The roaming atom pathway in formaldehyde decomposition

We present a detailed experimental and theoretical investigation of formaldehyde photodissociation to H(2) and CO following excitation to the 2(1)4(1) and 2(1)4(3) transitions in S(1). The CO velocity distributions were obtained using dc slice imaging of single CO rotational states (v=0, j(CO)=5-45). These high-resolution measurements reveal the correlated internal state distribution in the H(2) cofragments. The results show that rotationally hot CO (j(CO) approximately 45) is produced in conjunction with vibrationally "cold" H(2) fragments (v=0-5): these products are formed through the well-known skewed transition state and described in detail in the accompanying paper. After excitation of formaldehyde above the threshold for the radical channel (H(2)CO-->H+HCO) we also find formation of rotationally cold CO (j(CO)=5-28) correlated to highly vibrationally excited H(2) (v=6-8). These products are formed through a novel mechanism that involves near dissociation followed by intramolecular H abstraction [D. Townsend et al., Science 306, 1158 (2004)], and that avoids the region of the transition state entirely. The dynamics of this "roaming" mechanism are the focus of this paper. The correlations between the vibrational states of H(2) and rotational states of CO formed following excitation on the 2(1)4(3) transition allow us to determine the relative contribution to molecular products from the roaming atom channel versus the conventional molecular channel.     

Molded, high surface area polymer electrolyte membranes from cured liquid precursors

Polymer electrolyte membranes (PEMs) for fuel cells have been synthesized from easily processable, 100% curable, low molecular weight reactive liquid precursors that are photochemically cured into highly proton conductive solid membranes. The liquid precursors were directly cured into membranes of desired dimensions without the need for further processing steps such as melt extrusion or solvent casting. By employing chemical cross-linking, high proton conductivities can be achieved through the incorporation of significant levels of acidic groups without rendering the material water-soluble, which plagues commonly used non-cross-linked polymers. Fabrication of membrane electrode assemblies (MEAs) from these PEMs resulted in fuel cells that outperformed those based on commercial materials. Moreover, these liquid precursors enabled the formation of three-dimensional, patterned PEMs with high fidelity, micron-scale features by using soft lithographic/micromolding techniques. The patterned membranes provided a larger interfacial area between the membrane and catalyst layer than standard flat PEMs. MEAs composed of the patterned membranes demonstrated higher power densities over that of flat ones without an increase in the macroscopic area of the fuel cells. This can potentially miniaturize fuel cells and promote their application in portable devices.     

Use of solid-phase extraction, reverse osmosis and vacuum distillation for recovery of aromatic sulfonic acids from aquatic environment followed by their determination using liquid chromatography-electrospray ionization tandem mass spectrometry

Three different sample preparation techniques (i) solid-phase extraction, (ii) reverse osmosis and (iii) vacuum distillation have been investigated and the recoveries were compared for determination of highly water-soluble benzene and stilbene sulfonic acids in aqueous environment by liquid chromatography with photodiode array (PDA) and electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The recoveries were quite high using vacuum distillation (>90%) compared to solid phase extraction and reverse osmosis. The negative ion ESI mass spectra containing the peaks of quasimolecular ion [M-H]- allow the molecular mass determination of unknown compounds whereas the structures were proposed using fragments obtained from MS/MS analysis of [M-H]- ions. At lower fragmentation voltages only the quasimolecular ion [M-H]- was observed and as fragmentation voltages increased, it led to the formation of fragment ions corresponding to [M-H-SO3]-, [M-H-SO2]-, and SO3-. The detection limits were 1-28 microg/L with LC-ESI-MS. The sample collected from wastewater treatment plant was found to contain 21.1, 13.3, 12.1, 41.8 and 9.9 microg/L of cis-4,4(l)-diaminostilbene-2,2(l)-disulfonic acid (cis-DASDA), trans-4,4(l)-diaminostilbene-2,2(l)-disulfonic acid (trans-DASDA), 3-amino acetanilide-4-sulfonic acid (3-AASA), 4-chloroaniline-2-sulfonic acid (4-CASA), 2-chloroaniline-5-sulfonic acid (2-CASA), respectively.     

Synthesis of beta-hydroxysulfides from alkenes under supramolecular catalysis in the presence of beta-cyclodextrin in water

An environmentally benign and highly efficient procedure has been developed for the direct one-pot synthesis of beta-hydroxysulfides in good yields under neutral conditions from alkenes and thiophenols in the presence of aerial oxygen using beta-cyclodextrin in water. This protocol tolerates a wide variety of functional groups or substrates and does not require the use of either acid or base catalysts. beta-Cyclodextrin can be recovered and reused for a number of runs without any loss of activity.     

Effect of Biochemical Stimulants on Biomass Productivity and Metabolite Content of the Microalga, Chlorella sorokiniana

