Thermal Degradation Behavior and Kinetic Analysis of Biodegradable Polymers Using Various Comparative Models, 1

Thermal degradation behavior of a biodegradable polymer (PBS) has been investigated by conventional and MTGA methods. The kinetic parameters of degradation were calculated by a general analytical solution and by the Coats‐Redfern, Ozawa, Horowitz‐Metzger, and MTGA methods. The results reveal that the reaction mechanism at lower temperature is probably the F1 model through the reaction of random chain cleavage via cis‐elimination. However, the reaction mechanism at higher temperature is likely to be D1 model because of the dominant diffusion control effect.

     

Hierarchical Structure‐within‐Structure Morphologies in A‐block‐(B‐graft‐C) Molecules

We have used dissipative particle dynamics (DPD) to simulate the self‐assembling behavior of A‐block‐(B‐graft‐C) coil‐comb molecules, in which each B segment is covalently bonded with one C segment. In addition to the composition, we found that by varying any of the interaction parameters between each pair of components I and J, where I, J = A, B, C, we can also induce a series of morphology transitions associated with two length scales. Moreover, we observed that if the length of the BC‐comb block is not long enough, the resulting morphology is mainly in the large‐length‐scale, ordering between the A‐rich and C‐rich domains with most of the B in the interfaces. By increasing the length of the BC‐comb block, one may expect that both B and C can pack orderly to form a lamellar structure. As a result, various experimentally observed structure‐within‐structures have been simulated via DPD.

     

Unusual Intercalation of Cationic Smectite Clays with Detergent‐Ranged Carboxylic Ions

Summary: The organic intercalation of cationic smectite clays is achieved by using alkali salts of alkyl carboxylic acids, instead of using conventional quaternary ammonium salts as ionic exchanging agents. Various organic acid salts, such as CH₃(CH₂)₁₆COO⁻Na⁺, can be incorporated into divalent montmorillonite (M²⁺‐MMT) with a 30–40 wt.‐% organic embedding and an X‐ray diffraction basal spacing of 43 Å from the pristine 10 Å. The intercalation is generalized for carboxylate salts of different alkyl lengths and for alkali metal ions, including sodium and potassium ions, but is specific for the divalent MMT clay. This new type of organic species for clay modification allows the preparation of organoclays in the absence of quaternary ammonium salts. It is proposed that the organic embedding is driven by the formation of a thermodynamically stable RCOO⁻/M²⁺/SiO⁻ complex.

Graphical illustration of the carboxylic acid salt complex with the divalent cations on silicate K10.     

Polypeptide‐Shelled Poly(propylene imine) Dendrimers and Their Complexing Properties towards Copper(II) Ions

Summary: Polypeptide‐shelled poly(propylene imine) dendrimers were realized by ring‐opening polymerization of α‐amino acid N‐carboxyanhydrides, initiated by dendrimers as core molecules. Polypeptides with 2nd generation core were used as model compounds to investigate interior complexes between metal ion and surface‐modified dendrimers. Micro‐calorimetric measurements outlined the formation of approximate 1:1 complexes between Cu^II and polypeptide‐shelled dendrimers and the influence of polypeptide chain compositions on differential molar heats of complexation.

Composition of one of the polypeptides synthesized.     

Fabrication of Poly(lactic acid) Diacrylate Nanospheres with Double Bonds

Summary: In this paper, unsaturated groups were introduced into poly(lactic acid) (PLA) for fabricating PLA‐based nanospheres with carbon‐carbon double bonds as functional groups. The morphology dependencies on fabrication conditions, including the fabrication time as well as the stirring rate, were also investigated.

SEM‐EDX image of poly(lactic acid) diacrylate nanospheres after exposure to osmium tetroxide vapor for 14 h.     

Measurement of gut microbial metabolites in cardiometabolic health and translational research

The human gut microbiota is a functioning endocrine organ and stands at the intersection between dietary components and health or disease. There are very many microbial metabolites with numerous structures and functions arising from the gut microbial fermentation of foods and become signals for biological communication in the human body. These small molecules can be absorbed and delivered to distant organs through the circulatory system to build the gut–systemic axis. The gut microbial metabolomes are thus believed to play important roles in regulating cardiometabolic health and provide opportunities in mechanistic research and new drug discovery. Measurement of these novel microbial metabolites in clinical samples may serve as a tool for investigating disease biomarkers. In the past decade, the development of untargeted and targeted metabolomics approaches using NMR, LC/MS, and GC/MS has contributed to the exploration of gut microbial metabolomes in cardiometabolic health and disease. Some important targets are currently being translated into clinical applications. In this review article, we introduce an oral carnitine challenge test developed as an example to demonstrate the potential applications in personalized nutrition based on the function of gut microbiota. It is a method taking the gut microbiota as a bioreactor and provides fermentable materials as inputs and measures the outputs of targeted microbial byproducts in the blood or urine. This challenge test may be extended to measure metabolites from microbial fermentation related to other endocrinological or inflammatory diseases. We review current gut metabolome research approaches and propose a gut microbial functional measurement using a challenge test. We suggest that the maturation in measuring gut microbial metabolites may provide an important piece to complete the puzzle of precision medicine.     

