Benzyl Alcohol Solution Research Articles

Controllable introducing C, N-defects and oxygen-doping on carbon nitride to tune electronic structure and boost photocatalytic hydrogen evolution

In this work, one-step pyrolysis of molten urea and formaldehyde was adopted to introduce O atom, C and N defects in polymeric carbon nitride (CN) for tuning its electronic structures. Results confirmed that the introduced C, N-defects and O dopant could increase the light absorption (440–640 nm) and suppressed the photogenerated charge recombination of CN. The calculated free energies for H* adsorption revealed that the intrinsic H2 evolution activity of C, N-deficient and O-doped CN increased. Accordingly, the optimal sample exhibited an excellent photocatalytic H2 evolution rate (HER) of 18.95 mmol g−1 h−1 in 10% triethanolamine solution under visible light irradiation (1% Pt as a cocatalyst), which was 6.7 times higher than that of traditional CN (2.83 mmol g−1 h−1). In addition, the HER and yield of benzaldehyde were 1.04 and 4.20 mmol g−1 h−1, respectively in 5% benzyl alcohol solution. This work provides a simple and effective strategy to tune the heptazine and electronic structure of CN for large increasing its photocatalytic activity.

Photoreduction of Aqueous Protons Coupling with Alcohol Oxidation on a S-Scheme Heterojunction Photocatalyst MnO/Carbon Nitride.

Crystalline carbon nitride (CCN), derived from amorphous polymeric CN, is considered as a new generation of metal-free photocatalyst because of its high crystallinity. In order to further promote the photocatalytic performance of CCN, p-type MnO nanoparticles are in situ synthesized and merged with n-type CCN through a one-pot process to form p-n heterojunction. The formed interfacial electric field between the semiconductors with different work functions efficiently breaks the coulomb interaction between MnO and CCN. The prepared catalysts exhibit drastically increased photocatalytic hydrogen evolution (PHE) activity integrated with oxidation of alkyl and aryl alcohols under irradiation of visible light. In the aqueous solution of benzyl alcohol (BzOH), the hydrogen generation rate over MnO/CCN (39.58 µmol h-1) is nearly 7 times and 37 times that of pure CCN (5.76 µmol h-1) and CN (1.06 µmol h-1), respectively, combining with oxidation of BzOH to benzaldehyde. This work proposes an avenue for in situ construction of a novel 2D material-based S-scheme heterojunction and extends its application in solar energy conservation and utilization.

Construction of shell-core Co2P/Cd0.9Zn0.1S photocatalyst by electrostatic attraction for enhancing H2 evolution

Solar energy-driven photocatalytic decomposition of water to produce H2 is of great significance for promoting the development of clean energy. To improve the efficiency of H2 production, a novel spherical Co2P/Cd0.9Zn0.1S (Co2P/CZS) composite with shell-core structure was successfully synthesized by electrostatic attraction. Under visible light irradiation, the optimal Co2P/CZS achieves an excellent H2 rate of 16.05 mmol h−1 g−1 in benzyl alcohol (PhCH2OH) solution, with a quantum efficiency of 34.3% at 450 nm. The Co2P thin layer coated on the CZS surface not only facilitates the photogenerated charge transfer from Co2P to CZS under visible light illumination, but reduces the energy barrier of PhCH2OH oxidation and H2 evolution. The present results show that shell-core Co2P/CZS composite may be one of promising catalyst to enhance the activity of H2 evolution, which provides an important reference basis for new catalyst design and wide prospects for further application of metal sulfides.

Synthesis of water soluble copper(II), manganese(III) phthalocyanines and their photocatalytic performances in benzyl alcohol photoxidation

In this study, peripherally tetra-{[4-(3,5-dichlorophenyl)-5-pyridin-4-yl-4H-1,2,4-triazol-3-yl]thio} group substituted cobalt(II), manganese(III) phthalocyanines (BS-1-Cu, BS-1-Mn) and their water soluble derivatives (BS-1-CuQ, BS-1-MnQ) were synthesized via multistep reactions. The structure of new compounds were characterized by FT-IR, 1H-NMR, 13-CNMR, Mass, and UV visible spectroscopy. Then, photocatalytic properties of water soluble phthalocyanines (BS-1-CuQ, BS-1-MnQ) were investigated in benzyl alcohol (BA) photoxidation reaction. Photocatalytic results indicate that the former has high benzaldehyde selectivity (93%) and the latter employees with high product conversion (83%) at the same reaction conditions. The same yield of benzaldehyde (59%) was calculated with both photocatalysts at room temperature in water. The photocatalytic activity of BS-1-CuQ and BS-1-MnQ was evaluated by changing substrate amount and oxidant type. Additionally, the degradation of the BA were investigated in the presence of 0.05 g catalyst, 100 ml 0.015 M BA solution, 25 °C, 15 min in water. The recycling studies indicated that BS-1-MnQ can be used after 4 cycles, BS-1-CuQ can be used even after 3 cycles.

