Enhancing SMM properties in a family of [Mn6] clusters

The complex [Mn(6)O(2)(Et-sao)(6)(O(2)C(11)H(15))(2)(EtOH)(6)] has U(eff) = 80 K.     

A new N,N,O chelate for transition metal chemistry: Fe5 and Fe6 clusters from the use of 6-hydroxymethyl-2,2'-bipyridine (hmbpH)

The initial use of the anion of 6-hydroxymethyl-2,2'-bipyridine (hmbpH) as a chelate in coordination chemistry is described. The syntheses, crystal structures, and magnetochemical characterization are reported of four new iron(III) clusters [Fe5O2(OH)(O2CMe)5(hmbp)3](ClO4)2 (1) and [Fe6O2(OH)2(O2CR)6(hmbp)4](NO3)2 (R=Ph (2), Me (3), But (4); hmbpH=6-hydroxymethyl-2,2'-bipyridine). The reaction of Fe(ClO4)3, hmbpH, and sodium acetate in a 1:1: approximately 4 ratio in EtOH gave 1, and the reaction between [Fe3O(O2CR)6(H2O)3](NO3) (R=Ph, Me, But) and hmbpH in a 1:1 ratio in MeCN gave 2-4, respectively. The core of 1 consists of a [Fe4(mu3-O)2]8+ butterfly unit to which is attached a fifth Fe atom by bridging O atoms. The core of 2-4 also consists of a [Fe4(mu3-O)2]8+ butterfly unit to which are attached an Fe atom on either side by bridging O atoms. Variable-temperature (T) and -field (H) solid-state DC and AC magnetization (M) studies were carried out on complexes 1-4 in the 5.0-300 K range. Fitting of the data revealed that 1 has an S=5/2 ground state spin whereas 2-4 possess an S=5 ground state. Fitting of the M/NmicroB vs H/T data by matrix diagonalization and including only axial zero-field splitting (ZFS) gave values of the axial ZFS parameter |D| of 0.75, 0.36, 0.46, and 0.36 cm(-1) for 1-4, respectively.     

Viscoelastic Properties and Thermal Stability of Nanohydroxyapatite Reinforced Poly-Lactic Acid for Load Bearing Applications

We studied the reinforcing effects of treated and untreated nanohydroxyapatite (NHA) on poly-lactic acid (PLA). The NHA surface was treated with three different types of chemicals; 3-aminopropyl triethoxysilane (APTES), sodium n-dodecyl sulfate (SDS) and polyethylenimine (PEI). The nanocomposite samples were prepared using melt mixing techniques by blending 5 wt% untreated NHA and 5 wt% surface-treated NHA (mNHA). Based on the FESEM images, the interfacial adhesion between the mNHA filler and PLA matrix was improved upon surface treatment in the order of mNHA (APTES) > mNHA (SDS) > mNHA (PEI). As a result, the PLA-5wt%mNHA (APTES) nanocomposite showed increased viscoelastic properties such as storage modulus, damping parameter, and creep permanent deformation compared to pure PLA. Similarly, PLA-5wt%mNHA (APTES) thermal properties improved, attaining higher Tc and Tm than pure PLA, reflecting the enhanced nucleating effect of the mNHA (APTES) filler.     

A Halogen-Bond-Driven Artificial Chloride-Selective Channel Constructed from 5-Iodoisophthalamide-based Molecules

Despite considerable emphasis on advancing artificial ion channels, progress is constrained by the limited availability of small molecules with the necessary attributes of self-assembly and ion selectivity. In this study, a library of small molecules based on 5-haloisophthalamide and a non-halogenated isophthalamide were examined for their ion transport properties across the lipid bilayer membranes, and the finding demonstrates that the di-hexyl-substituted 5-iodoisophthalamide derivative exhibits the highest level of activity. Furthermore, it was established that the highest active compound facilitates the selective chloride transport that occurs via an antiport-mediated mechanism. The crystal structure of the compound unveils a distinctive self-assembly of molecules, forming a zig-zag channel pore that is well-suited for the permeation of anions. Planar bilayer conductance measurements proved the formation of chloride selective channels. A molecular dynamics simulation study, relying on the self-assembled component derived from the crystal structure, affirmed the paramount significance of intermolecular hydrogen bonding in the formation of supramolecular barrel-rosette structures that span the bilayer. Furthermore, it was demonstrated that the transport of chloride across the lipid bilayer membrane is facilitated by the synergistic effects of halogen bonding and hydrogen bonding within the channel.     

