Efficient green Cr(VI) adsorbent from sorghum waste: Eco-designed functionalized mesoporous silica FDU-12.

This paper presents an eco-design approach to the synthesis of a highly efficient Cr(VI) adsorbent, utilizing a positively charged surface mesoporous FDU-12 material (designated as MI-Cl-FDU-12) for the first time. The MI-Cl-FDU-12 anion-exchange adsorbent was synthesized via a facile one-pot synthesis approach using sodium silicate extracted from sorghum waste as a green silica source, 1-methyl-3-(triethoxysilylpropyl) imidazolium chloride as a functionalization agent, triblock copolymer F127 as a templating or pore-directing agent, trimethyl benzene as a swelling agent, KCl as an additive, and water as a solvent. The synthesis method offers a sustainable and environmentally friendly approach to the production of a so-called "green" adsorbent with a bimodal micro-/mesoporous structure and a high surface area comparable with the previous reports regarding FDU-12 synthesis. MI-Cl-FDU-12 was applied as an anion exchanger for the adsorption of toxic Cr(VI) oxyanions from aqueous media and various kinetic and isotherm models were fitted to experimental data to propose the adsorption behavior of Cr(VI) on the adsorbent. Langmuir model revealed the best fit to the experimental data at four different temperatures, indicating a homogeneous surface site affinity. The theoretical maximum adsorption capacities of the adsorbent were found to be 363.5, 385.5, 409.0, and 416.9 mg g-1 at 298, 303, 308, and 313 K, respectively; at optimal conditions (pH=2, adsorbent dose=3.0 mg, and contact time of 30 min), surpassing that of most previously reported Cr(VI) adsorbents in the literature. A regeneration study revealed that this adsorbent possesses outstanding performance even after six consecutive recycling.

Highly Active Cellulose-Supported Poly(hydroxamic acid)-Cu(II) Complex for Ullmann Etherification.

Highly active natural pandanus-extracted cellulose-supported poly(hydroxamic acid)-Cu(II) complex 4 was synthesized. The surface of pandanus cellulose was modified through graft copolymerization using purified methyl acrylate as a monomer. Then, copolymer methyl acrylate was converted into a bidentate chelating ligand poly(hydroxamic acid) via a Loosen rearrangement in the presence of an aqueous solution of hydroxylamine. Finally, copper species were incorporated into poly(hydroxamic acid) via the adsorption process. Cu(II) complex 4 was fully characterized by Fourier transform infrared (FTIR), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. The cellulose-supported Cu(II) complex 4 was successfully applied (0.005 mol %) to the Ullmann etherification of aryl, benzyl halides, and phenacyl bromide with a number of aromatic phenols to provide the corresponding ethers with excellent yield [benzyl halide (70-99%); aryl halide (20-90%)]. Cu(II) complex 4 showed high stability and was easily recovered from the reaction mixture. It could be reused up to seven times without loss of its original catalytic activity. Therefore, Cu(II) complex 4 can be commercially utilized for the preparation of various ethers, and this synthetic technique could be a part in the synthesis of natural products and medicinal compounds.

Synthesis of multi-organo-functionalized fibrous silica KCC-1 for highly efficient adsorption of acid fuchsine and acid orange II from aqueous solution.

Multi-functionalized fibrous silica KCC-1 (MF-KCC-1) bearing amine, tetrasulfide, and thiol groups was synthesized via a post-functionalization method and fully characterized by several methods such as FTIR, FESEM, EDX-Mapping, TEM, and N2 adsorption-desorption techniques. Due to abundant surface functional groups, accessible active adsorption sites, high surface area (572 m2 g-1), large pore volume (0.98 cm3 g-1), and unique fibrous structure, mesoporous MF-KCC-1 was used as a potential adsorbent for the uptake of acid fuchsine (AF) and acid orange II (AO) from water. Different adsorption factors such as pH of the dye solution, the amount of adsorbent, initial dye concentration, and contact time, affecting the uptake process were optimized and isotherm and kinetic studies were conducted to find the possible mechanism involved in the process. For both AF and AO dyes, the Langmuir isotherm model and the PFO kinetic model show the most agreement with the experimental data. According to the Langmuir isotherm, the calculated maximum adsorption capacity for AF and AO were found to be 574.5 mg g-1 and 605.9 mg g-1, respectively, surpassing most adsorption capacities reported until now which is indicative of the high potential of mesoporous MF-KCC-1 as an adsorbent for removal applications.

A novel and facile green synthesis method to prepare LDH/MOF nanocomposite for removal of Cd(II) and Pb(II).

