Competition between crystal growth and intracrystalline chain diffusion determines the lamellar thickness in semicrystalline polymers

The non-equilibrium thickness of lamellar crystals in semicrystalline polymers varies significantly between different polymer systems and depends on the crystallization temperature Tc. There is currently no consensus on the mechanism of thickness selection. Previous work has highlighted the decisive role of intracrystalline chain diffusion (ICD) in special cases, but a systematic dependence of lamellar thickness on relevant timescales such as that of ICD and stem attachment has not yet been established. Studying the morphology by small-angle X-ray scattering and the two timescales by NMR methods and polarization microscopy respectively, we here present data on poly(oxymethylene), a case with relatively slow ICD. It fills the gap between previously studied cases of absent and fast ICD, enabling us to establish a quantitative dependence of lamellar thickness on the competition between the noted timescales.

Formation and Evolution of sp2 Hybrid Conjugate Structure of Polyacrylonitrile Precursor during Stabilization

The generated sp2 hybrid conjugate structure of a C atom, which resulted from the chemical reaction affected by temperature and time, is an effective six-membered ring planar structure of the final carbon fiber. This kind of hybrid conjugate structure determined the formation of the final structure and mechanical properties of carbon fiber. In this paper, the formation and evolution of sp2 hybrid conjugated structures of PAN precursor during thermal stabilization were investigated by Raman, UV-vis and 13C-NMR methods. The results indicated that with the increase of stabilization temperature, the degree of the sp2 hybrid conjugated structure of stabilized PAN fiber increases “linearly”, while the content of the sp2 hybrid carbon atoms increases with “S-type”. The final sp2 hybrid conjugated ring structure is mainly composed of single-ring, double-ring, triple-ring, and double-bond structures. Compared with the time factor, the temperature effect plays a decisive role in the formation of the sp2 hybrid conjugate structure.

SpinSPJ: a novel NMR scripting system to implement artificial intelligence and advanced applications

Background Software for nuclear magnetic resonance (NMR) spectrometers offer general functionality of instrument control and data processing; these applications are often developed with non-scripting languages. NMR users need to flexibly integrate rapidly developing NMR applications with emerging technologies. Scripting systems offer open environments for NMR users to write custom programs. However, existing scripting systems have limited capabilities for both extending the functionality of NMR software’s non-script main program and using advanced native script libraries to support specialized application domains (e.g., biomacromolecules and metabolomics). Therefore, it is essential to design a novel scripting system to address both of these needs. Result Here, a novel NMR scripting system named SpinSPJ is proposed. It works as a plug-in in the Java based NMR spectrometer software SpinStudioJ. In the scripting system, both Java based NMR methods and original CPython based libraries are supported. A module has been developed as a bridge to integrate the runtime environments of Java and CPython. The module works as an extension in the CPython environment and interacts with Java via the Java Native Interface. Leveraging this bridge, Java based instrument control and data processing methods of SpinStudioJ can be called with the CPython style. Compared with traditional scripting systems, SpinSPJ better supports both extending the non-script main program and implementing advanced NMR applications with a rich variety of script libraries. NMR researchers can easily call functions of instrument control and data processing as well as developing complex functionality (such as multivariate statistical analysis, deep learning, etc.) with CPython native libraries. Conclusion SpinSPJ offers a user-friendly environment to implement custom functionality leveraging its powerful basic NMR and rich CPython libraries. NMR applications with emerging technologies can be easily integrated. The scripting system is free of charge and can be downloaded by visiting http://www.spinstudioj.net/spinspj.

Synthesis and mechanical and thermal properties of multiblock terpoly(ester-ether-amide) thermoplastic elastomers with variable mole ratio of ether and amide block

A series of the terpolymers of poly[(trimethylene terephthalate)-block-(oxytetramethylene)-block-laurolactam] with a variable molar ratio of ether and amide block and constant molecular weights of PA12 = 2000 g/mole and PTMO = 1000 g/mole have been obtained. The influence of changes of these molar ratios on the functional properties and the values of phase change temperatures of the products have been determined. The thermal properties and the phase separation of obtained systems were defined by DSC, DMTA and WAXS methods. The chemical structure of obtained materials was studied by FT-IR and 13C NMR methods. The mechanical and elastic properties of these polymers were evaluated.

Microalgae and Cyanobacteria Strains as Producers of Lipids with Antibacterial and Antibiofilm Activity

