Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

A self-penetrating and chemically stable zinc (ii)-organic framework as multi-responsive chemo-sensor to detect pesticide and antibiotics in water

Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)_0.5(bimb)]·H₂O}_n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {8⁶} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium.     

In vivo comprehensive multiphase NMR

Traditionally, due to different hardware requirements, nuclear magnetic resonance (NMR) has developed as two separate fields: one dealing with solids, and one with solutions. Comprehensive multiphase (CMP) NMR combines all electronics and hardware (magic angle spinning [MAS], gradients, high power Radio Frequency (RF) handling, lock, susceptibility matching) into a universal probe that permits a comprehensive study of all phases (i.e., liquid, gel-like, semisolid, and solid), in intact samples. When applied in vivo, it provides unique insight into the wide array of bonds in a living system from the most mobile liquids (blood, fluids) through gels (muscle, tissues) to the most rigid (exoskeleton, shell). In this tutorial, the practical aspects of in vivo CMP NMR are discussed including: handling the organisms, rotor preparation, sample spinning, water suppression, editing experiments, and finishes with a brief look at the potential of other heteronuclei (²H, ¹⁵N, ¹⁹F, ³¹P) for in vivo research. The tutorial is aimed as a general resource for researchers interested in developing and applying MAS-based approaches to living organisms. Although the focus here is CMP NMR, many of the approaches can be adapted (or directly applied) using conventional high-resolution magic angle spinning, and in some cases, even standard solid-state NMR probes.     

A DNA Switch for Detecting Single Nucleotide Polymorphism within a Long DNA Sequence Under Denaturing Conditions

DNA detection is usually conducted under nondenaturing conditions to favor the formation of Watson–Crick base-paring interactions. However, although such a setting is excellent for distinguishing a single-nucleotide polymorphism (SNP) within short DNA sequences (15–25 nucleotides), it does not offer a good solution to SNP detection within much longer sequences. Here we report on a new detection method capable of detecting SNP in a DNA sequence containing 35–90 nucleotides. This is achieved through incorporating into the recognition DNA sequence a previously discovered DNA molecule that forms a stable G-quadruplex in the presence of 7 molar urea, a known condition for denaturing DNA structures. The systems are configured to produce both colorimetric and fluorescent signals upon target binding.     

Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

Finite‐size corrections at the hard edge for the Laguerre β ensemble

A fundamental question in random matrix theory is to quantify the optimal rate of convergence to universal laws. We take up this problem for the Laguerre β ensemble, characterized by the Dyson parameter β, and the Laguerre weight , in the hard edge limit. The latter relates to the eigenvalues in the vicinity of the origin in the scaled variable . Previous work has established the corresponding functional form of various statistical quantities—for example, the distribution of the smallest eigenvalue, provided that . We show, using the theory of multidimensional hypergeometric functions based on Jack polynomials, that with the modified hard edge scaling , the rate of convergence to the limiting distribution is , which is optimal. In the case , general the explicit functional form of the distribution of the smallest eigenvalue at this order can be computed, as it can for and general . An iterative scheme is presented to numerically approximate the functional form for general .     

Elemental distribution by synchrotron X-ray microfluorescence of prostate 3D cell culture

Prostate cancer is a highly prevalent disease and ranks second among malignant neoplasms that affect men around the world, behind lung cancer alone. Trace elements are very important and are involved in many cellular processes. The X-ray microfluorescence technique is an advanced tool of high spatial resolution, sensitivity, multielemental analysis, and nondestructiveness for trace element study. This study aimed to investigate the elemental distribution in spheroids obtained through the following human prostate cell lines using synchrotron X-ray microfluorescence: tumor cell line androgen independent (DU145), tumor cell line androgen dependent (LNCaP), and normal cell line (RWPE-1). The measurements were performed with a standard geometry of 45° of incidence, excited by a white beam using a pixel of 25 μm and an acquisition time of 300 ms/pixel at the X-ray fluorescence beamline at the Synchrotron Light National Laboratory (Campinas, Brazil). The synchrotron X-ray microfluorescence results showed differences between groups in all elements analyzed and suggested that further studies should be performed to understand the relationship of these trace elements with the progression and development of the disease.     

A Hydroperoxide-Mediated Decarboxylation of α-Ketoacids Enables the Chemoselective Acylation of Amines

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information.