Diagnosing the Protonation Site of <Emphasis Type="BoldItalic">b</Emphasis><Subscript><Emphasis Type="BoldItalic">2</Emphasis></Subscript> Peptide Fragment Ions using IRMPD in the X–H (X = O,N, and C) Stretching Region

Charge-directed fragmentation has been shown to be the prevalent dissociation step for protonated peptides under the low-energy activation (eV) regime. Thus, the determination of the ion structure and, in particular, the characterization of the protonation site(s) of peptides and their fragments is a key approach to substantiate and refine peptide fragmentation mechanisms. Here we report on the characterization of the protonation site of oxazolone b ₂ ions formed in collision-induced dissociation (CID) of the doubly protonated tryptic model-peptide YIGSR. In support of earlier work, here we provide complementary IR spectra in the 2800–3800 cm^–1 range acquired on a table-top laser system. Combining this tunable laser with a high power CO₂ laser to improve spectroscopic sensitivity, well resolved bands are observed, with an excellent correspondence to the IR absorption bands of the ring-protonated oxazolone isomer as predicted by quantum chemical calculations. In particular, it is shown that a band at 3445 cm^–1, corresponding to the asymmetric N–H stretch of the (nonprotonated) N-terminal NH₂ group, is a distinct vibrational signature of the ring-protonated oxazolone structure.     

Facile green synthesis of gold nanoparticles using leaf extract of antidiabetic potent Cassia auriculata

A simple biological method for the synthesis of gold nanoparticles (AuNPs) using Cassia auriculata aqueous leaf extract has been carried out in the present study. The reduction of auric chloride led to the formation of AuNPs within 10 min at room temperature (28°C), suggesting a higher reaction rate than chemical methods involved in the synthesis. The size, shape and elemental analysis were carried out using X-ray diffraction, TEM, SEM-EDAX, FT-IR and visible absorption spectroscopy. Stable, triangular and spherical crystalline AuNPs with well-defined dimensions of average size of 15-25 nm were synthesized using C. auriculata. Effect of pH was also studied to check the stability of AuNPs. The main aim of the investigation is to synthesize AuNPs using antidiabetic potent medicinal plant. The stabilizing and reducing molecules of nanoparticles may promote anti-hyperglycemic if tested further.     

A synergistic approach to polycyclics via a strategic utilization of Claisen rearrangement and olefin metathesis

Olefin metathesis promoted by a well-defined metal carbene complex has evolved into an efficient method for the construction of a broad range of carbocyclic and heterocyclic rings of varying size. The synthetic potential of the olefin metathesis has been further increased by combining various other C-C bond forming processes either in tandem or in sequence. Herein, application of Claisen rearrangement and olefin metathesis to prepare various intricate and/or biologically important targets has been described.     

Application of advanced nuclear analytical techniques for the electrocatalyst's characterization: Paving the path for mechanistic investigations

As the application of electrocatalyst continues to expand, envisaging the hidden mechanisms occurring at various length scale affecting the catalytic efficiency became important. To enhance the stability of electrocatalyst and reduce the cost, it is of paramount importance to reveal the active site's dynamics (using in situ techniques for getting the real-time information) which directly affect the reactions such as oxygen evolution reaction, hydrogen evolution reaction, and so on. Since such reactions are crucial for many engineering and scientific applications, in situ characterization techniques are required, which could capture such reactions happening at a different length and time scale. This article analyzes the recent progress made in the field of electrocatalyst's characterization using in situ neutron techniques. The article also paves the future path and has delineated the future challenges involved in multiscale correlative techniques (e.g., neutron techniques in the combination of synchrotron or microscopic techniques) used for getting the multiscale (atomic to micrometer range) mechanistic information about the electrocatalyst's working and degradation.     

Structurally Stabilized Organosilane‐Templated Thermostable Mesoporous Titania

Structurally thermostable mesoporous anatase TiO₂ (m‐TiO₂) nanoparticles, uniquely decorated with atomically dispersed SiO₂, is reported for the first time. The inorganic Si portion of the novel organosilane template, used as a mesopores‐directing agent, is found to be incorporated in the pore walls of the titania aggregates, mainly as isolated sites. This is evident by transmission electron microscopy and high‐angle annular dark field scanning transmission electron microscopy, combined with electron dispersive X‐ray spectroscopy. This type of unique structure provides exceptional stability to this new material against thermal collapse of the mesoporous structure, which is reflected in its high surface area (the highest known for anatase titania), even after high‐temperature (550 °C) calcination. Control of crystallite size, pore diameter, and surface area is achieved by varying the molar ratios of the titanium precursor and the template during synthesis. These mesoporous materials retain their porosity and high surface area after template removal and further NaOH/HCl treatment to remove silica. We investigate their performance for dye‐sensitized solar cells (DSSCs) with bilayer TiO₂ electrodes, which are prepared by applying a coating of m‐TiO₂ onto a commercial titania (P25) film. The high surface area of the upper mesoporous layer in the P25–m‐TiO₂ DSSC significantly increases the dye loading ability of the photoanode. The photocurrent and fill factor for the DSSC with the bilayer TiO₂ electrode are greatly improved. The large increase in photocurrent current (ca. 56 %) in the P25–m‐TiO₂ DSSC is believed to play a significant role in achieving a remarkable increase in the photovoltaic efficiency (60 %) of the device, compared to DSSCs with a monolayer of P25 as the electrode.     

Two-step photoionization of Na2: dependence on alignment

Laser light is used for two-step photoionization of Na₂. the first step depends on the moleculer orientation, the second step doesnot. This yields a method for the analysis of molecular alignment.     

Can functionalized cucurbituril bind actinyl cations efficiently? A density functional theory based investigation

The feasibility of using cucurbituril host molecule as a probable actinyl cation binders candidate is investigated through density functional theory based calculations. Various possible binding sites of the cucurbit[5]uril host molecule to uranyl are analyzed and based on the binding energy evaluations, μ(5)-binding is predicted to be favored. For this coordination, the structure, vibrational spectra, and binding energies are evaluated for the binding of three actinyls in hexa-valent and penta-valent oxidation states with functionalized cucurbiturils. Functionalizing cucurbituril with methyl and cyclohexyl groups increases the binding affinities of actinyls, whereas fluorination decreases the binding affinities as compared to the native host molecule. Surprisingly hydroxylation of the host molecule does not distinguish the oxidation state of the three actinyls.