ZnCo2S4/Zn0.2Cd0.8 S Z-scheme heterojunction: Efficient photocatalytic H2 evolution coupling selective oxidation of benzyl alcohol

The Z-scheme heterojunction photocatalysts possess excellent photocatalytic activity benefitting from their properly matched edge potentials. In this work, ZnCo2S4 nanoparticles are anchored on Zn0.2Cd0.8S solid solution nanowires and assembled into binary ZnCo2S4/Zn0.2Cd0.8S nanocomposites. The as-synthesized ZnCo2S4/Zn0.2Cd0.8S nanocomposites act as bifunctional photocatalysts, which can be used for high-performance H2 production coupling synthesis of high-value-added benzaldehyde in low concentration benzyl alcohol solution. Under visible light irradiation, 20%-ZnCo2S4/Zn0.2Cd0.8S nanocomposite shows the highest H2 evolution rate of 23.02 mmol g−1 h−1 in the first photocatalytic cycle, which is 395.0 and 526.7 times higher than that of Zn0.2Cd0.8S and ZnCo2S4 under the same conditions. Eventually, after six-time cycles, the conversion rate and selectivity of benzyl alcohol oxidation to benzaldehyde are 54.3% and 92.2%, respectively. The enhancement of photocatalytic performance is mainly attributed to the Z-scheme heterojunction between ZnCo2S4 and Zn0.2Cd0.8S, which promote the separation and transfer of photogenerated charge carriers. This work provides strong support for the rational design of Z-scheme nano-heterojunction of highly efficient photocatalytic application in H2 evolution and fine chemicals production.

Understanding the Interaction of Gluconamides and Gluconates with Amino Acids in Hair Care.

A hair care mixture formed from a gluconamide derivative and 3-hydroxypropyl ammonium gluconate is known to strengthen hair fibers; however, the mechanism by which the mixture affects hair is unknown. To give insight into the aggregation of the target gluconamide and potential interactions between the gluconate-derived mixture and hair fibers, a range of systems were characterized by X-ray crystallography namely two polymorphic forms of the target gluconamide and three salts of 3-hydroxypropylammonium with sulfuric acid, methane sulfonic acid, and oxalic acid. The gluconamide proves to aggregate and becomes a supramolecular gelator in aniline and benzyl alcohol solution. The resulting gels were characterized by rheology, scanning electron microscopy, proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, and powder X-ray diffraction.

Efficient benzaldehyde photosynthesis coupling photocatalytic hydrogen evolution

Photosynthesis of organic compounds in coupling with promoted hydrogen evolution under mild conditions of light irradiation is considered as one of the most efficient and promising approach to obtain high purity hydrogen and value-added chemicals concurrently by utilizing green solar energy. Here, we report the synthesis of NiS nanoparticle-modified CdS nanorod composites (NiS/CdS) as an efficient bifunctional catalyst for the highly selective photocatalytic synthesis of high-value-added product benzaldehyde (BAD) from aqueous solution of benzyl alcohol (BA) under oxygen-free conditions, in accompanying with the efficient hydrogen evolution. The synergetic catalytic effect between NiS and CdS is proposed to play an important role in elevating the photo-redox performance. The composition-optimized 30% NiS/CdS catalyst affords an extraordinarily high H2 generation rate of 207.8 μmol h−1 and a simultaneous BAD generation rate of 163.8 μmol h−1 under visible light irradiation, which are respectively 139 and 950 times higher than those of CdS without NiS modification. To our knowledge, these are the highest photocatalytic production rates of both H2 and aldehyde ever reported on the concurrent photocatalytic of aldehyde synthesis and hydrogen evolution in green aqueous solution. This work provides a highly efficient photosynthesis strategy for the concurrent productions of high-value-added fine chemicals and hydrogen.

