Simple methods for the direct assembly, functionalization, and patterning of acid-terminated monolayers on Si111

This article describes mild methods to directly assemble, functionalize, and pattern monolayers of undecylenic acid on hydrogen-terminated Si(111). These monolayers were assembled under very mild conditions from a neat solution of undecylenic acid containing 0.1 mol % 4-(decanoate)-2,2,6,6-tetramethylpiperidinooxy at room temperature without the need for UV light. Because of these mild conditions, monolayers exposing carboxylic acids could be assembled in one step without the need to protect the acid prior to its assembly. The monolayers were extensively characterized by horizontal attenuated total reflection infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle goniometry. The monolayers bonded to the silicon surface preferentially through the olefin with no detectable bonds between the carboxylic acids and silicon. The crystallinity of the monolayer was studied by infrared spectroscopy through the antisymmetric--v(a)(CH(2))--and symmetric--v(s)(CH(2))--stretches for methylene. Because it is important for future applications to assemble functional surfaces, methods to react the acid-terminated monolayers with trifluoroacetic anhydride and triethylamine to yield a symmetric anhydride on the monolayer were studied. These anhydrides were reacted with a variety of milligram-quantity amines to yield amide-terminated surfaces. This method was general, and a variety of amines could be bonded to the monolayer. The stabilities of these monolayers upon exposure to ambient conditions and under a variety of solvents were described. Because patterned monolayers have found wide applications, we have developed methods to pattern 1-octadecylamine and poly(ethylenimine) on the micrometer scale using soft lithography. In addition, polymer brushes of polynorbornene with thicknesses from 32 to 150 nm were grown from monolayers patterned with the Grubbs' catalyst. The patterned surfaces were imaged by scanning electron microscopy, scanning probe microscopy, and ellipsometry to determine the thicknesses of the patterns and the fidelity of the method.     

A facile one‐pot synthesis of novel substituted 1,2,3,4‐tetrahydropyrimidine,part 2: Synthesis of 1‐(aralkyl/aryl)‐3‐(alkyl/aralkyl/aryl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines

1‐(Aralkyl/aryl)‐3‐(alkyyaralkyl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines ( 2a‐c ) have been synthesized by dethiomethylation of 5‐aroyl‐6‐methylthio‐1,2,3,4‐tetrahydropyrimidines ( 1a‐c ). An alternative one‐pot synthetic strategy has been developed for the title compounds 2a‐t by the reaction of enaminones 3 with pri mary amine and formaldehyde in refluxing methanol in good yields.     

Nuclear moments and the change in the mean square charge radius of neutron deficient thallium isotopes

The hyperfine structure, isotope and isomeric shifts in the atomic transition 6p ² P _3/2–7s ² S _1/2, =535 nm have been measured for theI=7 andI=2 states of^{190, 192, 194, 196}Tl; theI=1/2 andI=9/2 states of¹⁹¹Tl and the I=7 isomer of¹⁸⁸Tl. The thallium isotopes were prepared as fast atomic beams at the GSI on-line mass separator following fusion reactions and — in some cases — subsequent-decay. The nuclear dipole moments, electric quadrupole moments and the change in the nuclear mean square charge radius are evaluated. Theuu-isotopes show an isomeric shift which changes sign between¹⁹²Tl and¹⁹⁴Tl.Dedicated to P. Armbruster on the occasion of his 60th birthday     

Oxygen binding to sulfur in nitrosylated iron--thiolate complexes: relevance to the Fe-containing nitrile hydratases

Iron-nitrosyl complex containing S-bonded monosulfinate [PPN][(NO)Fe(S,SO2-C6H4)(S,S-C6H4)] (3) has been isolated from sulfur oxygenation of complex [PPN][(NO)Fe(S,S-C6H4)2] (2) which is obtained from addition of NO molecule to [PPN][(C4H8O)Fe(S,S-C6H4)2] (1) in organic solvents. This result reveals that binding of NO to the iron center promotes sulfur oxygenation of iron dithiolates by dioxygen and stabilizes the S-bonded sulfinate iron species. Analysis of the bond angles for complexes 2 and 3 reveals that iron is best described as existing in a distorted trigonal bipyramidal coordination environment surrounded by one NO, three thiolates, and one sulfinate in complex 3, whereas the distorted square pyramidal geometry is adopted in complex 2. Complex 3 further reacts in organic solvents with molecular oxygen in the presence of [PPN][NO2] to produce the dinuclear bis(sulfinate) complex [PPN]2[(NO)Fe(SO2,SO2-C6H4)(S,S-C6H4)]2 (4). Complex 3 showed reaction with PPh3 in THF/CH2Cl2 to yield complex 2 and Ph3PO. Upon photolysis of CH2Cl2 solution of complex 3 under N2 purge at ambient temperature, the UV-vis and IR spectra consistent with the formation of complex 2 demonstrate that complex 2 and 3 are photochemically interconvertible. Obviously, complex 3 is thermally quite stable but is photochemically active toward [O] release. Also described are the X-ray crystal structures of 3 and 4.     

