a b s t r a c tIron nanoparticles were produced using extracts of green tea leaves (GT-Fe NPs). The materials were characterized using TEM, SEM/EDX, XPS, XRD, and FTIR techniques and were shown to contain mainly iron oxide and iron oxohydroxide. The obtained nanoparticles were then utilized as a Fenton-like catalyst for decolorization of aqueous solutions containing methylene blue (MB) and methyl orange (MO) dyes. The related experiments investigated the removal kinetics and the effect of concentration for both MB and MO. The concentrations of dyes in aqueous solution were monitored using ultraviolet-visible (UV-vis) spectroscopy. The results indicated fast removal of the dyes with the kinetic data of MB following a second order removal rate, while those of MO were closer to a first order removal rate. The loading experiments indicated almost complete removal of both dyes from water over a wide range of concentration, 10-200 mg L −1 . Compared with iron nanoparticles produced by borohydride reduction, GT-Fe nanoparticles demonstrated more effective capability as a Fenton-like catalyst, both in terms of kinetics and percentage removal.

Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here, the mechanistic details and femtosecond time-resolved dynamics of H3+ formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3+ formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3+ formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3+, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.

Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. We present evidence for the existence of two different reaction pathways for H3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followed by the abstraction of a proton from the remaining CHOH2+ fragment by the roaming H2 molecule. This reaction has similarities to the H2 + H2 + mechanism leading to formation of H3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.

This study proposes a new sorbent for the removal of inorganic arsenic from aqueous solutions.Monodispersed nano zero-valent iron (nZVI) particles were nucleated at the surface of electrospun chitosan fibers (average fiber diameter of 195 ¡ 50 nm) by liquid phase reduction of FeCl 3 using NaBH 4 .The material was characterized using SEM, TGA, XPS, XRD, and FTIR. The diameter of iron nanoparticles was found to vary between 75-100 nm. A set of batch experiments were carried out to elucidate the efficiency of the composite sorbent toward fixation of arsenite and arsenate ions. The ion concentrations in the supernatant solutions were determined using inductively coupled plasma-mass spectrometry (ICP-MS). The results revealed that the chitosan fiber supported nZVI particles is an excellent sorbent material for inorganic arsenic uptake at concentrations ranging from 0.01 to 5.00 mg L 21 over a wide range of pH values. Based on XPS analysis, As(III) was found to undergo oxidation to As(V) upon sorption, while As(V) retained its oxidation state. By virtue of the successful combination of the electrospun fibers' mechanical integrity and the large reactivity of dispersed nZVI particles, the applicability of the resulting sorbent material in arsenic sorption holds broad promise.

Molecular reactivity can change dramatically with the absorption of a photon due to the difference of the electronic configurations between the excited and ground states. Here we report on the discovery of a modular system (Schiff base formed from an aldehyde and an amine) that upon photoexcitation yields a more basic imine capable of intermolecular proton transfer from protic solvents. Ultrafast dynamics of the excited state conjugated Schiff base reveals the pathway for proton transfer, culminating in a 14-unit increase in pK to give the excited state pK >20 in ethanol.

Roaming chemical reactions are often associated with neutral molecules. The recent findings of roaming processes in ionic species, in particular, ones that lead to the formation of H 3 + under strong-field laser excitation, are of considerable interest. Given that such gas-phase reactions are initiated by double ionization and subsequently facilitated through deprotonation, we investigate the strong-field photodissociation of ethanethiol, also known as ethyl mercaptan, and compare it to results from ethanol. Contrary to expectations, the H 3 + yield was found to be an order of magnitude lower for ethanethiol at certain laser field intensities, despite its lower ionization energy and higher acidity compared to ethanol. In-depth analysis of the femtosecond time-resolved experimental findings, supported by ab initio quantum mechanical calculations, provides key information regarding the roaming mechanisms related to H 3 + formation. Results of this study on the dynamics of dissociative halfcollisions involving H 3 + , a vital cation which acts as a Brønsted-Lowry acid protonating interstellar organic compounds, may also provide valuable information regarding the formation mechanisms and observed natural abundances of complex organic molecules in interstellar media and planetary atmospheres.

Differences in the excited state dynamics of molecules and photo-activated drugs either in solution or confined inside protein pockets or large biological macromolecules occur within the first few hundred femtoseconds. Shaped femtosecond laser pulses are used to probe the behavior of indocyanine green (ICG), the only Food and Drug Administration (FDA) approved near-infrared dye and photodynamic therapy agent, while free in solution and while confined inside the pocket of the human serum albumin (HSA) protein. Experimental findings indicate that the HSA pocket hinders torsional motion and thus mitigates the triplet state formation in ICG. Low frequency vibrational motion of ICG is observed more clearly when it is bound to the HSA protein.

Photosynthetic light harvesting can occur with a remarkable near-unity quantum efficiency. The B800–850 complex, also known as light-harvesting complex 2 (LH2), is the primary light-harvesting complex in purple bacteria and has been extensively studied as a model system. The bacteriochlorophylls of the B800–850 complex are organized into two concentric rings, known as the B800 and B850 rings. However, depending on the species and growth conditions, the number of constituent subunits, the pigment geometry, and the absorption energies vary. While the dynamics of some B800–850 variants have been exhaustively characterized, others have not been measured. Furthermore, a direct and simultaneous comparison of how both structural and spectral differences between variants affect these dynamics has not been performed. In this work, we utilize ultrafast transient absorption measurements to compare the B800 to B850 energy-transfer rates in the B800–850 complex as a function of the number of subunits, geometry, and absorption energies. The nonameric B800–850 complex from Rhodobacter (Rb.) sphaeroides is 40% faster than the octameric B800–850 complex from Rhodospirillum (Rs.) molischianum, consistent with structure-based predictions. In contrast, the blue-shifted B800–820 complex from Rs. molischianum is only 20% faster than the B800–850 complex from Rs. molischianum despite an increase in the spectral overlap between the rings that would be expected to produce a larger increase in the energy-transfer rate. These measurements support current models that contain dark, higher-lying excitonic states to bridge the energy gap between rings, thereby maintaining similar energy-transfer dynamics. Overall, these results demonstrate that energy-transfer dynamics in the B800–850 complex are robust to the spectral and structural variations between species used to optimize energy capture and flow in purple bacteria.