Photosynthesis in plants starts with the capture of photons by light-harvesting complexes (LHCs). Structural biology and spectroscopy approaches have led to a map of the architecture and energy transfer pathways between LHC pigments. Still, controversies remain regarding the role of specific carotenoids in light-harvesting and photoprotection, obligating the need for high-resolution techniques capable of identifying excited-state signatures and molecular identities of the various pigments in photosynthetic systems. Here we demonstrate the successful application of femtosecond stimulated Raman spectroscopy (FSRS) to a multichromophoric biological complex, trimers of LHCII. We demonstrate the application of global and target analysis (GTA) to FSRS data and utilize it to quantify excitation migration in LHCII trimers. This powerful combination of techniques allows us to obtain valuable insights into structural, electronic, and dynamic information from the carotenoids of LHCII trimers. We report spectral and dynamical information on ground- and excited-state vibrational modes of the different pigments, resolving the vibrational relaxation of the carotenoids and the pathways of energy transfer to chlorophylls. The lifetimes and spectral characteristics obtained for the S1 state confirm that lutein 2 has a distorted conformation in LHCII and that the lutein 2 S1 state does not transfer to chlorophylls, while lutein 1 is the only carotenoid whose S1 state plays a significant energy-harvesting role. No appreciable energy transfer takes place from lutein 1 to lutein 2, contradicting recent proposals regarding the functions of the various carotenoids (Son et al. Chem.2019, 5 (3), 575-584). Also, our results demonstrate that FSRS can be used in combination with GTA to simultaneously study the electronic and vibrational landscapes in LHCs and pave the way for in-depth studies of photoprotective conformations in photosynthetic systems.New langbeinite-type phosphates KPbCr2(PO4)3 and KPbFe2(PO4)3 are synthesized by solution method and characterized by powder X-ray diffraction, infrared spectra, thermogravimetric and differential thermal analysis, scanning electron microscope, and energy dispersive X-ray analysis. Rietveld refinement reveals that both of the compounds crystallize in the cubic system with P213 space group, and the calculated lattice parameters for Cr and Fe phases are 9.7332(2) and 9.8325(7) Å, respectively. The electron micrographs confirm the crystalline nature of the samples from their surface morphologies. Infrared spectra display the characteristic features of P-O and M-O vibrational bands for both of the phases. Thermal analysis of KPbCr2(PO4)3 and KPbFe2(PO4)3 indicates that they are thermally stable up to 1273 K. The axial thermal expansion is studied by high-temperature X-ray diffraction between 298 and 1073 K. The average thermal expansion coefficients of KPbCr2(PO4)3 and KPbFe2(PO4)3 are identified as 8.9 × 10-6 and 10.8 × 10-6 K-1, respectively. Magnetic study reveals both of the compounds follow Curie-Weiss behavior in the higher-temperature region, and antiferromagnetic interactions are dominant.Accumulation of cytotoxic lipofuscin bisretinoids may contribute to atrophic age-related macular degeneration (AMD) pathogenesis. Retinal bisretinoid synthesis depends on the influx of serum all-trans-retinol (1) delivered via a tertiary retinol binding protein 4 (RBP4)-transthyretin (TTR)-retinol complex. We previously identified selective RBP4 antagonists that dissociate circulating RBP4-TTR-retinol complexes, reduce serum RBP4 levels, and inhibit bisretinoid synthesis in models of enhanced retinal lipofuscinogenesis. However, the release of TTR by selective RBP4 antagonists may be associated with TTR tetramer destabilization and, potentially, TTR amyloid formation. We describe herein the identification of bispecific RBP4 antagonist-TTR tetramer kinetic stabilizers. Standout analogue (±)-44 possesses suitable potency for both targets, significantly lowers mouse plasma RBP4 levels, and prevents TTR aggregation in a gel-based assay. This new class of bispecific compounds may be especially important as a therapy for dry AMD patients who have another common age-related comorbidity, senile systemic amyloidosis, a nongenetic disease associated with wild-type TTR misfolding.Gas-phase enthalpies of formation are frequently obtained from electronic-structure calculations. For a compound containing elements that are not permanent gases, experimental data are needed to connect the ab initio energies with the elements in their standard states. Usually only one chemical reaction, such as atomization, is used to make this connection. Using a single reaction has the supposed advantage of producing a single value, but it remains challenging to estimate the associated uncertainty. Here, we propose using several chemical reactions instead of one. This yields several values for the target enthalpy of formation. The relative reliability of each reaction is estimated and used for weighted averaging of the corresponding enthalpies of formation. The resulting weighted mean is an estimate for the target quantity, and the standard deviation of the weighted mean is a reasonable estimate for the associated standard uncertainty. Two implementations are explored here and applied predictively to dihydrolevoglucosenone (cyrene), which has been proposed as a "green" polar aprotic solvent.Studies of the oxidative degradation of picric acid (2,4,6-trinitrophenol) by H2O2 catalyzed by a fluorine-tailed tetraamido macrocyclic ligand (TAML) activator of peroxides [FeIII4,5-Cl2C6H2-1,2-(NCOCMe2NCO)2CF2(OH2)]- (2) in neutral and mildly basic solutions revealed that oxidative degradation of this explosive demands components of phosphate or carbonate buffers and is not oxidized in their absence. The TAML- and buffer-catalyzed oxidation is subject to severe substrate inhibition, which results in at least 1000-fold retardation of the interaction between the iron(III) resting state of 2 and H2O2. NVP-ADW742 cell line The inhibition accounts for a unique pH profile for the TAML catalysis with the highest activity at pH 7. Less aggressive TAMLs such as [FeIIIC6H4-1,2-(NCOCMe2NCO)2CMe2(OH2)]- are catalytically inactive. The roles of buffer components in modulating catalysis have been clarified through detailed kinetic investigations of the degradation process, which is first order in the concentration of 2 and shows ascending hyperbolic dependencies in the concentrations of all three participants, i.