Double-quantum homonuclear correlation magic angle sample spinning nuclear magnetic resonance spectroscopy of dipolar-coupled quadrupolar nuclei

A double-quantum homonuclear correlation nuclear magnetic resonance experiment for dipolar-coupled half-integer quadrupolar nuclei in solids is presented. The experiment is based on rotary resonance dipolar recoupling and uses bracketed spin-lock pulses to excite double-quantum coherence and later to convert it to the zero-quantum one. A central-transition-selective pi pulse at the beginning of the t1 evolution period differentiates coherence transfer pathways of double-quantum coherences arising from coupled spins and from a single spin, so that the latter can be efficiently filtered out by phase cycling. The experiment was tested on an aluminophosphate molecular sieve AlPO4-14, a material with a variety of aluminum quadrupolar coupling constants, isotropic chemical shifts and homonuclear distances. In a two-dimensional spectrum aluminum dipolar couplings with internuclear distances between 2.9 and 5.5 A were resolved. Although the experiment requires an application of weak radio-frequency fields, frequency offsets did not affect its performance crucially.     

Convenient Synthesis of Naturally Occurring Methoxy-and Hydroxy Phthalides

A convenient method for the synthesis of phthalides (1–5), involving heteroatom directed lithiation reaction is described.     

Calculation of the light intensity distribution reflected by a planar corner-cube retroreflector array with the size of centimeter and above

The light intensity distribution (LID) reflected by a planar corner-cube retroreflector array with the size of centimeter and above (PCCRA) is calculated based on the Collins formula, coordinate transformation matrixes and vector algebra. The expression can be used for the PCCRAs with different parameters and different complex optical systems described by ABCD matrix. The expression indicates that the LID of a PCCRA is much different from a single corner-cube retroreflector (CCR) with equivalent aperture. Computer simulations are applied to explain the expression clearly. The results show that the LID of the PCCRA is more homogeneous than the single CCR with equivalent aperture under circumstances of both normal incident light and oblique incident light. In addition, the expression is proved by comparing the simulation result of the PCCRA only comprising a single CCR and the previous experimental result.     

Convenient Synthesis of 3-Styrylphthalides

A convenient, high yield, two-step method is described for 3-styrylphthalides (3a - e) from 3-phenacylphthalides (1a - e)     

A convenient approach to an advanced intermediate for (+)-lactacystin synthesis

A fully stereoselective preparation of the advanced intermediate 24 for the synthesis of (+)-lactacystin from known 1,2:5,6-di-O-isopropylidene-α-d-gulofuranose (2), as the source of chirality, has been achieved. The C-5 methyl group was introduced via a Wittig olefination followed by Pd/C-mediated hydrogenation of the conformationally restricted alkene 11 in a highly stereoselective manner. The stereogenic tetrasubstituted carbon centre at C-3, with an amino group, was installed stereoselectively via an Overman rearrangement, which was efficiently controlled by a saccharide environment.     

Molecular modelling studies on adamantane-based Ebola virus GP-1 inhibitors using docking,pharmacophore and 3D-QSAR

The pathogenic Ebola virus (EBOV) causes a potential health risk and global spread. To date, few drugs are available for the treatment of Ebola virus disease (EVD) that allow researchers to use computational methods for designing potential drugs. The developed PHASE-based common six-point pharmacophore hypothesis (AADHPR_1) showed the necessity of two hydrogen bond acceptor features, one hydrogen bond donor feature, one hydrophobic group feature, one positively ionizable and one aromatic ring feature for further designing. We developed best 3D-QSAR models with high regression coefficients for the training (r²>0.82) and test (Q²>0.5) sets for both atoms-based and field-based 3D-QSAR models. The molecule 1A-4 (docking score = –4.711 kcal/mol) was obtained as best docked (SP mode) on Ebola virus envelope glycoprotein (PDB ID-3CSY) as compared with the standards oseltamivir (docking score = –4.39 kcal/mol) and zanamivir (docking score = –3.392 kcal/mol). The obtained ZINC hit ZINC58935541 showed a good docking score of –4.892 kcal/mol. The ZINC58935541 molecule also showed a strong binding affinity towards the receptor cavity of Ebola virus envelope glycoprotein when simulated for 1.2 ns. The good QikProp parameters reflect the fact that this molecule, upon optimization into a lead, might become a good candidate for the treatment of EVD.     