On the dynamics of a tethered satellite system

The Hamiltonian structure for a fundamental model of a tethered satellite system is constructed. The model is composed of two point masses connected by a string with no restrictions on the motions of the two masses. A certain symmetry with respect to the special orthogonal group SO(3) for such a system is observed. The classical station-keeping mode for the tethered system is found to be nothing more than the relative equilibrium corresponding to the reduction of the system by the symmetry. The microgravity forces on the two point masses are responsible for the possible configurations of the string at the so-called radial relative equilibrium. A stability analysis is performed on the basis of the reduced energy-momentum method. Criteria for stability are derived, which could find potential applications in space technology.     

Hexacoordinate Phosphorus. 7. Synthesis and Characterization of Neutral Phosphorus(V) Compounds Containing Divalent Tridentate Diphenol Imine, Azo, and Thio Ligands

The reactions of bis(trimethylsilyl)ated forms of the Schiff base ligands N-(2-hydroxyphenyl)salicylideneamine {(HO)C(6)H(4)N(CH)C(6)H(4)(OH)}, N-(4-tert-butyl-2-hydroxyphenyl)salicylideneamine {(HO)((t)Bu)C(6)H(3)N(CH)C(6)H(4)(OH)}, N-(2-hydroxy-4-nitrophenyl)salicylideneamine {(HO)(O(2)N)C(6)H(3)N(CH)C(6)H(4)(OH)}, and the structurally related ligand 2,2'-azophenol with halogeno- and (trifluoromethyl)halogenophosphoranes yield a series of neutral hexacoordinate phosphorus(V) compounds by means of trimethylsilyl halide elimination. In all of these cases the ligands chelate in a meridional conformation in which bicyclic five- and six-membered chelate rings are formed through structures containing two phenolic P-O bonds and one N-P bond. The hexacoordinate nature of these compounds is evidenced by their high-field (31)P NMR chemical shifts and their characteristic J(PF) coupling patterns and is further substantiated by the crystal structures of {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3) and {OC(6)H(4)N=NC(6)H(4)O}PF(3). Crystal data for {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3): triclinic, space group P&onemacr; (No. 2), a = 11.167(1) ?, b = 15.684(1) ?, c = 17.047(2) ?, V = 2840(1) ?(3), Z = 2. Final R and R(w) values were 0.051 and 0.079, respectively. Crystal data for {OC(6)H(4)N=NC(6)H(4)O}PF(3): monoclinic, space group P2(1)/c (No. 14), a = 6.9393(8) ?, b = 12.450(2) ?, c = 13.907(2) ?, V = 1190.7(6) ?(3), Z = 4. Final R and R(w) values were 0.045 and 0.056, respectively. The molecular structures of {O((t)Bu)C(6)H(3)N(CH)C(6)H(4)O}PCl(3) and {OC(6)H(4)N=NC(6)H(4)O}PF(3) show that in both cases the Schiff base ligand chelates occupy the meridional plane about the six-coordinate phosphorus atom. In the case of {OC(6)H(4)N=NC(6)H(4)O}PF(3) the equivalent nitrogen atoms in the chelate rings are disordered to form half-occupancy pairs. The silylated form of the related thiobis(phenol), 2,2'-thiobis(4,6-tert-butylphenol), reacted similarly with pentavalent halides to form the six-coordinate complex [{2-O-3,5-((t)Bu)(2)C(6)H(2)}(2)S]PCl(3) which was also verified by a crystal structure. Crystal data for [{2-O-3,5-((t)Bu)(2)C(6)H(2)}(2)S]PCl(3): monoclinic P2(1)/n, a = 13.989(2), b = 13.594(2), c = 16.483(2) ?, beta = 97.98(2) degrees, V = 3104(2) ?(3), Z = 4; final R and R(w)() values were 0.039 and 0.052, respectively. In contrast to the above six coordinate complexes, this compound possesses a facial structure in which two phenoxy substituents form planar chelates centered on the bridging sulfur and intersecting at the P-S axis. The P-S bond length, 2.331(1) ?, is slightly shorter than has been previously observed in the example wherein the ligand possesses two tert-butyl groups and the phosphorus carries three OCH(2)CF(3 )substituents indicating stronger interaction between P and S in the present case.