Effect of n‐Alkyl Side Chain Length on the Thermal and Rheological Properties of PolyN‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl)acrylamide) Homopolymers

AbstractFour new N‐isopropylacrylamide‐ and N‐n‐alkyl amine‐based acrylamide monomers, N‐(3‐(alkylamino)‐N‐(3‐(isopropylamino)‐3‐oxopropyl) acrylamide (Mn) (n = 4, 8, 10, 12) are successfully synthesized and polymerized via reversible addition‐fragmentation chain‐transfer polymerization (polyMn, n = 4, 8, 10, and 12), which are characterized by gel permeation chromatography, 1H NMR, Fourier transform infra red spectroscopy, thermo‐gravimetry‐differential thermal analysis, differential scanning calorimetry (DSC), and rheology. All polymers are thermally stable and undergo a two‐step degradation process at ≈280 and ≈375 °C. Glass transition temperature (Tg)s of these polymers decrease gradually from 99.6 to 52.5 °C with increasing n‐alkyl side chain length. The rheology of these polymers in melt state agrees to a typical Rouse‐melt behavior and allows for confirming the Tg determined from DSC. Benzyl alcohol solution rheology proves a weak structural build‐up, in particular for polyM12. Comparison of the quantum chemical calculations of polyMns with n = 4–8 reveals increase in backbone helicity with increasing n‐alkyl side chain length.

Semi-Crystalline Hydrophobic Polyamidoamines: A New Family of Technological Materials?

The hitherto known polyamidoamines (PAAs) are not suitable as structural materials because they are usually water-soluble or swellable in water. This paper deals with the synthesis and characterization of semi-crystalline hydrophobic PAAs (H-PAAs) by combining different bis-sec-amines with bis-acrylamides obtained from C6–C12 bis-prim-amines. H-PAAs were initially obtained in a solution of benzyl alcohol, a solvent suitable for both monomers and polymers. Their number average molecular weights, , which were determined with 1H-NMR by evaluating the percentage of their terminal units, varied from 6000 to >10,000. The solubility, thermal properties, ignitability and water resistance of H-PAAs were determined. They were soluble in organic solvents, semi-crystalline and thermally stable. The most promising ones were also prepared using a bulk process, which has never been previously reported for PAA synthesis. In the form of films, these H-PAAs were apparently unaffected by water. The films underwent tensile and wettability tests. They showed similar Young moduli (260–263 MPa), whereas the maximum stress and the stress at break depended on the number of methylene groups of the starting bis-acrylamides. Their wettability was somewhat higher than that of common Nylons. Interestingly, none of the H-PAAs considered, either as films or powders, ignited after prolonged exposure to a methane flame.

Highly hydrophilic and stable polylactic acid surface achieved by argon plasma treatment

The effect of modifying additives such as low molecular weight polylactide (PLA) and benzyl alcohol (BA) on the degree of hydrophilicity of high molecular weight PLA before and after plasma treatment with low density and specific power per area was investigated. The lowest water contact angle (WCA) after modification was about 17°. A comparative evaluation of the formed functional groups amount, the hydrophilicity and stability of the plasma modification was carried out. WCA measurements of ageing of modified samples over time up to one year was carried out. It was found that plasma treated PLA films, obtained from tetrahydrofuran solution of high-molecular weight PLA and BA, demonstrated one of the highest ageing stability at high hydrophilicity. At the same time, the increase of the oxygen-containing functional groups amount on the modified PLA surface (about 40%, estimated by XPS) is close to the critical value in point of view of ensuring both high hydrophilicity and stability of the PLA surface after the modification.

In Situ Generation of Organic Peroxide to Create a Nanotubular Uranyl Peroxide Phosphate

AbstractCurrent synthetic pathways for uranyl peroxide materials introduce high initial concentrations of aqueous H2O2 that decline over time. Alternatively, in situ generation of organic peroxide would maintain constant concentrations of peroxide over prolonged periods of time and open new pathways to novel uranyl peroxide compounds. Herein, we demonstrate this concept through the synthesis of a nanotube‐like uranyl peroxide phosphate (NUPP), Na12[(UO2)(μ‐O2)(HPO4)]6(H2O)40, making use of the inhibited autoxidation of benzaldehyde in benzyl alcohol solutions in the presence of phosphonate ligands. The unique feature of NUPP is the bent dihedral angle U‐(μ‐O2)‐U (123.9°±0.4° to 124.6°±0.5°), which allows hexameric uranyl peroxide macrocycles to adopt the nanotubular topology and prevents the formation of nanocapsules. Raman spectroscopy of the solution phase confirms our mechanistic understanding of the reaction pathway and confirms that consistent levels of peroxide are generated in situ over an extended period of time.

In Situ Generation of Organic Peroxide to Create a Nanotubular Uranyl Peroxide Phosphate.

