Green chemistry: Analytical and chromatography

Nowadays, the environment protection and the personal health and safety are given more consideration in the field of chemistry, thus resulting in an increased number of published researches about how to work according to green instructions, to follow up the recommendations of environmental agencies and to obtain better clean handling of chemistry. In this review, green chemistry definition, importance, principles, and some recent applications in the field of green chemistry were discussed. In addition, the review summarizes the evolution of green analytical chemistry (GAC) with its specific principles and how to make the analytical process more environmentally benign with special emphasis on recent applications of GAC. Moreover, the green chromatography, its methods, and some of its applications were outlined. Finally, different techniques available up till now for the assessment of greening of the methods were also presented.     

TIME-RESOLVED SPECTROSCOPIC STUDIES ON PHOTOPHYSICAL PROPERTIES OF BENOXAPROFEN IN MICELLAR SOLUTIONS: AN INTRAMICELLAR FLUORESCENCE QUENCHING

The micellar dependencies of the photophysical properties of benoxaprofen (BXP), a 2-phenyl benzoxazole derivative, have been investigated using fluorescence spectroscopy and laser flash photolysis techniques. The fluorescence of BXP in aqueous solution has been observed to be remarkably quenched upon addition of a surfactant, cetyltrimethyl ammonium bromide (CTAB) or Triton X-100, in contrast to its enhancement in sodium dodecyl sulfate (SDS) micellar solution. Time-resolved fluorescence measurements show that the fluorescence decays biexponentially in the micellar solution, indicating the relaxation of micellar environments surrounding the excited BXP. The major component of fluorescence lifetimes in CTAB or Triton X-100 micellar phase is even shorter (330–427ps) than in SDS micellar phase (731 ps). The nonradiative decay constants are significantly larger (ca 3.0 times 10⁹ s^?1) in the CTAB or Triton X-100 micellar phase than in SDS micelles by a factor of ca 10. The major nonradiative decay is interpreted to be the internal conversion due to nuclear geometric change of BXP in the first excited singlet state. This is consistent with the observation that the quantum yields of intersystem crossing are very low (less than 0.01) in the micellar solutions as determined by the laser flash photolysis technique. The laser-induced transient absorption spectrum of BXP in CTAB or Triton X-100 micellar solution shows that the decay kinetics of the transients in CTAB or Triton X-100 are significantly different from first order kinetics in SDS.     

Synthesis of 2‐(2‐, 3‐, and 4‐pyridyl)benzoxazoles by the reaction of phenolic schiff bases with thianthrene cation radical

2‐(2‐, 3‐, and 4‐Pyridyl)benzoxazole derivatives were prepared in excellent yields by the oxidative cyclization of phenolic Schiff bases with thianthrene cation radical perchlorate in the presence of 2,6‐di‐tert‐butyl‐4‐methylpyridine.     

Cation Recognition by Picolyl-Armed Calix[4]crown-5-azacrown-5s

A series of N-pivot calix[4]crown-5-azacrown-5 ethers substituted by 2-picolyl, 3-picolyl and benzyl groups respectively were synthesized. The nitrogen atom of the 2-picolyl group is found to participate in the silver ion complexation through three dimensional encapsulation.     

Tunable Bacterial Agglutination and Motility Inhibition by Self‐Assembled Glyco‐Nanoribbons

We explored a method of controlling bacterial motility and agglutination by using self‐assembled carbohydrate‐coated β‐sheet nanoribbons. To this aim, we synthesized triblock peptides that consist of a carbohydrate, a polyethylene glycol (PEG) spacer, and a β‐sheet‐forming peptide. An investigation into the effect of PEG‐spacer length on the self‐assembly of the triblock peptides showed that the PEG should be of sufficiently length to stabilize the β‐sheet nanoribbon structure. It was found that the stabilization of the nanoribbon led to stronger activity in bacterial motility inhibition and agglutination, thus suggesting that antibacterial activity can be controlled by the stabilization strategy. Furthermore, another level of control over bacterial motility and agglutination was attained by co‐assembly of bacteria‐specific and ‐nonspecific supramolecular building blocks. The nanoribbon specifically detected bacteria after the encapsulation of a fluorescent probe. Moreover, the detection sensitivity was enhanced by the formation of bacterial clusters. All these results suggest that the carbohydrate‐coated β‐sheet nanoribbons can be developed as promising agents for pathogen capture, inactivation, and detection, and that the activity can be controlled at will.     