The influence of 12 biochemical stimulants, namely 2-phenylacetic acid (PAA; 30 ppm), indole-3 butyric acid (IBA; 10 ppm), 1-naphthaleneacetic acid (NAA; 2.5, 5 and 10 ppm ), gibberellic acid (GA3, 10 ppm), zeatin (ZT; 0.002 ppm), thidiazuron (0.22 ppm), humic acid (20 ppm), kelp extract (250 ppm), methanol (500 ppm), ferric chloride (3.2 ppm ), putrescine (0.09 ppm), spermidine (1.5 ppm) were prescreened for their impact on growth and chlorophyll for the green alga—Chlorella sorokiniana. C. sorokiniana responded best to phytohormones in the auxin family, particularly NAA. Thereafter, two studies were conducted on combinations of phytohormones to compare blends from within the auxin family as well as against other families. These treatments were NAA_{5 ppm}+PAA_{30 ppm}, NAA_{2.5 ppm}+PAA_15 ppm, NAA_5 ppm+IBA_10 ppm, NAA_5 ppm+GA3_10 ppm, NAA_5 ppm+ZT_1 ppm, and NAA_5 ppm+GA3_10 ppm+ZT_1 ppm. Combinations of NAA with other auxins did not have synergistic or antagonistic effects on the growth. However, combinations of compounds from different phytohormone families, such as NAA_5 ppm+GA3_10 ppm+ZT_1 ppm, dramatically increased the biomass productivity by 170% over the control followed by the treatments: NAA _5 ppm+GA3_10 ppm (138%), NAA _5 ppm+ZT_1 ppm (136%), and NAA _5 ppm ( 133%). The effect of biochemical stimulants were also measured on metabolites such as chlorophyll, protein, and lipids in C. sorokiniana. Renewed interest in microalgae for biotechnology and biofuel applications may warrant the use of biochemical stimulants for cost reduction in large-scale cultivation through increased biomass productivity.     

Scaffold hopping for identification of novel D2 antagonist based on 3D pharmacophore modelling of illoperidone analogs

The dopamine D(2) receptor is involved in the etiology of a number of disorders, such as Parkinson's disease, Huntington's Chorea, tardive dyskinesia and schizophrenia. Antagonism of D(2) receptors is implicated in the treatment of various psychiatric disorders. In order to understand essential structural features required for D(2) antagonism, this research article elaborates on the generation of a four-point 3D pharmacophore model which was extracted from a series of 45 novel 3-[[(aryloxy)alkyl]piperidinyl]-1,2-benzisoxazole derivatives. The best pharmacophore model generated consisted of four PRRR features: a positively charged group (P), and three aromatic rings (R). Based on the model generated, a statistically valid 3D-QSAR with good predictability (Q(2) = 0.756) was derived. For the validation of the pharmacophore hypothesis, active compounds were docked against the 3D structure of the D(2) receptor which was constructed through homology modeling. Further, the derived pharmacophore was used as a query to search the Zinc 'clean drug-like' database. Hits retrieved were passed progressively through filters, such as fitness score, predicted activity and docking scores. The resulting hits present new scaffolds with a strong potential for D(2) antagonist.     

Rietveld refinement and impedance spectroscopy of calcium titanate

Single phase perovskite CaTiO₃ has been synthesized by conventional solid state reaction technique. The ceramic was characterized by XRD at room temperature and its Rietveld refinement inferred orthorhombic crystal structure with the space group Pbnm. The field dependence of dielectric relaxation and conductivity was measured over a wide frequency range from room temperature to 673 K. Analysis of Nyquist plots of CaTiO₃ revealed the contribution of many electrically active regions corresponding to bulk mechanism, distribution of grain boundaries and electrode processes. The dc conductivity depicted a semiconductor to metal type transition. Frequency dependence of dielectric constant (ε′) and tangent loss (tan δ) show a dispersive behavior at low frequencies and is explained on basis of Maxwell-Wagner model and Koop's theory. Both conductivity and electric modulus formalisms have been employed to study the relaxation dynamics of charge carriers. The variation of ac conductivity with frequency at different temperatures obeys the universal Jonscher's power law (σ_ac α ω^s). The values of exponent ‘s’ lie in the range 0.13 ≤ s ≤ 0.33, which in light of CBH model suggest a large polaron hopping type of conduction mechanism.     

The COVID19-NMR Consortium: A Public Report on the Impact of this New Global Collaboration

The outbreak of COVID-19 in December 2019 required the formation of international consortia for a coordinated scientific effort to understand and combat the virus. In this Viewpoint Article, we discuss how the NMR community has gathered to investigate the genome and proteome of SARS-CoV-2 and tested them for binding to low-molecular-weight binders. External factors including extended lockdowns due to the global pandemic character of the viral infection triggered the transition from locally focused collaborative research conducted within individual research groups to digital exchange formats for immediate discussion of unpublished results and data analysis, sample sharing, and coordinated research between more than 50 groups from 18 countries simultaneously. We discuss key lessons that might pertain after the end of the pandemic and challenges that we need to address.     

A Novel Electroanalytical Biosensor Based on ZIF-8/Acetylcholinesterase Bio-nanohybrids for Early Management of Hirschsprung Disease

Hirschsprung's disease (HD) is characterised by missing nerve cells in the colon of infants and children which results in strained bowel movement. Under such situations, undiagnosed and untreated cases often lead to a cascade of gastrointestinal infections eventually resulting in Hirschsprung-assisted enterocolitis which has significantly high mortality rate. This is further exacerbated by the absence of suitable, sensitive and efficient technologies to detect the pathological segment of the intestine, which could significantly reduce surgery duration in the operation theatre, as well as associated risks to patients. It therefore becomes a matter of extreme importance to develop a point-of-care platform for early and efficient management/identification of the occurrence of HD in neonates and older children during its onset, before it proves fatal with life-threatening outcomes. The present work reports an electrochemical enzymatic biosensor using Zeolitic Imidazolate Framework-8 (ZIF-8) modified with acetylcholinesterase enzyme (AchE), for detection of HD as a function of the key biomarker – acetylcholine. The developed sensor was initially characterized using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS), while the analytical performance and insights onto interfacial redox kinetics were assessed using Differential Pulse Voltammetry (DPV) and EIS respectively. The sensor exhibited limit of detection and sensitivity of 0.19 μM and sensitivity of 0.42 μA/μM/mm² with a shelf life of 1 month, while remaining unperturbed in the presence of common interferants. The performance of developed sensor was also examined in spiked serum samples and was observed to yield a high degree of linearity.