Accelerated Nuclear Magnetic Resonance Spectroscopy with Deep Learning

Nuclear magnetic resonance (NMR) spectroscopy serves as an indispensable tool in chemistry and biology but often suffers from long experimental times. We present a proof-of-concept of the application of deep learning and neural networks for high-quality, reliable, and very fast NMR spectra reconstruction from limited experimental data. We show that the neural network training can be achieved using solely synthetic NMR signals, which lifts the prohibiting demand for a large volume of realistic training data usually required for a deep learning approach.     

基于深紫外激光-光发射电子显微技术的高分辨率磁畴成像

基于磁二色效应的光发射电子显微镜磁成像技术是研究薄膜磁畴结构的一种重要研究手段,具有空间分辨率高、可实时成像以及对表面信息敏感等优点.以全固态深紫外激光(波长为177.3 nm;能量为7.0 eV)为激发光源的光发射电子显微技术相比于传统的光发射电子显微镜磁成像技术(以同步辐射光源或汞灯为激发源),摆脱了大型同步辐射光源的限制;同时又解决了当前阈激发研究中由于激发光源能量低难以实现光电子直接激发的技术难题,在实验室条件下实现了高分辨磁成像.本文首先对最新搭建的深紫外激光-光发射电子显微镜系统做了简单介绍.然后结合超高真空分子束外延薄膜沉积技术,成功实现了L10-FePt垂直磁各向异性薄膜的磁畴观测,其空间分辨率高达43.2 nm,与利用X射线作为激发源的光发射电子显微镜磁成像技术处于同一量级,为后续开展高分辨磁成像提供了便利.最后,重点介绍了在该磁成像技术方面取得的一些最新研究成果:通过引入Cr的纳米"台阶",成功设计出FePt的(001)与(111)双取向外延薄膜;并在"台阶"区域使用线偏振态深紫外激光观测到了磁线二色衬度,其强度为圆二色衬度的4.6倍.上述研究结果表明:深紫外激光-光发射电子显微镜磁成像技术在磁性薄膜/多层膜体系磁畴观测方面具备了出色的分辨能力,通过超高真空系统与分子束外延薄膜制备系统相连接,可以实现高质量单晶外延薄膜制备、超高真空原位传输和高分辨磁畴成像三位一体的功能,为未来磁性薄膜材料的研究提供了重要手段.     

Characterization of Hydrogels Made of a Novel Spider Silk Protein eMaSp1s and Evaluation for 3D Printing

Recombinantly produced spider silk proteins have high potential for bioengineering and various biomedical applications because of their biocompatibility, biodegradability, and low immunogenicity. Here, the recently described small spider silk protein eMaSp1s is assembled into hydrogels, which can be 3D printed into scaffolds. Further, blending with a recombinantly produced MaSp2 derivative eADF4(C16) alters the mechanical properties of the resulting hydrogels. Different spider silk hydrogels also show a distinct recovery after a high shear stress deformation, exhibiting the tunability of their features for selected applications.     

Frontal Polymerization of Deep Eutectic Solvents Composed of Acrylic and Methacrylic Acids

Frontal polymerization of deep eutectic solvents (DESs) made with acrylic or methacrylic acid as the monomer and hydrogen bond donor was studied. Fronts with acrylic acid and choline chloride propagated more uniformly than with pure acrylic acid, so an exploration into how the DES affected frontal polymerization was performed. The hydrogen bond acceptor of the DES was replaced by several analogs to determine the effect on the DES front behavior. The analogs used were talc, DMSO, lauric acid, and stearic acid, which acted as a heat sink, inert diluent, hydrogen bonding diluent, and inert phase change material, respectively. None of the methacrylic acid‐analog systems were able to sustain a front. While the acrylic acid‐analog systems did sustain a front (with the exception of stearic acid), none of the fronts replicated the acrylic acid DES behavior. The acrylic acid–talc sample behaved more violently—like pure acrylic acid polymerization—than the acrylic acid DES, and the DMSO and lauric acid samples produced slower fronts than that of the acrylic acid DES. We propose that the reactivity of the acrylic acid and methacrylic acid is enhanced in the DES. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 4046–4050     

Magneto-optical study of magnetite nanoparticles prepared by chemical and biomineralization process

This paper deals with a magneto-optical study of suspensions of magnetosomes. These magnetosomes are synthesized by biomineralization process of magnetotactic bacteria, followed by steps of isolation and purification in order to obtain stable suspensions. The structural analysis evidences the good crystallinity of the magnetite particles with a diameter of 34 nm. Magneto-induced linear and circular anisotropy confirms the important role played by the chains in the orientation mechanism of such magnetic dipoles. Numerical adjustments of the linear anisotropy curves using a classical Langevin orientation model give the average number of magnetosomes per chain, about 12.     