Prepackaged Ramberg-Bäcklund reagents: useful tools for organic synthesis

The synthesis and reactions of several α,β-unsaturated chloromethyl sulfones is presented, for example [(chloromethyl)sulfonyl]-1,3-propadiene (4), [(chloromethyl)sulfonyl]ethene (5), [(dichloromethyl)sulfonyl]ethene (6) and (E,Z)-1,2-bis[(chloromethyl)sulfonyl]ethene (7). These compounds serve as ‘prepackaged’ Ramberg-Bäcklund reagents, which following an appropriate first step, such as Diels-Alder addition, react with base giving Ramberg-Bäcklund products.     

Chiral Co(III)(salen)-catalysed hydrolytic kinetic resolution of racemic epoxides in ionic liquids

In the chiral Co(III)(salen)-catalysed HKR of racemic epoxides, in the presence of ionic liquids, Co(II)(salen) complex is oxidised without acetic acid to catalytically active Co(III)(salen) complex during reaction and, moreover, this oxidation state is stabilised against reduction to Co(II) complex which enables the reuse of the recovered catalyst for consecutive reactions without extra reoxidation.     

Surface ordering of a perfluorinated, self-assembled, dendrimer on a water subphase

We have investigated the surface ordering of a synthetic, asymmetric, fan-shaped dendrimer containing a carboxyl core and perfluorinated tails which was obtained by the esterification of the intermediary. X-ray diffraction patterns and transmission electron microscopy (TEM) images show the molecules self-assemble into a hexagonal, cylindrical mesophase. Surface pressure-area isotherms and Brewster angle microscopy measurements show the molecule forms a stable monolayer at the air-water interface with a single phase transition. As a condensed monolayer, the perfluorinated tails are well-packed with hexagonal symmetry with (10) spacing of approximately 0.5 nm from molecular-scale atomic force microscopy (AFM) images. Such dense molecular-scale packing has not been observed in other dendritic molecules thus far. Compared to the case of conventional dendritic molecules with alkyl tails, these molecules occupy a much smaller molecular area due to the strong microphase separation between the carboxylic core and perfluorinated tails at the air-water interface. After monolayer collapse, the irregular islands with terrace morphology are observed in contrast with conventional alkyl-terminated self-assembled dendritic molecules where irregular islands do not appear. The interfacial and internal structure of every terrace shows planar columnar morphology from AFM and TEM imaging. From these results, we discuss the stability of perfluorinated, self-assembled dendrimers on water, as well as how to generate planar morphology on a hydrophilic surface.     

Poly(l‐Lactic Acid)/Gelatin Fibrous Scaffold Loaded with Simvastatin/Beta‐Cyclodextrin‐Modified Hydroxyapatite Inclusion Complex for Bone Tissue Regeneration

Recently, the application of nanostructured materials in the field of tissue engineering has garnered attention to mediate treatment and regeneration of bone defects. In this study, poly(l ‐lactic acid) (PLLA)/gelatin (PG) fibrous scaffolds are fabricated and β‐cyclodextrin (βCD) grafted nano‐hydroxyapatite (HAp) is coated onto the fibrous scaffold surface via an interaction between βCD and adamantane. Simvastatin (SIM), which is known to promote osteoblast viability and differentiation, is loaded into the remaining βCD. The specimen morphologies are characterized by scanning electron microscopy. The release profile of SIM from the drug loaded scaffold is also evaluated. In vitro proliferation and osteogenic differentiation of human adipose derived stem cells on SIM/HAp coated PG composite scaffolds is characterized by alkaline phosphatase (ALP) activity, mineralization (Alizarin Red S staining), and real time Polymerase chain reaction (PCR). The scaffolds are then implanted into rabbit calvarial defects and analyzed by microcomputed tomography for bone formation after four and eight weeks. These results demonstrate that SIM loaded PLLA/gelatin/HAp‐(βCD) scaffolds promote significantly higher ALP activity, mineralization, osteogenic gene expression, and bone regeneration than control scaffolds. This suggests the potential application of this material toward bone tissue engineering.