Simplex Optimized LC Analysis of Plant Coumarins and Furanocoumarins

Sequential simplex methods are common and efficient optimization techniques applied in analytical chemistry. This study reports on the optimization of LC separation of coumarins using a variable-size simplex algorithm. The solvent systems consisted of methanol, water and tetrahydrofuran. Using an optimized method, seven standard simple coumarins and furanocoumarins derived from plants were successfully separated in one chromatographic run. The mobile phase at the point corresponding to the optimum consisted of 34% MeOH, 59% H₂O and 7% THF. Applying a solvent mixture in this proportion permitted separation of all critical pairs, such as esculetin/scopoletin, scopoletin/umbelliferone, umbelliferone/coumarin and xanthotoxin/psoralen. The retention ratio factors k for coumarins at the optimum of the simplex algorithm lay in the range 1 < k < 4. The optimal conditions assigned to the coumarin standards were then applied to the plant matter: herb of the rue (Ruta graveolens L., Rutae herba), anthodium of the camomile (Chamomilla recutita L., Chamomillae anthodium), herb of the southernwood (Artemisia abrotanum L., Abrotani herba), and radix of the lovage (Levisticum officinale K., Levistici radix). The validity of the method was confirmed with respect to these samples.     

Squeezing,Then Stacking: From Breathing Pores to Three‐Dimensional Ionic Self‐Assembly under Electrochemical Control

We demonstrate the spontaneous and reversible transition between the two‐ and three‐dimensional self‐assembly of a supramolecular system at the solid–liquid interface under electrochemical conditions, using in situ scanning tunneling microscopy. By tuning the interfacial potential, we can selectively organize our target molecules in an open porous pattern, fill these pores to form an auto‐host–guest structure, or stack the building blocks in a stratified bilayer. Using a simple electrostatic model, we rationalize which charge density is required to enable bilayer formation, and conversely, which molecular size/charge ratio is necessary in the design of new building blocks. Our results may lead to a new class of electrochemically controlled dynamic host–guest systems, artificial receptors, and smart materials.     

A Facile and Efficient Synthesis of 2‐(5‐(4‐Substitutedphenyl)‐4, 5‐dihydro‐3‐phenylpyrazol‐1‐yl)‐6‐Substitutedbenzothiazoles and Their Biological Studies

A series of new 1‐substituted 3, 5‐diarylpyrazolines ( 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ) were synthesized in good yield by both conventional and microwave‐assisted synthesis from α, β‐ unsaturated ketones ( 6 , 7 , 8 , 9 ) in n‐butanol and benzothiazole hydrazines ( 2 , 3 , 4 , 5 ). All the new compounds were characterized by IR, NMR, and mass spectral data. The synthesized compounds ( 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ) were evaluated for antibacterial and anthelmintic activities. The compounds showed potent anthelmintic activity against earthworm species (Eudrilus eugeniae) and moderate antibacterial activity against bacterial strains such as Gram positive bacteria, Enterococcus faecalis, Staphylococcus aureus, and Bacillus subtilis, and Gram negative bacteria, Escherichia coli and Proteus mirabilis.     

MnOx Nanoparticles Supported on a New Mesostructured Silicate with Textural Porosity

A two‐step synthesis of a novel mesostructured silicate, KIL‐2, and its manganese‐containing analogue, Mn/KIL‐2, has been developed. KIL‐2 possesses interparticle mesopores with pore dimensions between 5 and 60 nm and a surface area of 448 m². The mesopores are formed by the aggregation of silica nanoparticles, which creates a network with interparticle voids. The particle size and the pore diameters depend on the temperature of the ageing step (first step) and on the solvothermal treatment in ethanol (second step), respectively. Mn/KIL‐2 contains octahedrally coordinated Mn³⁺ (80 %) and tetrahedrally coordinated Mn²⁺ (20 %) ions. Mn³⁺ ions are present in the extra‐framework MnO_x nanoparticles with typical dimensions of 2 nm, which are homogeneously distributed throughout the material. Mn²⁺ ions occur as isolated manganese framework sites. The material is also able to retain its structure characteristics after the hydrothermal treatment in boiling water. Because of its non‐toxic nature and cost‐effective synthesis, Mn/KIL‐2 thus exhibits properties that are needed for an environment‐friendly catalyst.