p-Toluenesulfonic acid-promoted organic transformations for the generation of molecular complexity.

Since the beginning of this century, p-toluenesulfonic acid (p-TSA) catalysed organic transformations have been an active area of research for developing efficient synthetic methodologies. Often, catalysis using p-TSA is associated with many advantages, such as operational simplicity, high selectivity, excellent yields, and ease of product isolation, which make organic synthesis convenient and versatile. Notably, p-TSA is a non-toxic, commercially available, inexpensive solid organic compound that is soluble in water, alcohols, and other polar organic solvents. p-TSA is a strong acid compared to many protic or mineral acids and its high acidity helps activate different organic functional groups. p-TSA-promoted conversions are fast, have a high atom and pot economy, and feature a multiple bond-forming index. Therefore, the utilization of p-TSA enables the synthesis of many important structural scaffolds without any hazardous metals, making it desirable in numerous applications of sustainable and green chemistry. Recently, this emerging area of research has become one of the pillars of synthetic organic chemistry to synthesise biologically relevant, complex carbocycles and heterocycles. This study provides a comprehensive summary of methods, applications, and mechanistic insights into p-TSA-catalysed organic transformations, covering the literature reports that have appeared since 2012.

A 2D Coordination Network That Detects Nitro Explosives in Water, Catalyzes Baylis-Hillman Reactions, and Undergoes Unusual 2D→3D Single-Crystal to Single-Crystal Transformation.

The solvothermal reaction of Zn(NO3)2·6H2O and a linear dicarboxylate ligand H2L, in the presence of urotropine in N,N'-dimethylformamide (DMF), gives rise to a new porous two-dimensional (2D) coordination network, {[Zn3(L)3(urotropine)2]·2DMF·3H2O}n (1), with hxl topology. Interestingly, framework 1 exhibits excellent emission properties owing to the presence of naphthalene moiety in the linker H2L, that can be efficiently suppressed by subtle quantity of nitro explosives in aqueous medium. Furthermore, presence of urotropine molecules bound to the metal centers, 1 is found to be an excellent heterogeneous catalyst meant for atom-economical C-C bond-forming Baylis-Hillman reactions. Additionally, crystals of 1 undergo complete transmetalation with Cu(II) to afford isostructural 1Cu. Moreover, the 2D framework of 1 allows replacement of urotropine molecules by 4,4'-azopyridine (azp) linker resulting in a three-dimensional (3D) metal-organic framework, {[Zn(L)(azp)]·4DMF 2H2O}n (2). The 1→2 transformation takes place in single-crystal-to-single crystal manner supported by powder X-ray diffraction, atomic force microscopy, high-resolution transmission electron microscopy, and morphological studies. Remarkably, during this 2D→3D transformation, the original trinuclear [Zn3(COO)6] secondary building unit changes to a mononuclear node, which is unprecedented.

A porous two-dimensional Zn(ii)-coordination polymer exhibiting SC-SC transmetalation with Cu(ii): efficient heterogeneous catalysis for the Henry reaction and detection of nitro explosives.

The linker 5-(benzylamino)isophthalic acid (H2L) forms a robust 2D Zn(ii)-coordination polymer, {[Zn8(L)6(µ3-OH)4(H2O)6]·(DMF)·(H2O)2.5}n(1Zn) consisting of [Zn4(µ3-OH)2]6+ SBUs. It further shows strong ππ interactions between the layers to form an overall 3D structure with well-defined channels. Metal bound water molecules are directed towards these channels. Upon heating, these metal bound water molecules are lost along with lattice solvent molecules to afford coordinatively unsaturated metal centers that can be utilized as an efficient heterogeneous catalyst for the C-C bond forming nitroaldol or Henry reaction. The solid catalyst can be recycled at least three times without losing its catalytic activity. The easily accessible channels in 1Zn are found suitable for the SC-SC transmetalation reaction with Cu(ii) producing 1Cu. The catalytic activity of 1Cu is found to be comparable to that of 1Zn. Furthermore, the framework 1Zn gives high emission in DMSO, which can be efficiently quenched by trace amounts of nitro explosives. All the complexes have been characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR, thermogravimetry and elemental analysis.

Development and validation of a noncontact spectroscopic device for hemoglobin estimation at point-of-care.

Anemia severely and adversely affects human health and socioeconomic development. Measuring hemoglobin with the minimal involvement of human and financial resources has always been challenging. We describe a translational spectroscopic technique for noncontact hemoglobin measurement at low-resource point-of-care settings in human subjects, independent of their skin color, age, and sex, by measuring the optical spectrum of the blood flowing in the vascular bed of the bulbar conjunctiva. We developed software on the LabVIEW platform for automatic data acquisition and interpretation by nonexperts. The device is calibrated by comparing the differential absorbance of light of wavelength 576 and 600 nm with the clinical hemoglobin level of the subject. Our proposed method is consistent with the results obtained using the current gold standard, the automated hematology analyzer. The proposed noncontact optical device for hemoglobin estimation is highly efficient, inexpensive, feasible, and extremely useful in low-resource point-of-care settings. The device output correlates with the different degrees of anemia with absolute and trending accuracy similar to those of widely used invasive methods. Moreover, the device can instantaneously transmit the generated report to a medical expert through e-mail, text messaging, or mobile apps.