To date, many nanoadsorbents have been developed and used to eliminate heavy metal contamination, however, one of the challenges ahead is the preparation of adsorbents from processes in which toxic organic solvents are used in the least possible amount. Herein, we have developed a new carboxylic acid-functionalized layered double hydroxide/metal-organic framework nanocomposite (LDH/MOF NC) using a simple, effective, and green in situ method. UiO-66-(Zr)-(COOH)2 MOF nanocrystals were grown uniformly over the whole surface of COOH-functionalized Ni50Co50-LDH ultrathin nanosheets in a green water system under a normal solvothermal condition at 100 °C. The synthesized LDH/MOF NC was used as a potential adsorbent for removal of toxic Cd(II) and Pb(II) from water and the influence of important factors on the adsorption process was monitored. Various non-linear isotherm and kinetic models were used to find plausible mechanisms involved in the adsorption, and it was found that the Langmuir and pseudo-first-order models show the best agreement with isotherm and kinetic data, respectively. The calculated maximum adsorption capacities of Cd(II) and Pb(II) by the LDH/MOF NC were found to be 415.3 and 301.4 mg g-1, respectively, based on the Langmuir model (pH = 5.0, adsorbent dose = 0.02 g, solution volume = 20 mL, contact time = 120 min, temperature = 25 â„ƒ, shaking speed 200 rpm).

Synthesis of Silica-Supported Hydroxamic Ligand for Removal of Metals Ions from Water.

Mesoporous silica supported adsorbents have been used towards metal ion removal from water due to their thermally stability and good sorption capacity. Thus, mesoporous silica-based methyl acrylate monomer (Silica-APTES-DPNO) was converted into hydroxamic acid (SBHA) by using oximation reaction and all products are analyzed by by FT-IR. The SBHA showed satisfactory binding properties with copper, cobalt, nickel and lead are 242, 206, 195 and 516 mg g-1, respectively, with the batch adsorption system was set to pH 6. The kinetics of metal ions binding obeyed the pseudo-1st-order process up to 60 min. In this study also consider the Langmuir and Freundlich isotherm to find out the sorption behavior. The isotherm study demonstrated the well fit with Freundlich isotherm (R² > 0.99). Thus, adsorption take place as a multilayer system, therefore, SBHA material is useful for the metal ions removal from water.

Facile synthesis of CuO/CdS heterostructure photocatalyst for the effective degradation of dye under visible light.

In this work, the photocatalytic property of p-type CuO was tailored by creating a heterojunction with n-type CdS. The CuO/CdS nanocomposite photocatalyst was synthesized by the ultrasound-assisted-wet-impregnation method and the physicochemical and optical properties of the catalysts were evaluated by using N2 physisorption, X-Ray Diffraction (XRD),X-Ray Photoelectron Spectroscopy (XPS), Raman spectroscopy, Transmission electron microscopy (TEM), Energy dispersive X-Ray (EDX) mapping, Field Emission Scanning Electron Microscope (FE-SEM), UV-Vis and photoluminescence spectroscopy experiments. Detailed characterization revealed the formation of a nanocomposite with a remarkable improvement in the charge carrier (electron/hole) separation. The photocatalytic degradation efficiencies of CuO and CuO/CdS were investigated for different dyes, for instance, rhodamine B (RhB), methylene blue (MLB), methyl blue (MB) and methyl orange (MO) under visible light irradiation. The obtained dye degradation efficiencies were ~93%, ~75%, ~83% and ~80%, respectively. The quantum yield for RhB degradation under visible light was 6.5 × 10-5. Reusability tests revealed that the CuO/CdS photocatalyst was recyclable up to four times. The possible mechanisms for the photocatalytic dye degradation over CuO/CdS nanocomposite were elucidated by utilizing various scavengers. Through these studies, it can be confirmed that the conduction band edges of CuO and CdS play a significant role in producing O2-. The produced O2- degraded the dye molecules in the bulk solution whereas the valence band position of CuO acted as the water oxidation site. In conclusion, the incorporation of CuO with CdS was demonstrated to be a viable strategy for the efficient photocatalytic degradation of dyes in aqueous solutions.

Poly(amidoxime) ligand derived from waste palm fiber for the removal of heavy metals from electroplating wastewater.

A waste material known as palm oil empty fruit bunch (EFB) is used as a source of cellulose for the development of polymeric materials for the removal of metal ions from industrial wastewater. A poly(acrylonitrile)-grafted palm cellulose copolymer was synthesized by a conventional free radical initiating process followed by synthesis of a poly(amidoxime) ligand by oximation reaction. The resulting products were characterized by FT-IR, FE-SEM, EDX, TGA, DSC, and XPS. The poly(amidoxime) ligand was used to coordinate with and extract a series of transition metal ions from water samples. The binding capacity (qe) of the ligand with the metal ions such as copper, iron, cobalt, nickel, and lead were 260, 210, 168, 172, and 272 mg g-1, respectively at pH 6. The adsorption process followed the pseudo-first-order kinetic model (R2 > 0.99) and as well as the Freundlich isotherm model (R2 > 0.99) indicating the occurrence of a multi-layer adsorption process in the amidoxime ligand adsorbent. Results from reusability studies show that the ligand can be recycled for at least 10 cycles without any significant losses to its initial adsorption capacity. The synthesized polymeric ligand was shown to absorb heavy metals from electroplating wastewater with up to 95% efficiency.

