A post-sulfonated one-pot synthesized magnetic cellulose nanocomposite for Knoevenagel and Thorpe-Ziegler reactions.

The development of biodegradable and active cellulosic-based heterogeneous catalysts for the synthesis of different organic compounds would be attractive in pharmaceutical and petrochemical-related industries. Herein, a post-sulfonated composite of one-pot synthesized magnetite (Fe3O4) and cellulose nanocrystals (CNCs) was used as an effective and easily separable heterogeneous catalyst for activating the Knoevenagel and Thorpe-Ziegler reactions. The composite was developed hydrothermally from microcrystalline cellulose (MCC), iron chlorides, urea, and hydrochloric acid at 180 °C for 20 h in a one-pot reaction. After collecting the magnetic CNCs (MCNCs), post-sulfonation was performed using chlorosulfonic acid (ClSO3H) in DMF at room temperature producing sulfonated MCNCs (SMCNCs). The results confirmed the presence of sulfonated Fe3O4 and CNCs with a hydrodynamic size of 391 nm (±25). The presence of cellulose was beneficial for preventing Fe3O4 oxidation or the formation of agglomerations without requiring the presence of capping agents, organic solvents, or an inert environment. The SMCNC catalyst was applied to activate the Knoevenagel condensation and the Thorpe-Ziegler reaction with determining the optimal reaction conditions. The presence of the SMCNC catalyst facilitated these transformations under green procedures, which enabled us to synthesize a new series of olefins and thienopyridines, and the yields of some isolated olefins and thienopyridines were up to 99% and 95%, respectively. Besides, the catalyst was stable for five cycles without a significant decrease in its reactivity, and the mechanistic routes of both reactions on the SMCNCs were postulated.

One-pot synthesis of magnetic cellulose nanocrystal and its post-functionalization for doxycycline adsorption.

The composite of magnetite (Fe3O4) and cellulose nanocrystal (CNC) is considered a potential adsorbent for water treatment and environmental remediation. In the current study, a one-pot hydrothermal procedure was utilized for magnetic cellulose nanocrystal (MCNC) development from microcrystalline cellulose (MCC) in the presence of ferric chloride, ferrous chloride, urea, and hydrochloric acid. The x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and Fourier-transform infrared spectroscopy analysis confirmed the presence of CNC and Fe3O4, while transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis verified their respective sizes (< 400 nm and ≤ 20 nm) in the generated composite. To have an efficient adsorption activity for doxycycline hyclate (DOX), the produced MCNC was post-treated using chloroacetic acid (CAA), chlorosulfonic acid (CSA), or iodobenzene (IB). The introduction of carboxylate, sulfonate, and phenyl groups in the post-treatment was confirmed by FTIR and XPS analysis. Such post treatments decreased the crystallinity index and thermal stability of the samples but improved their DOX adsorption capacity. The adsorption analysis at different pHs revealed the increase in the adsorption capacity by reducing the basicity of the medium due to decreasing electrostatic repulsions and inducing strong attractions.

Ag@TiO2 Nanocomposite as an Efficient Catalyst for Knoevenagel Condensation.

In the present study, a new series of different heterocycles was synthesized through base-free Knoevenagel condensation of various aldehydes and active methylene-containing compounds using the hydrothermal developed Ag@TiO2 as a heterogeneous catalyst. The catalyst was synthesized by mixing TiO2 (P25) with AgNO3 and hydrothermally treated in ethanol at 180 °C for 12 h. The developed Ag@TiO2 catalyst was directly applied for Knoevenagel condensation, and the optimized procedure involved stirring the aldehydes and active methylene-containing compounds with Ag@TiO2 in ethanol at 65 °C. The reaction scope was investigated for various aromatic and heterocyclic aldehydes with active methylene-containing compounds, and the isolated yields were significantly high. The reusability of the catalyst was investigated for up to five cycles, where an insignificant decrease in the catalyst's reactivity was observed. Also, the reaction could proceed in water as a solvent, and the isolated yield was 40%. Hence, this protocol features mild reaction conditions, a facile procedure, and clean reaction profiles.

Relationship between the subgingival microbiome and menopausal hormone therapy use: The Buffalo OsteoPerio study.