Lipids are one of the primary metabolites of microalgae and cyanobacteria, which enrich their utility in the pharmaceutical, feed, cosmetic, and chemistry sectors. This work describes the isolation, structural elucidation, and the antibiotic and antibiofilm activities of diverse lipids produced by different microalgae and cyanobacteria strains from two European collections (ACOI and LEGE-CC). Three microalgae strains and one cyanobacteria strain were selected for their antibacterial and/or antibiofilm activity after the screening of about 600 strains carried out under the NoMorFilm European project. The total organic extracts were firstly fractionated using solid phase extraction methods, and the minimum inhibitory concentration and minimal biofilm inhibitory concentration against an array of human pathogens were determined. The isolation was carried out by bioassay-guided HPLC-DAD purification, and the structure of the isolated molecules responsible for the observed activities was determined by HPLC-HRESIMS and NMR methods. Sulfoquinovosyldiacylglycerol, monogalactosylmonoacylglycerol, sulfoquinovosylmonoacylglycerol, α-linolenic acid, hexadeca-4,7,10,13-tetraenoic acid (HDTA), palmitoleic acid, and lysophosphatidylcholine were found among the different active sub-fractions selected. In conclusion, cyanobacteria and microalgae produce a great variety of lipids with antibiotic and antibiofilm activity against the most important pathogens causing severe infections in humans. The use of these lipids in clinical treatments alone or in combination with antibiotics may provide an alternative to the current treatments.

Structural Studies of β-Diketones and Their Implications on Biological Effects

The paper briefly summarizes methods to determine the structure of β-diketones with emphasis on NMR methods. Density functional calculations are also briefly treated. Emphasis is on the tautomeric equilibria of β-diketones in relation to biological effects. Relevant physical parameters such as acidity and solubility are treated. A series of biologically active molecules are treated with respect to structure (tautomerism). Characteristic molecules or groups of molecules are usnic acids, tetramic and tetronic acids, o-hydroxydibenzoylmethanes, curcumines, lupulones, and hyperforines.

Characterization of Microbial Degradation Products of Steviol Glycosides

Steviol glycosides were subjected to bacteria present in a soil sample collected from a Stevia plantation in Paraguay. During the incubation experiments, next to the aglycon steviol, steviol degradation products were also formed. X-ray analysis and NMR methods in combination with chemical synthesis and GIAO NMR calculations were used to fully characterize the structure of these compounds as a tricyclic ketone and the corresponding reduced form. They were nicknamed monicanone and monicanol. The latter has the (S)-configuration at the alcohol site.

Advanced NMR methodologies in rock core analysis

<p>¹H NMR techniques have gained extensive acceptance in petrophysics for the evaluation of fluid-saturating reservoir rocks. This thesis presents the development of new NMR methods regarding the reserves (determination of pore length scales and surface relaxivities), productivity (estimates of permeability) and recovery of fluids (resolves of saturation evolution) in rocks. Traditionally, pore lengths are evaluated from the ground relaxation eigenmodes of spin-bearing molecules in pore space. This evaluation is not straightforward since it is affected by surface relaxivity. Here, we use an approach to determine pore length from detecting the high relaxation eigenmodes, in which way the eigenvalue spectrum directly scales to the pore size distribution. Based on this, we extend this approach for the use with low-field NMR spectrometers and 2D NMR eigenmode correlation methods. Surface relaxivity can be further extracted from these 2D correlation maps, which is in agreement with an independent NMR measurement. Permeability is generally estimated from surface relaxation via empirical pore-network models. However, for heterogeneous rocks a single (or averaged) permeability value may not be adequate. Therefore, we measure surface relaxation in conjunction with MRI techniques. Permeability profiles can then be obtained from spatially resolved relaxation maps yielding local connectedness between adjacent slices. The results are confirmed by the comparison of brine-permeability measurements. MRI experiments of fluids in rocks at reservoir-like conditions may yield optimized recovery strategies of reservoir fluids. In this context we combine MRI with diffusion-relaxation correlation measurements during flooding intervals. The results provide substantial information, such as flooding front and saturation profiles of immiscible fluids discriminated by fluid type.</p>

Advanced NMR methodologies in rock core analysis

<p>¹H NMR techniques have gained extensive acceptance in petrophysics for the evaluation of fluid-saturating reservoir rocks. This thesis presents the development of new NMR methods regarding the reserves (determination of pore length scales and surface relaxivities), productivity (estimates of permeability) and recovery of fluids (resolves of saturation evolution) in rocks. Traditionally, pore lengths are evaluated from the ground relaxation eigenmodes of spin-bearing molecules in pore space. This evaluation is not straightforward since it is affected by surface relaxivity. Here, we use an approach to determine pore length from detecting the high relaxation eigenmodes, in which way the eigenvalue spectrum directly scales to the pore size distribution. Based on this, we extend this approach for the use with low-field NMR spectrometers and 2D NMR eigenmode correlation methods. Surface relaxivity can be further extracted from these 2D correlation maps, which is in agreement with an independent NMR measurement. Permeability is generally estimated from surface relaxation via empirical pore-network models. However, for heterogeneous rocks a single (or averaged) permeability value may not be adequate. Therefore, we measure surface relaxation in conjunction with MRI techniques. Permeability profiles can then be obtained from spatially resolved relaxation maps yielding local connectedness between adjacent slices. The results are confirmed by the comparison of brine-permeability measurements. MRI experiments of fluids in rocks at reservoir-like conditions may yield optimized recovery strategies of reservoir fluids. In this context we combine MRI with diffusion-relaxation correlation measurements during flooding intervals. The results provide substantial information, such as flooding front and saturation profiles of immiscible fluids discriminated by fluid type.</p>