Ion-Imprinted Polymer for Selective Separation of Cerium(III) Ions from Rare Earth Mixture.

Ion-imprinting polymers (IIPs) materials draw the great recognition because of the powerful selectivity to the desired metal ions. Therefore, the ion-imprinting polymer (Ce-IIP) was prepared by using cerium metal with amidoxime ligand as the complexing agent, in addition ethylene glycol dimethacrylate (EGDMA) and 2,2-azobisisobutyronitrile (AIBN) are crosslinking agent and free radical initiator, respectively. Aqueous HCl was applied to leach the cerium ions from the imprinted polymer for the creation of cavities of template, which is utilized for further cerium ions adsorption with high selectivity. The Ce-IIP was characterized by using ICP-MS, FE-SEM and also solid state analysis by UV-vis NIR spectroscopy. FT-IR study confirmed the complexation of the Ce-IIP was successful. The optimum pH was found to be 6 and the highest adsorption capacity was estimated about 145 mg g-1. Thus, the prepared Ce-IIP gave very good selectivity to cerium ions in the presence of lanthanide ions and also Ce-IIP can be reused 10 times without a substantial loss in adsorption capacity.

Cellulose Supported Pd(II) Complex Catalyzed Carbon-Carbon Bonds Formation.

Corn-cobs are an agro-industrial waste and composed of cellulose mostly. In this study cellulose was isolated from the waste corn-cobs and modified to polymeric hydroxamic acid palladium complex 1 and characterized by using a variety of spectroscopic methods such as field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The complex 1 exhibited high catalytic activity towards Suzuki and Heck coupling reactions of activated and deactivated aryl halides to give the respective coupling products with high yield. Moreover, the complex 1 was recovered and recycled five times with no considerable loss of catalytic overall performance.

Colchicine prodrugs and codrugs: Chemistry and bioactivities.

Antimitotic colchicine possesses low therapeutic index due to high toxicity effects in non-target cell. However, diverse colchicine analogs have been derivatized as intentions for toxicity reduction and structure-activity relationship (SAR) studying. Hybrid system of colchicine structure with nontoxic biofunctional compounds modified further affords a new entity in chemical structure with enhanced activity and selectivity. Moreover, nanocarrier formulation strategies have been used for colchicine delivery. This review paper focuses on colchicine nanoformulation, chemical synthesis of colchicine prodrugs and codrugs with different linkers, highlights linker chemical nature and biological activity of synthesized compounds. Additionally, classification of colchicine prodrugs based on type of conjugates is discussed, as biopolymers prodrugs, fluorescent prodrug, metal complexes prodrug, metal-labile prodrug and bioconjugate prodrug. Finally, we briefly summarized the biological importance of colchicine nanoformulation, colchicine prodrugs and codrugs.

Tapioca Cellulose Based Copper Nanoparticles for Chemoselective N-Alkylation.

Biomaterials as a support for catalysts are of prime importance. Tapioca root which is an abundant biopolymer source was used to synthesize cellulose supported bio-heterogeneous poly(hydroxamic acid) copper nanoparticles (CuN@PHA) and was characterized by Fourier transform infrared spectroscopy (FTIR), ultraviolet­visible spectroscopy (UV-Vis), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), transmission electron microscopy (TEM) analyses. The tapioca cellulose supported CuN@PHA (50 mol ppm) effectively catalyzed N-alkylation reaction of aliphatic amines with α,ß-unsaturated compounds to give the corresponding alkylated products. High yields up to 95% were achieved for the converted products. The reusability of the cellulose supported nanoparticles was found to be excellent with no significant reduction of its catalytic activity over several cycles. The catalyst showed high catalytic activity having turnover number (TON) 18000 and turnover frequency (TOF) 2250 h⁻¹.

Bio-waste corn-cob cellulose supported poly(hydroxamic acid) copper complex for Huisgen reaction: Waste to wealth approach.

Corn-cob cellulose supported poly(hydroxamic acid) Cu(II) complex was prepared by the surface modification of waste corn-cob cellulose through graft copolymerization and subsequent hydroximation. The complex was characterized by IR, UV, FESEM, TEM, XPS, EDX and ICP-AES analyses. The complex has been found to be an efficient catalyst for 1,3-dipolar Huisgen cycloaddition (CuAAC) of aryl/alkyl azides with a variety of alkynes as well as one-pot three-components reaction in the presence of sodium ascorbate to give the corresponding cycloaddition products in up to 96% yield and high turn over number (TON 18,600) and turn over frequency (TOF 930h-1) were achieved. The complex was easy to recover from the reaction mixture and reused six times without significant loss of its catalytic activity.

