Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions imp... more Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions important to numerous organisms. Eumelanin is also a promising redox-active material for energy conversion and storage, but the chemical structures present in this heterogeneous pigment remain unknown, limiting understanding of the properties of its light-responsive subunits. Here, we introduce an ultrafast vibrational fingerprinting approach for probing the structure and interactions of chromophores in heterogeneous materials like eumelanin. Specifically, transient vibrational spectra in the double-bond stretching region are recorded for subsets of electronic chromophores photoselected by an ultrafast excitation pulse tuned through the UV-visible spectrum. All subsets show a common vibrational fingerprint, indicating that the diverse electronic absorbers in eumelanin, regardless of transition energy, contain the same distribution of IR-active functional groups. Aggregation of chromophores ...
The catechol functional motif is thought to play both a structural and photochemical role in the ... more The catechol functional motif is thought to play both a structural and photochemical role in the ubiquitous natural pigment, eumelanin. Intramolecular and intermolecular hydrogen bonding interactions lead to a variety of geometries involving the two O-H groups in catechol, but its photophysical behavior in these situations has not been comprehensively characterized. Toward this end, we monitor the UV-induced O-H bond photodissociation reaction in an exemplar catechol derivative, 4- tert-butylcatechol, possessing different intramolecular and intermolecular hydrogen bonding geometries using femtosecond transient absorption spectroscopy measurements in the UV-visible and mid-infrared regions following 265 nm photoexcitation. Three different hydrogen bonding arrangements are obtained by tuning solution complexation equilibria of the catechol with the hydrogen bond acceptor, diethyl ether (Et2O), and are verified computationally. We find that intermolecular hydrogen bonding to the free O-H group in catechol increases its first excited singlet state (S1) lifetime by 2 orders of magnitude (i.e., ∼ 16 to 1410 ps), and that O-H bond dissociation is prevented because Et2O is a poor hydrogen atom acceptor. Complexation of both O-H groups with multiple Et2O molecules further elongates the S1 lifetime to 1670 ps due to shifting of the solution equilibria that describe complex formation. Weakening of the characteristic, intramolecular hydrogen bond of the catechol derivative by intermolecular hydrogen bonding to one or more Et2O molecules does not enhance the rate of O-H bond dissociation.
Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions imp... more Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions important to numerous organisms. Eumelanin is also a promising redox-active material for energy conversion and storage, but the chemical structures present in this heterogeneous pigment remain unknown, limiting understanding of the properties of its light-responsive subunits. Here, we introduce an ultrafast vibrational fingerprinting approach for probing the structure and interactions of chromophores in heterogeneous materials like eumelanin. Specifically, transient vibrational spectra in the double-bond stretching region are recorded for subsets of electronic chromophores photoselected by an ultrafast excitation pulse tuned through the UV-visible spectrum. All subsets show a common vibrational fingerprint, indicating that the diverse electronic absorbers in eumelanin, regardless of transition energy, contain the same distribution of IR-active functional groups. Aggregation of chromophores ...
The catechol functional motif is thought to play both a structural and photochemical role in the ... more The catechol functional motif is thought to play both a structural and photochemical role in the ubiquitous natural pigment, eumelanin. Intramolecular and intermolecular hydrogen bonding interactions lead to a variety of geometries involving the two O-H groups in catechol, but its photophysical behavior in these situations has not been comprehensively characterized. Toward this end, we monitor the UV-induced O-H bond photodissociation reaction in an exemplar catechol derivative, 4- tert-butylcatechol, possessing different intramolecular and intermolecular hydrogen bonding geometries using femtosecond transient absorption spectroscopy measurements in the UV-visible and mid-infrared regions following 265 nm photoexcitation. Three different hydrogen bonding arrangements are obtained by tuning solution complexation equilibria of the catechol with the hydrogen bond acceptor, diethyl ether (Et2O), and are verified computationally. We find that intermolecular hydrogen bonding to the free O-H group in catechol increases its first excited singlet state (S1) lifetime by 2 orders of magnitude (i.e., ∼ 16 to 1410 ps), and that O-H bond dissociation is prevented because Et2O is a poor hydrogen atom acceptor. Complexation of both O-H groups with multiple Et2O molecules further elongates the S1 lifetime to 1670 ps due to shifting of the solution equilibria that describe complex formation. Weakening of the characteristic, intramolecular hydrogen bond of the catechol derivative by intermolecular hydrogen bonding to one or more Et2O molecules does not enhance the rate of O-H bond dissociation.
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Papers by Alex Hanes