Current synthetic pathways for uranyl peroxide materials introduce high initial concentrations of aqueous H2 O2 that decline over time. Alternatively, in situ generation of organic peroxide would maintain constant concentrations of peroxide over prolonged periods of time and open new pathways to novel uranyl peroxide compounds. Herein, we demonstrate this concept through the synthesis of a nanotube-like uranyl peroxide phosphate (NUPP), Na12 [(UO2 )(μ-O2 )(HPO4 )]6 (H2 O)40 , making use of the inhibited autoxidation of benzaldehyde in benzyl alcohol solutions in the presence of phosphonate ligands. The unique feature of NUPP is the bent dihedral angle U-(μ-O2 )-U (123.9°±0.4° to 124.6°±0.5°), which allows hexameric uranyl peroxide macrocycles to adopt the nanotubular topology and prevents the formation of nanocapsules. Raman spectroscopy of the solution phase confirms our mechanistic understanding of the reaction pathway and confirms that consistent levels of peroxide are generated in situ over an extended period of time.

Application of Spectral Methods to Study the Stability of Amiodarone Hydrochloride Micellar Solutions

The stability of micellar solutions of amiodarone hydrochloride in the presence of polysorbate-80 and benzyl alcohol was studied using fluorescence spectrometry with λex = 420 m and λem = 506 nm. A formation scheme for mixed micelles consisting of nonionizable surfactant polysorbate-80 and cationic amiodarone with chloride counterion was proposed. Benzyl alcohol was found to lower the stability of the mixed micelles and lead to crystallization of amiodarone hydrochloride. The counterion was replaced in the presence of acetate so that crystals of amiodarone acetate with a characteristic band for acetate carbonyl stretching vibrations νC=O at 1734 cm–1 were formed. The solubilities of amiodarone hydrochloride and acetate in H2O at 20°C were determined to be 0.33 and 0.058 mg/mL. A change of the amiodarone hydrochloride to polysorbate-80 mole ratio and avoidance of benzyl alcohol and acetate-containing solutions are recommended to improve the stability of the parenteral dosage form.

Toxicity assessment of the extractables from multi-layer coextrusion poly ethylene bags exposed to pH=5 solution containing 4% benzyl alcohol and 0.1 M sodium acetate

A non-target analysis was developed for the analysis of extractables from multi-layer coextrusion bags exposed to 4% benzyl alcohol solution and 0.1 M sodium acetate at pH = 5 for defined periods (15 day, 45 day and 90 day) according to manufacturer instructions based on the ultra-performance liquid chromatography (UPLC) quadrupole-time of flight mass spectrometry (Q-TOF MS). In order to confirm the extractables, principal component analysis (PCA) was used to indicate the differences among samples of different periods. Then, the extractables were identified based on searching the self-built library or online searching. The total content of extractables of 90 day samples was 589.78 μg/L, and the content was in the range of acceptable levels for pharmaceutical manufacturers. The risk assessment of the extractables were evaluated by Toxtree and T.E.S.T. software to avoid the animals bioexperiment.

3D imaging of cleared human skin biopsies using light-sheet microscopy: A new way to visualize in-depth skin structure.

Human skin is composed of the superimposition of tissue layers of various thicknesses and components. Histological staining of skin sections is the benchmark approach to analyse the organization and integrity of human skin biopsies; however, this approach does not allow 3D tissue visualization. Alternatively, confocal or two-photon microscopy is an effective approach to perform fluorescent-based 3D imaging. However, owing to light scattering, these methods display limited light penetration in depth. The objectives of this study were therefore to combine optical clearing and light-sheet fluorescence microscopy (LSFM) to perform in-depth optical sectioning of 5mm-thick human skin biopsies and generate 3D images of entire human skin biopsies. A benzyl alcohol and benzyl benzoate solution was used to successfully optically clear entire formalin fixed human skin biopsies, making them transparent. In-depth optical sectioning was performed with LSFM on the basis of tissue-autofluorescence observations. 3D image analysis of optical sections generated with LSFM was performed by using the Amira® software. This new approach allowed us to observe in situ the different layers and compartments of human skin, such as the stratum corneum, the dermis and epidermal appendages. With this approach, we easily performed 3D reconstruction to visualise an entire human skin biopsy. Finally, we demonstrated that this method is useful to visualise and quantify histological anomalies, such as epidermal hyperplasia. The combination of optical clearing and LSFM has new applications in dermatology and dermatological research by allowing 3D visualization and analysis of whole human skin biopsies.

Facile Synthesis of Optically Active and Thermoresponsive Star Block Copolymers Carrying Helical Polyisocyanide Arms and Their Thermo-Triggered Chiral Resolution Ability.