Synthesis of new liquid crystals embedded gold nanoparticles for photoswitching properties.

A new series of liquid crystals decorated gold nanoparticles is synthesized whose molecular architecture has azobenzenes moieties as the peripheral units connected to gold nanoparticles (Au NPs) via alkyl groups. The morphology and mesomorphic properties were investigated by field emission scanning electron microscope, high-resolution transmission electron microscopy, differential scanning calorimetry and polarizing optical microscopy. The thiolated ligand molecules (3a-c) showed enantiotropic smectic A phase, whereas gold nanoparticles (5a-c) exhibit nematic and smectic A phase with monotropic nature. HR-TEM measurement showed that the functionalized Au NPs are of the average size of 2nm and they are well dispersed without any aggregation. The trans-form of azo compounds showed a strong band in the UV region at ∼378nm for the π-π(∗) transition, and a weak band in the visible region at ∼472nm due to the n-π(∗) transition. These molecules exhibit attractive photoisomerization behaviour in which trans-cis transition takes about 15s whereas the cis-trans transition requires about 45min for compound 5c. The extent of reversible isomerization did not decay after 10 cycles, which proved that the photo-responsive properties of 5c were stable and repeatable. Therefore, these materials may be suitably exploited in the field of molecular switches and the optical storage devices.

Amphiphilic self-assembled polymeric copper catalyst to parts per million levels: click chemistry.

Self-assembly of copper sulfate and a poly(imidazole-acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO(4) via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO(4) to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5-45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h(-1), respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

Self-assembled poly(imidazole-palladium): highly active, reusable catalyst at parts per million to parts per billion levels.

Metalloenzymes are essential proteins with vital activity that promote high-efficiency enzymatic reactions. To ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, it is important to develop metalloenzyme-inspired polymer-supported metal catalysts. Here, we present a highly active, reusable, self-assembled catalyst of poly(imidazole-acrylamide) and palladium species inspired by metalloenzymes and apply our convolution methodology to the preparation of polymeric metal catalysts. Thus, a metalloenzyme-inspired polymeric imidazole Pd catalyst (MEPI-Pd) was readily prepared by the coordinative convolution of (NH(4))(2)PdCl(4) and poly[(N-vinylimidazole)-co-(N-isopropylacrylamide)(5)] in a methanol-water solution at 80 °C for 30 min. SEM observation revealed that MEPI-Pd has a globular-aggregated, self-assembled structure. TEM observation and XPS and EDX analyses indicated that PdCl(2) and Pd(0) nanoparticles were uniformly dispersed in MEPI-Pd. MEPI-Pd was utilized for the allylic arylation/alkenylation/vinylation of allylic esters and carbonates with aryl/alkenylboronic acids, vinylboronic acid esters, and tetraaryl borates. Even 0.8-40 mol ppm Pd of MEPI-Pd efficiently promoted allylic arylation/alkenylation/vinylation in alcohol and/or water with a catalytic turnover number (TON) of 20,000-1,250,000. Furthermore, MEPI-Pd efficiently promoted the Suzuki-Miyaura reaction of a variety of inactivated aryl chlorides as well as aryl bromides and iodides in water with a TON of up to 3,570,000. MEPI-Pd was reused for the allylic arylation and Suzuki-Miyaura reaction of an aryl chloride without loss of catalytic activity.

Enantio- and stereoselective route to the phoslactomycin family of antibiotics: formal synthesis of (+)-fostriecin and (+)-phoslactomycin B.

A general methodology applicable for the synthesis of the phoslactomycin family of antibiotics, potent and selective protein phosphatase inhibitors, has been developed starting from a beta-isocupreidine-catalyzed asymmetric Baylis-Hillman reaction of 3-(4-methoxybenzyloxy)propanal with hexafluoroisopropyl acrylate, and thereby formal syntheses of (+)-fostriecin and (+)-phoslactomycin B have been accomplished.

Highly enantioselective aryl transfer to aldehydes: a remarkable effect of sulfur substitution in amino thioacetate ligands.

Chiral amino thioacetate ligands were prepared from the corresponding amino alcohols and used as catalysts for enantioselective aryl transfer reaction. The amino thioacetates were remarkably superior to the corresponding amino alcohols. Low catalyst loadings of only 1-2.5 mol % were sufficient to achieve excellent enantioselectivity as well as high conversion in short reaction time. The results reveal that the thioacetoxy moiety of the amino thioacetates has a surprisingly beneficial effect in enhancing the asymmetric induction.