BACKGROUND: This study investigated the association between menopausal hormone therapy (HT) use and the subgingival microbiome, for which published information is limited. METHODS: This cross-sectional study included 1270 postmenopausal women, aged 53-81 years, who completed clinical examinations. Detailed information on HT use (type, delivery mode, duration) was obtained from questionnaires. HT use was categorized into three groups (never, former, current). 16S rRNA sequencing was performed on subgingival plaque samples obtained during dental examinations. Operational taxonomic units were centered log2-ratio (CLR) transformed to account for the compositional data structure. Analysis of variance was used to compare mean microbial relative abundances across HT categories with Benjamini-Hochberg correction. RESULTS: Significantly higher alpha diversity (Shannon Index) and beta diversity (Aitchison distance) was observed in never compared with current HT users (p < 0.05, each). Of the total 245 microbial taxa identified, 18 taxa differed significantly among the three HT groups, 11 of which were higher in current users and seven of which were lower in current users as compared with never users (p < 0.05, each). Differences in relative abundance between never and current HT users were materially unchanged after adjustment for age, body mass index, and oral hygiene. CONCLUSIONS: Relative abundance of several subgingival bacteria differed significantly between never and current HT users in a cohort of postmenopausal women. Additional studies are needed to determine the extent that these relationships might account for the previously reported inverse association between HT use and periodontal disease in older women.

Base-Free Synthesis and Photophysical Properties of New Schiff Bases Containing Indole Moiety.

Schiff bases represent an essential class in organic chemistry with antitumor, antiviral, antifungal, and antibacterial activities. The synthesis of Schiff bases requires the presence of an organic base as a catalyst such as piperidine. Base-free synthesis of organic compounds using a heterogeneous catalyst has recently attracted more interest due to the facile procedure, high yield, and reusability of the used catalyst. Herein, we present a comparative study to synthesize new Schiff bases containing indole moieties using piperidine as an organic base catalyst and Au@TiO2 as a heterogeneous catalyst. In both methods, the products were isolated in high yields and fully characterized using different spectral analysis techniques. The catalyst was reusable four times, and the activity was slightly decreased. The presence of Au increases the number of acidic sites of TiO2, resulting in C=O polarization. Yields of the prepared Schiff bases in the presence of Au@TiO2 and piperidine were comparable. However, Au@TiO2 is an easily separable and recyclable catalyst, which would facilitate the synthesis of organic compounds without applying any hazardous materials. Furthermore, the luminescence behavior of the synthesized Schiff bases exhibited spectral shape dependence on the substituent group. Interestingly, the compounds also displayed deep-blue fluorescence with Commission Internationale de l'Éclairage (CIE) coordinates of y < 0.1. Thus, these materials may contribute to decreasing the energy consumption of the emitting devices.

Hierarchical porous zeolitic imidazolate frameworks (ZIF-8) and ZnO@N-doped carbon for selective adsorption and photocatalytic degradation of organic pollutants.

Removing organic contaminants such as dyes from water is essential to purify wastewater. Herein, zeolitic imidazolate framework-8 (ZIF-8) and ZnO@N-doped C are reported as effective adsorbents and photocatalysts for the adsorption and degradation of organic dyes. The materials showed effective and selective adsorption toward anionic dyes such as methyl blue (MeB) dye in the presence of fluorescein (FLU) dye. The adsorption capacities of ZnO@N-doped C for MeB and FLU dyes are 900 mg g-1 and 100 mg g-1, respectively. According to UV-Vis diffuse reflectance spectroscopy (DRS) data, ZnO@N-doped C has a lower bandgap (2.07 eV) than ZIF-8 (4.34 eV) and ZnO (3.12 eV). Thus, ZnO@N-doped C serves as an effective photocatalyst for the degradation of both dyes under UV exposure. The degradation efficiency capacity of the dye (50 mg L-1) is >90% using 200 mg L-1 of the photocatalyst. The mechanism of adsorption and photocatalysis is investigated. The photodegradation pathway of the dye involved the generation of oxidative hydroxy radicals (OH˙), which can degrade the dyes. The degradation products of FLU were recorded using mass spectrometry.

Controlled Growth of Organosilane Micropatterns on Hydrophilic and Hydrophobic Surfaces Templated by Vacuum Ultraviolet Photolithography.