Chiroptical Probing of Lanthanide‐Directed Self‐Assembly Formation Using btp Ligands Formed in One‐Pot Diazo‐Transfer/Deprotection Click Reaction from Chiral Amines

A series of enantiomeric 2,6‐bis(1,2,3‐triazol‐4‐yl)pyridines (btp)‐containing ligands was synthesized by a one‐pot two‐step copper‐catalyzed amine/alkyne click reaction. The Eu^III‐ and Tb^III‐directed self‐assembly formation of these ligands was studied in CH₃CN by monitoring their various photophysical properties, including their emerging circular dichroism and circularly polarized luminescence. The global analysis of the former enabled the determination of both the stoichiometry and the stability constants of the various chiral supramolecular species in solution.     

Main‐chain chiral poly(2‐oxazoline)s: Influence of alkyl side‐chain on secondary structure formation in solution

The synthesis and microwave‐assisted polymerization of a series of chiral 2‐oxazolines with varying alkyl pendant groups, namely R‐2‐ethyl‐4‐ethyl‐2‐oxazoline (R‐EtEtOx), R‐2‐butyl‐4‐ethyl‐2‐oxazoline (R‐BuEtOx), R‐2‐octyl‐4‐ethyl‐2‐oxazoline, 2‐nonyl‐4‐ethyl‐2‐oxazoline, and R‐2‐undecyl‐4‐ethyl‐2‐oxazoline (R‐UndeEtOx), are reported. A kinetic investigation of the polymerization of R‐EtEtOx revealed a living polymerization mechanism. The poly(2‐oxazoline)s containing an ethyl, butyl, and octyl pendant group form similar chiral structures according to circular dichroism measurements. When the pendant group is further elongated, the chiral structure becomes more flexible in trifluoroethanol and the thermal response in hexafluoroisopropanol (HFIP) significantly changes. The short‐range structure of poly‐R‐BuEtOx dissolved in HFIP is thermoresponsive in a complex way, due to HFIP hydrogen bonding to the polymeric amide groups, whereas the long‐range structure determined from small angle neutron scattering is insensitive to temperature demonstrating that only the local secondary structure changes with temperature. In addition, the chiral structure of poly‐R‐UndeEtOx depends on the polarity of the solvent. The short‐range structure becomes more flexible in polar solvents, most likely due to interactions with the amide groups disturbing the secondary structure. In contrast, the long‐range structural transition from an ellipsoid in the apolar n‐hexane to a rod structure in the polar n‐butanol is ascribed to better solvation of the long aliphatic side chains. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A Pyrene-Modified Serinol Nucleic Acid Nanostructure Converts the Chirality of Threoninol Nucleic Acids into Circularly Polarized Luminescence Signals

Herein is reported a circularly polarized luminescent (CPL) probe that can respond to the chirality of nucleic acids. An achiral nanostructure was prepared by the hybridization of symmetric serinol nucleic acid (SNA) containing pyrene-modified residues. When chiral oligomers that were complementary to the SNA were added, they induced helicity into the SNA nanowire. Efficient circular dichroism (CD) signal amplification was observed when pyrene was attached to uracil bases through a rigid alkynyl linker. Both CPL and CD signals were observed; they depended on the chirality of the added acyclic threoninol nucleic acid (aTNA) oligomer. This system can be used to convert the chirality of chiral biomolecules into chiroptical signals.     

Tuning the Efficiency of Dendritic Nanocarriers using Conformational Constraints

A series of deoxycholic and cholic acid‐derived oligomers were synthesized and their ability to extract hydrophilic dye molecules of different structure, size, and functional groups into nonpolar media was studied. The structure of the dye and “dendritic effect” in the extraction process was examined using absorption spectroscopy and dynamic light scattering (DLS). The efficiency of structurally preorganized oligomers in the aggregation process was evaluated by 1‐anilinonaphthalene‐8‐sulfonic acid (ANS) fluorescence studies. The possible formation of globular structures for higher‐generation molecules was investigated by molecular modeling studies and the results were correlated with the anomaly observed in the extraction process with this molecule. The ability of these molecules for selective extraction of specific dyes from blended colors is also reported.     

Ionothermal Synthesis and Structural Characterization of a Novel Open Framework Zinc Diphosphonate with Carboxylate‐like Linker

A novel crystalline zinc diphosphonate, (CH₃NH₃ )₄Zn₂ (xbp)₂•H₂O , denoted as compound 1 , was ionothermally synthesized from tetraethyl‐p ‐xylylenebisphosphonate (Texbp) and Zn(OAc )₂ in a protic eutectic mixture with urea/methylamine hydrochloride. Its structure was determined by single‐crystal X‐ray diffraction data and had a special three‐dimensional open framework with rhombic channels. Compound 1 belongs to the monoclinic system (space group C2 /c ), with lattice parameters a =22.6876(19) Å, b =8.73 76(7) Å, c =8.1673(9) Å, β =108.146(2)°, V =1538.5(2) ų, Z =2. Its structure is totally different from the typical organic pillared structure, only two oxygens of the phosphonate group are coordinated with zinc atoms, and the third oxygen exists in the terminal form, which is similar to the popular dicarboxylate linkers in MOFs . The organic cations [CH₃NH₃ ]⁺ of the eutectic mixture played a structure‐directing role for constructing this framework and were confined in the pore channels to balance the negative charges resulting from the zinc phosphonate inorganic chains.