Nickel‐Catalyzed Barton Decarboxylation and Giese Reactions: A Practical Take on Classic Transforms

Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH₃) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry.     

In Vivo Endoscopic Tissue Identification by Rapid Evaporative Ionization Mass Spectrometry (REIMS)

Gastrointestinal cancers are a leading cause of mortality, accounting for 23 % of cancer‐related deaths worldwide. In order to improve outcomes from these cancers, novel tissue characterization methods are needed to facilitate accurate diagnosis. Rapid evaporative ionization mass spectrometry (REIMS) is a technique developed for the in vivo classification of human tissue through mass spectrometric analysis of aerosols released during electrosurgical dissection. This ionization technique was further developed by utilizing surface induced dissociation and was integrated with an endoscopic polypectomy snare to allow in vivo analysis of the gastrointestinal tract. We tested the classification performance of this novel endoscopic REIMS method in vivo. It was shown to be capable of differentiating between healthy layers of the intestinal wall, cancer, and adenomatous polyps based on the REIMS fingerprint of each tissue type in vivo.     

A simple CdS nanoparticles cascading approach for boosting N3 dye/ZnO nanoplates DSSCs overall performance

Enhanced photosensitization in presence of CdS nanoparticles is achieved in electrochemically deposited ZnO nanoplates and N3 loaded dye-sensitized solar cells. Chemically embedded CdS nanoparticles act as a sandwiching layer between ZnO nanoplates and dye molecules by overcoming current limiting serious Zn²⁺/dye insulating complex formation and CdS photo-corrosion issues. The X-ray diffraction and the scanning electron microscopy confirm the ZnO with vertically aligned nanoplates, perpendicular to the substrate surface. Amorphous CdS is monitored using electron dispersive X-ray analysis. The low and high resolution transmission electron microscope images confirm the presence of CdS nanoparticles over ZnO nanoplates which later is supported by an increase in optical absorbance and shift in band edge. About 400% increase in solar conversion efficiency with this cascade arrangement is achieved when compared with without CdS which could be fascinating while designing solid state solar cells in presence of suitable p-type layer.     

Unexpected regio- and stereoselective [4 + 3] cycloaddition reaction of azomethine ylides with benzylidene thiazolidinediones: synthesis of pharmacologically active spiroindoline oxazepine derivatives and theoretical study

Molecular Diversity - An unexpected regio- and stereoselective [4?+?3] cycloaddition reaction of azomethine ylides with 5-benzylidenethiazolidine-2,4-diones has been successfully...     

Neighboring Group Participation in Glycosylation Reactions by 2,6-Disubstituted 2-O-Benzoyl groups: A Mechanistic Investigation

Variable yields and glycosylation stereoselectivity were obtained for NIS/TfOH-medi- ated reaction of 4-methoxyphenyl 2,4,6-tetra-O-acetyl-β-D-galactopyranoside and thiogalactosides bearing acetyl, benzoyl, 2,6-dimethoxylbenzoyl, 2,4,6-trimethylbenzoyl, or 2,6-dichlorobenzoyl groups at the 2-positions and acetyl at the remainder. X-ray structures of 4-methylphenyl 2,3,4,6-tetra-O-(2,4,6-trimethylbenzoyl)-1-thio-β-D-galactopyr anoside and 4-methylphenyl 3,4-O-isopropylidene-2,6-di-O-(2,4,6-trimethylbenzoyl)-1-thio-β-D-galactopyranoside revealed slightly distorted ⁴ C ₁ chair conformations. Variable temperature NMR revealed that activation of 4-methylphenyl 2,3,4,6-tetra-O-(2,4,6-trimethylbenzoyl)-1-thio-β-D-galactopyranoside afforded only dioxolenium ion, whereas 4-methylphenyl 3,4,6-tri-O-acetyl-2-O-(2,4,6-trimethylbenzoyl)-1-thio-β-D-galactopyranoside gave a 1:1 mixture of dioxolenium ion and glycosyl triflate. However, the reaction intermediates formed from these deactivated donors do not influence the glycosylation stereoselectivity; instead, it is influenced by steric and electronic interactions at the transition states.     