A left-handed helical poly(phenyl isocyanide) bearing a norbornene unit and a Pd(II) complex on each terminus was prepared. The norbornene terminus was core cross-linked with a bisnorbornene linker via ring-opening metathesis polymerization (ROMP), yielding a star polymer carrying left-handed helical arms decorated with Pd(II) units at the exterior. The optical activities of the helical arms were maintained after the cross-linking reaction. The Pd(II) units on the surface of the star polymer were chain extended with a new phenyl isocyanide bearing three hydrophilic triethylene glycol monomethyl chains, which afforded an amphiphilic star block copolymer carrying helical arms. Such a star block copolymer showed excellent thermoresponsiveness with the lower critical solution temperature (LCST) around 55 °C. This optically active and thermoresponsive star polymer can enantioselectively capture the S-enantiomer of racemic methyl benzyl alcohol solution at a temperature lower than the LCST and precipitated when the temperature was higher than the LCST, leaving the R-enantiomer in the solution. The enantiomeric excess (ee) of the isolated enantiomer is up to 75%.

Dopant-dependent crystallization and photothermal effect of Sb-doped SnO2 nanoparticles as stable theranostic nanoagents for tumor ablation.

Ideal theranostic nanoagents should be "all-in-one" type nanocrystals that have a single-semiconductor component and all-required properties (such as imaging and photothermal effects), but most semiconductor nanocrystals do not have these required properties. With SnO2 as a model of a typical wide-band semiconductor, we report the tuning from UV-responsive SnO2 to blue SnO2 nanocrystals with imaging ability and a Sb-doping-dependent photothermal effect. Sb-Doped SnO2 nanocrystals were prepared by heating SbCl3 and SnCl4 in benzyl alcohol solution through a facile solvothermal route. When the SbCl3/SnCl4 molar ratio increases from 0 to 0.2/1, the obtained samples exhibit an increased photothermal effect under the irradiation of a 1064 nm laser, accompanied by gradually decreased size and crystallinity. With a further increase of the molar ratio from 0.3/1.0 to 1.0/1.0, the resulting samples demonstrate the tetragonal SnO2 phase with amorphous-like compounds and they show no obvious enhancement of a photothermal effect. After a surface modification with biological molecules, the optimized Sb0.2-SnO2 nanocrystals demonstrated good stability and a high photothermal conversion efficiency of 48.3% as well as low cytotoxicity. When Sb0.2-SnO2 was injected into a tumor of mice, the tumor could be simultaneously detected by X-ray computed tomography (CT) and photoacoustic (PA) imaging, and then thermally ablated when exposed to a 1064 nm laser. Therefore, these nanocrystals can be used as "all-in-one" type nanoagents for imaging guided photothermal ablation of tumors under the irradiation of a laser in the second bio-transparent window.

Life Sciences Discovery and Technology Highlights

Life Sciences Discovery and Technology Highlights

Ionic liquid-assisted synthesis of unusual Pd particles with enhanced electrocatalytic performance for ethanol and methanol oxidation

A facile ionic liquid-assisted route is proposed for the morphology-controllable synthesis of Pd particles in benzyl alcohol solution. Flower-like, raspberry-like and chain-like Pd particles can be synthesized by the present route. Specifically, the flower-like particles are constructed with concave tetrahedral subunits which are completely different from the reported inorganic flower-like particles usually with flat flakes. The ionic liquid played an important role in the formation of these interesting particles. In particular, the synthesized flower-like Pd particles exhibited remarkably improved electrocatalytic activity towards ethanol and methanol oxidation compared with that of the commercial Pd black catalyst.

Immunostaining, Dehydration, and Clearing of Mouse Embryos for Ultramicroscopy

This protocol describes the preparation of mouse embryos for ultramicroscopy (UM), a powerful imaging technique that achieves precise and accurate three-dimensional (3D) reconstructions of intact macroscopic specimens with micrometer resolution. In UM, a specimen in the size range of ∼1-15 mm is illuminated perpendicular to the observation pathway by two thin counterpropagating sheets of laser light. In combination with fluorescein isothiocyanate (FITC) immunostaining, UM allows visualization of somatic motor and sensorial nerve fibers in whole mouse embryos. Even the fine branches of the sensomotoric fibers can be visualized over a distance of up to several millimeters. In this protocol, mouse embryos are fixed and immunostained in preparation for UM. Because UM requires the excitation light sheet to travel throughout the entire horizontal width of the specimen, specimens usually have to be rendered transparent before microscope inspection. Here, the embryos are dehydrated in ethanol and then cleared in a solution of benzyl alcohol and benzyl benzoate.