Rahimi M. Yusop

Palladium-mediated intracellular chemistry

Many important intracellular biochemical reactions are modulated by transition metals, typically in the form of metalloproteins. The ability to carry out selective transformations inside a cell would allow researchers to manipulate or interrogate innumerable biological processes. Here, we show that palladium nanoparticles trapped within polystyrene microspheres can enter cells and mediate a variety of Pd(0)-catalysed reactions, such as allylcarbamate cleavage and Suzuki-Miyaura cross-coupling. The work provides the basis for the customization of heterogeneous unnatural catalysts as tools to carry out artificial chemistries within cells. Such in cellulo synthesis has potential for a plethora of applications ranging from cellular labelling to synthesis of modulators or inhibitors of cell function.

Synthesis, reactivity and application studies for different biolubricants

Vegetable oils have different unique properties owing to their unique chemical structure. Vegetable oils have a greater ability to lubricate and have higher viscosity indices. Therefore, they are being more closely examined as base oil for biolubricants and functional fluids. In spite of their many advantages, vegetable oils suffer from two major drawbacks of inadequate oxidative stability and poor low-temperature properties, which hinder their utilization as biolubricant base oils. Transforming alkene groups in fatty acids to other stable functional groups could improve the oxidative stability, whereas reducing structural uniformity of the oil by attaching alkyl side chains could improve the low-temperature performance. In that light, the epoxidation of unsaturated fatty acids is very interesting as it can provide diverse side chains arising from the mono- or di-epoxidation of the unsaturated fatty acid. Oxirane ring opening by an acid-catalyzed reaction with a suitable reagent provides interesting polyfunctional compounds.

Copper Catalysis in Living Systems and In Situ Drug Synthesis

The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has proven to be a pivotal advance in chemical ligation strategies with applications ranging from polymer fabrication to bioconjugation. However, application in vivo has been limited by the inherent toxicity of the copper catalyst. Herein, we report the application of heterogeneous copper catalysts in azide-alkyne cycloaddition processes in biological systems ranging from cells to zebrafish, with reactions spanning from fluorophore activation to the first reported in situ generation of a triazole-containing anticancer agent from two benign components, opening up many new avenues of exploration for CuAAC chemistry.

Effect of Nano ZnO on the Optical Properties of Poly(vinyl chloride) Films

Optical properties of pure and doped poly(vinyl chloride) (PVC) films, prepared by using casting technique, with different nanosize zinc oxide (ZnO) concentrations (1–20) wt% have been studied. Parameters such as extinction coefficient, refractive index, real and imaginary parts, Urbach energy, optical conductivity, infinitely high frequency dielectric constant, and average refractive index were studied by using the absorbance and transmittance measurement from computerized UV-visible spectrophotometer (Shimadzu UV-1601 PC) in the spectral range 200–800 nm. This study reveals that the optical properties of PVC are affected by the doping of ZnO where the absorption increases and transmission decreases as ZnO concentration increases. The extinction coefficient, refractive index, real and imaginary parts, infinitely high frequency dielectric constant, and average refractive index values were found to increase with increasing impurity percentage. The Urbach energy values are found to be decreasing with increasing ZnO concentration. The optical conductivity increased with photon energy after being doped and with the increase of ZnO concentration.

Preparation and characterization of HypoGel-supported Pd nanocatalysts for Suzuki reaction under mild conditions

Abstract A new heterogeneous catalyst composed of Pd nanoparticles immobilized within a HypoGel resin has been prepared in the absence of any ligands using an extensive cross-linking method. This newly developed nanocatalyst was characterized by N 2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy and inductively coupled plasma-mass spectrometer (ICP-MS) techniques. TEM and XRD results revealed that the Pd nanoparticles were well dispersed with diameters in the range of 4–12 nm, and an average size of about 8 nm. The cross-linked Pd catalyst demonstrated excellent catalytic activity towards the synthesis of a series of biaryl compounds by the reaction of various aryl halides (e.g., bromides andiodides) with phenylboronic acid in the presence of tetrabutylammonium bromide. ICP-MS analysis indicated that there was only 0.25% weight loss of Pd (0.55 ± 0.02 ppm) from the supported catalyst after the first cycle reaction. Furthermore, the catalyst showed excellent reusability (up to five uses) with consistently high levels of catalytic activity following its recovery by filtration.

