiments performed on 3α-Dns-ChA whose emission behavior was found to be strongly medium dependent. In particular, speciation diagrams of sodium glycocholate (NaGCh), sodium taurocholate (NaTCh), sodium chenodeoxycholate (NaCDCh), sodium glycochenodeoxycholate (NaGCDCh), sodium deoxycholate (NaDCh), and sodium ursodeoxycholate (NaUDCh) were successfully built up.

Photophysical probes to assess the potential of cholic acid aggregates as drug carriers.

The two enantiomers of the nonsteroidal antiinflammatory drug naproxen and of its methyl ester have been selected as representative probes with markedly different hydrophobicity to assess the potential of cholic acid aggregates as drug carriers by means of photophysical techniques. The different distribution of the probes between bulk solution and aggregates has been assessed by quenching of their singlet and triplet excited states by iodide and nitrite anions, respectively. This straightforward photophysical methodology can, in principle, be extended to a variety of drugs containing a photoactive chromophore.

La infancia contemporánea / Contemporary childhood

Exponemos el resultado analítico de una consulta de un “corpus” documental representativo en la investigación social sobre el estado actual de los estudios sobre la infancia. Los criterios para elaborar el análisis y exposición de los resultados son: la variedad de concepciones sociales; el origen histórico y la perspectiva sociológica; la experiencia social de la infancia; las imágenes o representaciones que la sociedad tiene de ella; los desarrollos conflictivos de los derechos de la infancia en términos de educación y castigo jurídico; y el porvenir de la infancia moderna como sujeto de medios de comunicación. Historiadores e historiadoras, antropólogos y antropólogas, pedagogos y pedagogas, juristas y sociólogos y sociólogas, analizan los diversos sistemas de representación de la infancia constituidos en el tiempo y en el espacio.

We present the analytical results of the consultation of a representative documentary "corpus" from the social research about the current status of the studies on childhood. The criteria to undertake the analysis and presentation of the results are: variety of social conceptions; historical origin and sociological perspective; the social experience of childhood; images or representations that society has thereof; the conflicting developments of children's rights in terms of education and legal punishment; and the future of modern childhood as subject of the media. Historians, anthropologists, teachers, jurists and sociologists analyze the different systems of childhood representations constituted in time and space.