In this report, micropatterns of (3-aminopropyl)trimethoxysilane (APTMS) were developed on hydrophilic and hydrophobic surfaces after patterning using 172 nm vacuum ultraviolet (VUV) photolithography. Self-assembled monolayers (SAMs) formed on Si substrates through UV hydrosilylation of 1-hexadecene (HD) and 10-undecenoic acid (UDA) were used as hydrophilic and hydrophobic surfaces, respectively. For templating the HD- and UDA-SAMs, the VUV light was exposed to HD- and UDA-SAMs from the slits of photomasks in atmospheric and evacuated environments, respectively. Various oxygenated groups were generated at the exposed domains of HD-SAM, while the COOH groups were trimmed from the irradiated domains of UDA-SAM. The APTMS molecules were immobilized on the domains that were terminated by oxygenated groups after chemical vapor deposition (CVD). The thicknesses of the developed APTMS micropatterns increased significantly by raising the CVD temperature and in the presence of ambient air in the CVD Teflon container as well. The increase in thicknesses was ascribed to the formation of APTMS multilayers, which were mediated by H3N+ ions. Also, the developed APTMS micropatterns on the UDA-SAM patterned by VUV light irradiation in a high-vacuum environment (HV-VUV) were thicker than those on the VUV/(O) patterned HD-SAM due to the presence of inactive oxygenated groups at the surface of VUV/(O)-terminated domains of HD-SAM such as COO-C and C-O-C groups. The presence of water or ambient air facilitated the silane coupling between the silyl groups with the oxygenated and amino groups The combination of VUV photolithography and the CVD method with control of the conditions would enable us to control the thicknesses and shapes of the developed APTMS micropatterns. These findings illustrate the applicability of VUV photolithography for templating hydrophobic and hydrophobic surfaces toward the development of organosilane architectures, which can be feasible for several applications.

Formation of submicron-sized silica patterns on flexible polymer substrates based on vacuum ultraviolet photo-oxidation.

Formation of precise and high-resolution silica micropatterns on polymer substrates is of importance in surface structuring for flexible device fabrication of optics, microelectronic, and biotechnology. To achieve that, substrates modified with affinity-patterns serve as a strategy for site-selective deposition. In the present paper, vacuum ultraviolet (VUV) treatment is utilized to achieve spatially-controlled surface functionalization on a cyclo-olefin polymer (COP) substrate. An organosilane, 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), preferentially deposits on the functionalized regions. Well-defined patterns of TMCTS are formed with a minimum feature of ∼500 nm. The secondary VUV/(O)-treatment converts TMCTS into SiO x , meanwhile etches the bare COP surface, forming patterned SiO x /COP microstructures with an average height of ∼150 nm. The resulting SiO x patterns retain a good copy of TMCTS patterns, which are also consistent with the patterns of photomask used in polymer affinity-patterning. The high quality SiO x patterns are of interests in microdevice fabrication, and the hydrophilicity contrast and adjustable heights reveal their potential application as a "stamp" for microcontact printing (µCP) techniques.

1,2-Epoxyalkane: Another Precursor for Fabricating Alkoxy Self-Assembled Monolayers on Hydrogen-Terminated Si(111).

This work describes the UV alkoxylation of a series of 1,2-epoxyalkanes on the hydrogen-terminated silicon (H-Si) substrate. The formation of alkoxy self-assembled monolayers (SAMs) and the nature of bonding at the surface of H-Si were examined using water contact angle goniometer, spectroscopic ellipsometer, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy. UV exposure to 1,2-epoxyalkane mesitylene solution for 60 min formed alkoxy-SAMs onto H-Si with hydrophobic properties. The local molecular environment of the alkyl chains transitioned from a disordered, liquid-like state to an ordered, crystalline-like structure with increasing the chain length. XPS and FTIR indicated that the reaction of H-Si with 1,2-epoxyalkane produced Si-O-C linkages. The Si-H bond homolysis and electron/hole were the plausible mechanistic routes for the grafting of 1,2-epoxyalkanes.

Vacuum Ultraviolet Treatment of Acid- and Ester-Terminated Self-Assembled Monolayers: Chemical Conversions and Friction Reduction.

