Gold Nanocages as Effective Photothermal Transducers in Killing Highly Tumorigenic Cancer Cells

Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL^?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL^?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells.     

Maximum-likelihood estimator for dual phase extraction in holographic moire

A maximum-likelihood (ML) method based on spectral estimation theory for the extraction of dual phase distributions in holographic moire in the presence of nonsinusoidal waveforms, noise, and the miscalibration of piezoelectric (PZT) devices is proposed. The extraction of these phases requires incorporating two PZTs into the moire setup. ML estimators are asymptotically efficient for sufficient data samples. The approach presented uses a direct stochastic algorithm called probabilistic global search Lausanne for minimizing the ML function.     

Total syntheses of naturally occurring antiviral indolosesquiterpene alkaloids,xiamycins C–F via Csp3–H functionalization

Concise total syntheses of naturally occurring antiviral indolosesquiterpene alkaloids, xiamycin C (2a), D (2b), E (2c) and F (2d), have been achieved via a late-stage oxidative δ-Csp³–H functionalization of an advanced pentacyclic enone intermediate 8. This strategy takes advantage of ipso-nitration of naturally occurring abietane diterpenoids to synthesize o-bromo nitroarene derivative 11. A Suzuki–Miyaura coupling of 11 with phenylboronic acid followed by Cadogan''s ring closure provided a modular approach to a carbazole ring required for a functionalized pentacyclic core of indolosesquiterpene alkaloids.

Enantioenriched enone 8 was synthesized via three key transformations: ipso-nitration of abietane diterpenoids to furnish o-bromo nitroarene 11, Suzuki coupling with phenylboronic acid, and Cadogan''s reductive ring closure to craft a carbazole ring.     

Nitrite and Nitric Oxide Interconversion at Mononuclear Copper(II): Insight into the Role of the Red Copper Site in Denitrification

Nitrite (NO₂⁻) and nitric oxide (NO) interconversion is crucial for maintaining optimum NO flux in mammalian physiology. Herein we demonstrate that [ L ₂Cu^II(nitrite)]⁺ moieties (in 2 a and 2 b ; where, L = Me₂PzPy and Me₂PzQu ) with distorted octahedral geometry undergo facile reduction to provide tetrahedral [ L ₂Cu^I]⁺ (in 3 a and 3 b ) and NO in the presence of biologically relevant reductants, such as 4-methoxy-2,6-di-tert-butylphenol (4-MeO-2,6-DTBP, a tyrosine model) and N-benzyl-1,4-dihydronicotinamide (BNAH, a NAD(P)H model). Interestingly, the reaction of excess NO gas with [ L ₂Cu^II(MeCN)₂]²⁺ (in 1 a ) provides a putative {CuNO}¹⁰ species, which is effective in mediating the nitrosation of various nucleophiles, such as thiol and amine. Generation of the transient {CuNO}¹⁰ species in wet acetonitrile leads to NO₂⁻ as assessed by Griess assay and ¹⁴N/¹⁵N-FTIR analyses. A detailed study reveals that the bidirectional NO_x-reactivity, namely, nitrite reductase (NIR) and NO oxidase (NOO), at a common Cu^II site, is governed by the geometric-preference-driven facile Cu^II/Cu^I redox process. Of broader interest, this study not only highlights potential strategies for the design of copper-based catalysts for nitrite reduction, but also strengthens the previous postulates regarding the involvement of red copper proteins in denitrification.     

Mass spectral study of substituted allyl aryl and allyl alkyl selenides and some analogous sulfides

The electron impact (EI) mass spectra of allyl aryl selenides showed abundant molecular ions and many fragment ions containing the selenium atom. alpha-Cleavage is the dominant process in the fragmentation of selenides, and cleavage product ions are characteristic of the substituents. In the case of 3-methyl allyl and related aryl selenides, characteristic delta-hydrogen migration to the selenium atom is observed. A McLafferty-type rearrangement is found in benzyl allyl selenides and substituted alkyl allyl selenides. The charge on the rearrangement products preferably remains on the fragments containing the phenyl group. The [M - SeH](+), [M - CH(3)](+) and [M - C(2)H(4)](+) ions are found only in the EI mass spectrum of allyl phenyl selenide, and are attributed to a Claisen rearrangement in the source of the mass spectrometer. All structurally informative fragmentation processes are supported by collision induced dissociation spectra of molecular ions. The fragmentation patterns found in methane chemical ionization (CI) spectra of the selenides were significantly different from those observed in EI. The EI and CI mass spectra of analogous sulfides showed similar behaviour to that observed in the corresponding selenides. Copyright 1999 John Wiley & Sons, Ltd.     

Chinese Oak Tasar Silkworm Antheraea pernyi Silk Proteins: Current Strategies and Future Perspectives for Biomedical Applications

Chinese nonmulberry temperate oak tasar/tussah, Antheraea pernyi (Ap) silk is a natural biopolymer that has attracted considerable attention as a biomaterial. The proteinaceous components of Ap silk proteins, namely fibroin and sericin may represent an alternative over mulberry Bombyx mori silk proteins. In fact, the silk fibroin (SF) of Ap is rich in Arginyl‐Glycyl‐Aspartic acid (RGD) peptides, which facilitate the adhesion and proliferation of various cell types. The possibility of processing Ap silk proteins into different distinct 2D‐ and 3D‐based matrices is described in earlier studies, such as membranes, nanofibers, scaffolds, and micro/nanoparticles, contributing to a different rate of degradation, mechanical properties, and biological performance useful for various biomedical applications. This review summarizes the current advances and developments on nonmulberry Chinese oak tasar silk protein (fibroin and sericin)‐based biomaterials and their potential uses in tissue engineering, regenerative medicine, and therapeutic delivery strategies.     

Basic alumina supported one-pot synthesis of structurally diverse pyridine/quinolinine-fused novel diazepanium, diazocanium, imidazodilinium and tetrahydro-pyrimidiniums

Basic alumina supported solvent-free one-pot synthesis of pyridine-fused polycyclic diazepaniums was achieved under microwave irradiation. The process was successfully extended to the synthesis of pyridine-fused bicyclic imidazolidiniums and tetrahydro-pyrimidiniums and also of tri- and tetracyclic diaza-heterocycle-fused quinoliniums. The dual characteristic of basic alumina, a solid support as well as a base, was successfully employed in the current investigation. The method emerged to be an effective route in terms of product yield, reaction time, and ease of purification and most importantly for environment friendly protocols.     

Magnesium-induced regiospecific C-silylation of suitably substituted enoates and dienoates

The β-aryl-β-silyl and β,β-disilyl propionates have been synthesized from cinnamates and β-silyl acrylates by a regiospecific reductive C-silylation using Mg/silyl chloride/DMF system at room temperature. These reductive C-silylation conditions have also been applied to δ-aryl substituted dienoates wherein silylation took place at the δ-position leading to the synthesis of single regioisomeric allylsilanes with very high stereoselectivity.     

The role of ion-pairing in peak deformations in overloaded reversed-phase chromatography of peptides

The paper reports a study on the role of ion-pairing behind peak deformations, e.g. peak splitting and even peak disappearance, during the elution of a peptide at highly overloaded conditions in reversed-phase chromatography. Deformation of component peaks is not uncommon in chromatography. There are reports which discuss their occurrence, but mostly at analytical scale, while their occurrence is quite common also in the preparative scale, as in the case discussed in this work. This paper first describes the conditions leading to peak splitting and peak disappearance of an industrial peptide, then explains the plausible reasons behind such behaviour, and finally with experimental analysis demonstrates the role of ion-pairing in causing such behaviour.