In Vitro Anticancer Activity of Methanolic Extract of Justicia adhatoda Leaves with Special Emphasis on Human Breast Cancer Cell Line

Natural products are being targeted as alternative anticancer agents due to their non-toxic and safe nature. The present study was conducted to explore the in vitro anticancer potential of Justicia adhatoda (J. adhatoda) leaf extract. The methanolic leaf extract was prepared, and the phytochemicals and antioxidant potential were determined by LCMS analysis and DPPH radical scavenging assay, respectively. A docking study performed with five major alkaloidal phytoconstituents showed that they had a good binding affinity towards the active site of NF-κB. Cell viability assay was carried out in five different cell lines, and the extract exhibited the highest cytotoxicity in MCF-7, a breast cancer cell line. Extract-treated cells showed a significant increase in nitric oxide and reactive oxygen species production. Cell cycle analysis showed an arrest in cell growth at the Sub-G0 phase. The extract successfully inhibited cell migration and colony formation and altered mitochondrial membrane potential. The activities of superoxide dismutase and glutathione were also found to decrease in a dose-dependent manner. The percentage of apoptotic cells was found to increase in a dose-dependent manner in MCF-7 cells. The expressions of caspase-3, Bax, and cleaved-PARP were increased in extract-treated cells. An increase in the expression of NF-κB was found in the cytoplasm in extract-treated cells. J. adhatoda leaf extract showed a potential anticancer effect in MCF-7 cells.     

Chemical Profiles and Pharmacological Properties with in Silico Studies on Elatostema papillosum Wedd

The current study attempted, for the first time, to qualitatively and quantitatively determine the phytochemical components of Elatostema papillosum methanol extract and their biological activities. The present study represents an effort to correlate our previously reported biological activities with a computational study, including molecular docking, and ADME/T (absorption, distribution, metabolism, and excretion/toxicity) analyses, to identify the phytochemicals that are potentially responsible for the antioxidant, antidepressant, anxiolytic, analgesic, and anti-inflammatory activities of this plant. In the gas chromatography-mass spectroscopy analysis, a total of 24 compounds were identified, seven of which were documented as being bioactive based on their binding affinities. These seven were subjected to molecular docking studies that were correlated with the pharmacological outcomes. Additionally, the ADME/T properties of these compounds were evaluated to determine their drug-like properties and toxicity levels. The seven selected, isolated compounds displayed favorable binding affinities to potassium channels, human serotonin receptor, cyclooxygenase-1 (COX-1), COX-2, nuclear factor (NF)-κB, and human peroxiredoxin 5 receptor proteins. Phytol acetate, and terpene compounds identified in E. papillosum displayed strong predictive binding affinities towards the human serotonin receptor. Furthermore, 3-trifluoroacetoxypentadecane showed a significant binding affinity for the KcsA potassium channel. Eicosanal showed the highest predicted binding affinity towards the human peroxiredoxin 5 receptor. All of these findings support the observed in vivo antidepressant and anxiolytic effects and the in vitro antioxidant effects observed for this extract. The identified compounds from E. papillosum showed the lowest binding affinities towards COX-1, COX-2, and NF-κB receptors, which indicated the inconsequential impacts of this extract against the activities of these three proteins. Overall, E. papillosum appears to be bioactive and could represent a potential source for the development of alternative medicines; however, further analytical experiments remain necessary.     

Accessing C2-Functionalized 1,3-(Benz)azoles through Transition Metal-Catalyzed C−H Activation

The skeletal presence of 1,3-azoles in a variety of bioactive natural products, pharmacophores, and organic materials demands the derivatization of such heteroarenes regioselectively. Plenty of cross-coupling as well as cyclocondensation reactions have been performed to build up these skeletons but remained commercially unrealizable. A couple of severe drawbacks are faced by these traditional protocols that require a more straightforward strategy to obviate them. Transition metal-catalyzed C−H functionalization has emerged as a superior alternative in that context. 1,3-Azoles and their benzo counterparts have been extensively functionalized exploiting both noble and earth-abundant transition metals. Lately, C-2 functionalization have gained much traction due to the ease of attaining high regioselectivity and installation of synthetically manipulative functionalities. This critical review presents a bird‘s eye view of all major C-2 functionalization of (benz)azoles catalyzed by a diverse set of metals performed over the past 15 years.     

Electrochemical parameters of aluminum oxide film in situ during anodization of aluminum by white light-optical interferometry

Optical Review - Both Fabry–Pérot interferometry and the DC electrochemical method have been simultaneously used for the first time to measure in situ the anodic current density (J) of...