We have prepared COOH- and COOCH3-terminated self-assembled monolayers (SAMs) from undec-10-enoic acid (UDA) and methyl undec-10-enoate (MUDO) molecules on hydrogen-terminated silicon (H-Si) substrates through ultraviolet (UV) irradiation. The as-prepared UDA- and MUDO-SAMs were exposed to 172 nm vacuum-UV (VUV) light in a high vacuum environment (HV, <10-3 Pa) for different periods. The presence of COO components at the surfaces of these SAMs without prior oxidation would simplify the understanding of the origin of the chemical conversions and the changes of surface properties, as the prior oxidation would change the surface properties and generate different oxygenated groups. After the HV-VUV treatment, the abundance of COOH and COOCH3 components of these SAMs decreased without significant dissociation of their C-C backbones. Degradation of these components occurred through dissociating their C-O bonds, resulting in different C═O components. Also, the occurrence of Norrish type pathways resulted in a slight decrease of carbon content and produced CH3 components. We have applied the HV-VUV lithography to control the abundance of COOH and COOCH3 components in well-defined areas and to investigate the friction differences between the irradiated and masked areas. The irradiated areas exhibited lower friction than the masked areas without observing significant height contrasts between these areas. The reduction in friction was attributed to the conversion of the COOH and COOCH3 components to less adhesive components such as C═O and CH3. These experiments suggest the HV-VUV treatments as an approach for low damage dry surface modifications and reductive lithographic techniques at surfaces terminated by acid and ester groups.

Low Damage Reductive Patterning of Oxidized Alkyl Self-Assembled Monolayers through Vacuum Ultraviolet Light Irradiation in an Evacuated Environment.

Through 172 nm vacuum ultraviolet light irradiation in a high vacuum condition (HV-VUV), well-defined micropatterns with a varied periodic friction were fabricated at the surface of self-assembled monolayers (SAMs) terminated with oxygenated groups. No apparent height contrast between the HV-VUV-irradiated and -masked areas was observed, which indicated the stability of the C-C skeleton of the assembled molecules. The trimming of oxygenated groups occurred through dissociating the C-O bonds and promoting the occurrence of α- and ß-cleavages in the C═O-containing components. Hence, the HV-VUV treatment trimmed the oxygenated groups without degrading the C-C skeleton. The HV-VUV treatment influenced the order of the assembled molecules, and the step-terrace structure was distorted. The decrease in friction at the HV-VUV-irradiated domains was attributed to the dissociation of oxygenated groups. (3-Aminopropyl)trimethoxysilane (APTMS) aggregated at the masked areas of the HV-VUV-patterned SAM, where the oxygenated groups worked as anchors. APTMS aggregations did not exist at the irradiated areas, indicating the trimming of the oxygenated groups at these areas. The direct assembling of APTMS on the Si substrate at the irradiated areas was prevented by the remaining C-C skeleton.

Correction: Chemical conversion of self-assembled hexadecyl monolayers with active oxygen species generated by vacuum ultraviolet irradiation in an atmospheric environment.

Correction for 'Chemical conversion of self-assembled hexadecyl monolayers with active oxygen species generated by vacuum ultraviolet irradiation in an atmospheric environment' by Ahmed I. A. Soliman et al., Soft Matter, 2015, 11, 5678-5687.

Chemical conversion of self-assembled hexadecyl monolayers with active oxygen species generated by vacuum ultraviolet irradiation in an atmospheric environment.

Vacuum ultraviolet (VUV, λ = 172 nm) irradiation of alkyl self-assembled monolayers (SAMs) in the presence of dry air alters their surface properties. In this work, UV photochemically prepared hexadecyl (HD)-SAMs on hydrogen-terminated silicon substrates were irradiated by VUV light in dry air, which generated active oxygen species upon excitation of the atmospheric oxygen molecules. These active oxygen species converted the terminal methyl groups of the SAMs to polar functional groups, which were examined quantitatively by X-ray photoelectron spectroscopy (XPS) and chemical labeling. At the first stage of VUV irradiation, the surface of SAMs was functionalized, and the ratios of the generated polar functional groups markedly increased. With the elongation of the irradiation period, the SAMs gradually degraded, and the total polar group percentages gradually decreased. The difference between the oxygenated carbon components derived by the deconvolution of the XPS carbon (C1s) spectrum and the chemical labeling of polar groups revealed enormous quantities of ethereal and ester groups that cannot react with the labeling reagents but are included in the C1s spectral envelope. These modifications were reflected on morphological structures of SAMs, which were gradually distorted until a complete amorphous structure was obtained after the complete elimination of HD-SAMs.