Effect of Y3+ substitution on the structural,dielectric, and electrical properties of nanosized ZnAl 2 O 4 spinel

In the present work, we have studied the structural, dielectric, and electrical properties of a series of nanosized $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ ( $x = 0.00$ , 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, and 0.10) system prepared by chemical coprecipitation method. Powder X-ray diffraction (XRD) was carried out to study the influence of $\mathrm{Y}^{3+}$ substitution on the crystal structure of these samples. High Resolution Transmission Electron Microscopy (HRTEM) images reveal the nanocrystalline nature of the samples. The Fourier Transform Infrared (FTIR) spectra confirmed the preference of $\mathrm{Y}^{3+}$ ions at the octahedral B site. The variation of dielectric constant and loss tangent (1 kHz to 1 MHz) at room temperature for all the samples show the normal behavior of spinel compounds. AC conductivity study reveals that the conduction is due to small polaron hopping. The electrical modulus analysis shows that nanocrystalline $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ system exhibits non-Debye-type relaxation. The DC electrical resistivity measured in the temperature range 303–373 K was found to increase with temperature and yttrium content.     

Ecionines A and B, two new cytotoxic pyridoacridine alkaloids from the Australian marine sponge, Ecionemia geodides

Chemical investigations of the Australian marine sponge Ecionemia geodides resulted in the isolation of two new pyridoacridine alkaloids, ecionines A (1) and B (2), along with the previously isolated marine natural products, biemnadin (3) and meridine (4). Compounds 1 and 2 both contain an imine moiety, which is rare for the pyridoacridine structure class. The chemical structures of 1 and 2 were determined by extensive 1D and 2D NMR and MS data analyses. All compounds were tested against a panel of human bladder cancer cell lines, the increasingly metastatic TSU-Pr1 series (TSU-Pr1, TSU-Pr1-B1 and TSU-Pr1-B2) and the superficial bladder cancer cell line 5637. Ecionine A (1) displayed cytotoxicity against all cell lines, with IC₅₀ values ranging from 3 to 7 μM. This is the first report of chemistry from the sponge genus Ecionemia.     

Phytochemical fabrication,characterization, and antioxidant application of copper and cobalt oxides nanoparticles using <Emphasis Type="Italic">Sesbania sesban</Emphasis> plant

In this work, an ecofriendly and economic strategy for synthesize of CuO and Co₃O₄ were developed using extracted Sesbania sesban solution (ESS) as a reducing and stabilizing agent, and bioreactor. These novel nano metal oxides (NMOs) were characterized by high-resolution-transmission electron microscopy (TEM), EDAX thermo gravimetric analysis and X-ray diffraction (XRD). Morphology and size of them were investigated by TEM and the average sizes of for spherical CuO and Co₃O₄ nanoparticles are 20–40 and 15–30 nm, respectively. The XRD and EDAX confirmed the high purity for NMOs. The thermal behaviors of the NMOs exhibited good crystallographic stability within the investigated temperature range. The antioxidant and antibacterial activities of NMOs were investigated and compared to manganese(III) meso-tetraphenylporphyrin complex/Ag nanocomposite (Ag/P nanocomposite) synthesizing by ESS. The results obtained from this work showed that copper(II) oxide, cobalt oxide nanoparticles, and Ag/P nanocomposite have DPPH scavenging activity. On the other hand, NMOs have no antibacterial activity against Gram-negative bacterial strains. Cobalt oxide nanoparticles have antibacterial activity against Staphylococcus aureus, while Ag/P nanocomposite showed the antibacterial activities against both Gram-negative and Gram-positive bacterial strains.     

Rapid Photoactivated Generation of Nitroxyl (HNO) under Neutral pH Conditions

Directly obtaining kinetic and mechanistic data for the reactions of nitroxyl (HNO) with biomolecules (k≈10³–10⁷ m ^?1 s^?1) is not feasible for many systems because of slow HNO release from HNO donor molecules (t_1/2 is typically minutes to hours). To address this limitation, we have developed a photoactivatable HNO donor incorporating the (3‐hydroxy‐2‐naphthalenyl)methyl phototrigger, which rapidly releases HNO on demand. A “proof of concept” study is reported, which demonstrates that, upon continuous xenon light excitation, rapid decomposition of the HNO donor occurs within seconds. The amount of HNO generated is strongly dependent on solvent and the rate of the reaction is dependent on the light intensity.