QuadraPure-Supported Palladium Nanocatalysts for Microwave-Promoted Suzuki Cross-Coupling Reaction under Aerobic Condition

Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4–10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.

Laser Induced Modification of the Optical Properties of Nano-ZnO Doped PVC Films

The effect of continuous CO2 laser radiation on the optical properties of pure polyvinyl chloride and doped of ZnO nanoparticles with two different concentrations (10, 15%) has been investigated. All samples were prepared using casting method at room temperature. Optical properties (absorption, transmission, absorption coefficient, extinction coefficient, refractive index, and optical conductivity) of all films after CO2 laser irradiated have been studied as a function of the wavelength in the range (200–800) nm for three energies (300, 400 and 500 mJ). It has been found that the transmission, energy gap, and refractive index increase with increasing laser energy. The values of absorption, Urbach energy, absorption coefficient, extinction coefficient, and optical conductivity were decreased.

Spectroscopic and photochemical stability of polystyrene films in the presence of metal complexes

Abstract Five metal complexes containing Ni(II), Cu(II), Zn(II), Cd(II) and Sn (II) metals and 4-amino-5-(pyridine-4-yl)-4H-1,2,4-triazole-3-thiol have been prepared for use as polystyrene photostabilizers. The additives (0.5% by weight) were mixed with polystyrene in chloroform to produce modified PS using the casting method. PS films were irradiated (λ = 250–380 nm) with a light absorption intensity of 6.02 × 10−9 ein dm−3 s−1 at room temperature. The photostabilization activity of the films was determined by monitoring various changes, such as the carbonyl index, hydroxyl index, weight loss, viscosity average molecular weight, surface morphology and quantum yield of the chain scission.

Poly(vinyl chloride) derivatives as stabilizers against photodegradation

Abstract The photo-stabilization of polymers derived from poly(vinyl chloride) (PVC) films was investigated. The PVC and modified PVC films were produced by the casting method from tetrahydrofuran (THF) solvent. The photostabilization activities of these compounds were determined by monitoring the carbonyl, polyene and hydroxyl indices with irradiation time. The changes in viscosity average molecular weight of PVC with irradiation time were also tracked (using THF as a solvent). The quantum yield of the chain scission (Φcs) of these complexes in PVC films was evaluated and found to range between 4.79 × 10−8 and 7.50 × 10−8. Results obtained showed that the rate of photostabilization of PVC in the presence of the additive followed the trend:

Highly Active Ruthenium Supported on Magnetically-Recyclable Chitosan-Based Nanocatalyst for Nitroarenes Reduction

A Ru supported on a magnetically separable chitosan‐based nanomaterial (Mn@CS@Ru) was prepared by wet impregnation based on ionic gelation using sodium tripolyphosphate as a cross‐linking agent. The ionic gelation of chitosan leads to a supporting matrix to promote the embedding of manganese(II) ferrite and Ru nanoparticles (NPs) by electrostatic interactions. The effects of the formulation and method parameters on the fabrication process were investigated, and the resulting as‐prepared Mn@CS@Ru nanocatalyst was characterized. The catalytic activity of the Mn@CS@Ru nanomaterial was evaluated in the reduction of 4‐nitrophenol (4‐NP) and 4‐nitroaniline (4‐NA) in the presence of sodium borohydride as a reducing agent at room temperature. The turnover frequency values in the reduction of 4‐NP and 4‐NA were 273.9 and 336.5 min−1, respectively, which were attributed to the very small size of the hybrid nanomaterial (32.0±2.8 nm with 3.9±0.1 nm Ru NPs) that provided a large surface‐area‐to‐volume ratio for the chemical reaction. Furthermore, the hybrid nanocatalyst was recovered easily by magnetic separation after the catalytic reaction and could be reused in at least 10 cycles without a loss of catalytic activity, which confirms its high stability. The present route is a new approach to synthesize highly active magnetic heterogeneous catalysts for the reduction of nitroarenes based on metallic NPs with easy accessibility, excellent activity, and convenient recovery.