Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal–metal σ-bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.     

Wurtzite CuGaS2 with an In-Situ-Formed CuO Layer Photocatalyzes CO2 Conversion to Ethylene with High Selectivity

We present surface reconstruction-induced C−C coupling whereby CO₂ is converted into ethylene. The wurtzite phase of CuGaS_2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO₂ to ethylene (C₂H₄). Upon illumination, the catalyst efficiently converts CO₂ to C₂H₄ with 75.1 % selectivity (92.7 % selectivity in terms of R_electron) and a 20.6 μmol g⁻¹ h⁻¹ evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu²⁺, with the assistance of existing Cu⁺, functioning as an anchor for the generated *CO and thereby facilitating C−C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO₂ reduction reaction pathway to selective formation of ethylene.     

Co-Catalyzed Metal-Ligand Cooperative Approach for N-alkylation of Amines and Synthesis of Quinolines via Dehydrogenative Alcohol Functionalization

Herein we report a cobalt-catalyzed sustainable approach for C−N cross-coupling reaction between amines and alcohols. Using a well-defined Co-catalyst 1 a bearing 2-(phenyldiazenyl)-1,10-phenanthroline ligand, various N-alkylated amines were synthesized in good yields. 1 a efficiently alkylates diamines producing N, N′-dialkylated amines in good yields and showed excellent chemoselectivity when oleyl alcohol and β-citronellol, containing internal carbon-carbon double bond were used as alkylating agents. 1 a is equally compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols. 1H-Indole was synthesized via an intramolecular dehydrogenative N-alkylation reaction, and various substituted quinolines were synthesized by coupling of 2-aminobenzyl alcohol and secondary alcohols. A few control reactions and spectroscopic experiments were conducted to illuminate the plausible reaction mechanism, indicating that the 1 a -catalyzed N-alkylation proceeds through the borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout the reaction; the hydrogen eliminated during dehydrogenation of alcohols was set aside in the ligand backbone and subsequently gets transferred in the reductive amination step to imine intermediates yielding N-alkylated amines. On the other hand, 1 a -catalyzed quinoline synthesis proceeds through dehydrogenation followed by successive C−C and C−N coupling steps forming H₂O₂ as a by-product under air.     

An atom-based explanation for the absence of excimer emission in the fluorescence of dilute solutions of poly(pentafluorostyrene)

The steady-state fluorescence emission spectrum of poly(pentafluorostyrene) in dilute fluid solution shows no excimer emission. An atomic level modeling study explains why this polymer cannot form an excimer. Repulsive Coulombic interactions prohibit the attainment of the extensive overlap of the two rings in the classic face-to-face sandwich conformation of a singlet excimer.     

Polyoxometalate-Engineered Building Blocks with Gold Cores for the Self-Assembly of Responsive Water-Soluble Nanostructures

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle-like organizations. Using cryo-TEM imaging and ¹H DOSY NMR spectroscopy, we then provide an unprecedented “solution-state” picture of how the micelle-like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes. These findings provide a versatile new option for transforming very small AuNPs into precisely tailored building blocks for the rational design of functional water-soluble assemblies.     

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

The self‐assembled structures of atomically precise, ligand‐protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding‐directed self‐assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p‐mercaptobenzoic acid (pMBA)‐protected atomically precise silver nanocluster, Na₄[Ag₄₄(pMBA)₃₀], and pMBA‐functionalized GNRs were used. High‐resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H‐bonding, leading to octahedral symmetry. The use of water‐dispersible gold nanoclusters, Au_≈250(pMBA)_n and Au₁₀₂(pMBA)₄₄, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities.     

Synthesis and structural characterization of functionalized dimeric aluminophosphonates and a monomeric gallophosphonate anion

Reaction of t-BuP(O)(OSiMe(3))(OH) with Me(3)Al leads to the formation of [Me(2)Al(mu-O)(2)P(OSiMe(3))(t-Bu)](2) (1) whereas Me(2)AlCl reacts with Ph(2)P(O)(OH) to yield [(Cl)(Me)Al(mu-O)(2)PPh(2)](2) (2). These compounds represent the first examples of functionalized dimeric four-ring type aluminophosphonate systems. The double four-ring type gallophosphonate, namely, [t-BuPO(3)GaMe](4), reacts with n-Bu(4)NHF(2) under ambient conditions, resulting in the formation of a monomeric gallophosphonate [n-Bu(4)N][MeGa[t-BuPO(2)(OH)](3)] (3). These derivatives have been adequately characterized using various spectroscopic techniques and X-ray diffraction studies.     

ICP-MS multielement determination in fly ash after microwave-assisted digestion of samples

A microwave assisted digestion procedure has been developed for dissolution of fly ash samples prior to the inductively coupled plasma-mass spectrometric determination of their elemental composition. The developed methodology was validated by carrying out the analysis of two high-silicate containing reference materials (CRM 134R sewage amended soil and NIES JR 1 rock) and by means of the comparison between results found by microwave-assisted digestion and ICP-MS of fly ash samples with those found by neutron activation analysis (NAA) for Sb, Cs, Cr, Co, Fe, U and Zn determination. The method developed can be recommended for routine multielement analysis of fly ash.     

Interpreting nucleation as a network formation process

In this paper we interpret nucleation as a network formation process. Inspired by this interpretation we propose a social network model which produces networks with communities.     

Carrageenan for encapsulation and immobilization of flavor,fragrance, probiotics,and enzymes: A review

Carrageenans are sulfated polysaccharides obtained from sea weed. There are six types of carrageenans. They have been explored as gelling agents, control release vehicles, and encapsulating agents. It has been established that carrageenans, in the form of gels, beads and films, can efficiently encapsulate flavors, fragrances, probiotics, and enzymes. Flavors and fragrances are encapsulated to reduce their volatility. Probiotic encapsulation results in enhanced stability. Immobilization of enzymes in carrageenans improves their biocatalytic performance and stability. This review has summarized how carrageenans have been extensively investigated as potential encapsulating agents for the above-mentioned attributes.