Gastroprotective Effects of Biological Macromolecule: Polysaccharides

The large molecular weight of the macromolecules sets them apart from all other components. This may range from 10 000 to over a million. While the molecular weight of other plant metabolites is seldom beyond 1000. Chemically, macromolecules are made up of long chains and little “building pieces,” which are joined covalently in a variety of ways. Biological macromolecules are large, naturally occurring cellular building blocks that play a range of crucial roles in the development and existence of living organisms. Biomacromolecules are essential in the biomedical field and other related professions. They feature a variety of beneficial properties, including excellent biodegradability, suitable mechanical strength, enhanced bioavailability, etc. They also have significant biocompatibility. They display a variety of biological characteristics, such as antimalignant, antidiabetic, antibacterial, antioxidant, and immunomodulatory. The use of essential carbohydrates including alginate, chitosan, pectin, starches, carrageenan, fucoidan, etc. is common in commercial applications. Natural substance-based pharmacotherapy is now considered to be a highly promising future alternative to conventional medicine. Along with proteins and polynucleotides, polysaccharide is a vital biomacromolecule that has a crucial function in the growth and expansion of living things. A crucial element of higher plants, cell membranes of animal, and cell walls of microbes is polysaccharide. It is intimately tied to physiological processes as well. The importance of polysaccharides as a significant class of bioactive natural compounds has received more attention recently. Numerous studies have shown that natural polysaccharides contain bioactivities, which have led to the use of polysaccharides in the treatment of illness. The many parts of the research findings on the bioactivities of polysaccharides in gastro-protection are included in this paper.     

Synthesis of Naked-eye Detectable Fluorescent 2<Emphasis Type="Italic">H-</Emphasis>chromen-2-One 2, 6-Dicyanoanilines: Effect of Substituents and pH on Its Luminous Behavior

A variety of new coumarin derivatives containing C-4 bridged 2,6-dicyanoanilines (4a-4d) were synthesized via multicomponent one pot approach. These novel sensors were characterized by spectral analysis and a series of pH sensing fluorescence studies were performed, the results indicating that the sensors are highly selective and more effective at various pH. The fluorescence colour changes at different pH could be directly detected by naked eyes.     

Exploiting phosphonate chemistry in metal-mediated dearomatization: stereoselective construction of functionalized spirolactams from arene ruthenium complexes

Arene ruthenium complexes possessing beta-amido phosphonate side chains participate in intramolecular spirocyclization reactions to deliver stable cyclohexadienyl ruthenium adducts. Spirocyclization is accomplished via a tandem two-step sequence that involves stereoselective nucleophilic aromatic addition to the ipso position of the coordinated arene, followed by intermolecular Horner-Wadsworth-Emmons olefination. The resulting eta5-cyclohexadienyl complexes can then be diastereoselectively converted to metal-free azaspiro[4.5]decane derivatives upon oxidative demetalation in the presence of suitable nucleophiles. An asymmetric spirocyclization was demonstrated through application of this procedure to a beta-amido phosphonate prepared from (S)-(-)-alpha-methyl benzylamine. The expected spirolactam product was obtained as a single enantiomer.     

Bioligninolysis: Recent Updates for Biotechnological Solution

Bioligninolysis involves living organisms and/or their products in degradation of lignin, which is highly resistant, plant-originated polymer having three-dimensional network of dimethoxylated (syringyl), monomethoxylated (guaiacyl), and non-methoxylated (p-hydroxyphenyl) phenylpropanoid and acetylated units. As a major repository of aromatic chemical structures on earth, lignin bears paramount significance for its removal owing to potential application of bioligninolytic systems in industrial production. Early reports illustrating the discovery and cloning of ligninolytic biocatalysts in fungi was truly a landmark in the field of enzymatic delignification. However, the enzymology for bacterial delignification is hitherto poorly understood. Moreover, the lignin-degrading bacterial genes are still unknown and need further exploration. This review deals with the current knowledge about ligninolytic enzyme families produced by fungi and bacteria, their mechanisms of action, and genetic regulation and reservations, which render them attractive candidates in biotechnological applications.     

Fracto-mechanoluminescence and mechanics of fracture of solids

The present paper explores the correlation between fracto-mechanoluminescence and fracture of solids and thereby provides a clear understanding of the physics of fracto-mechanoluminescence. When a fluorescent or non-photoluminescent crystal is fractured impulsively by dropping a load on it, then initially the mechanoluminescence (ML) intensity increases linearly with time, attains a maximum value I_m at a particular time t_m and later on it decreases exponentially with time. However, when a phosphorescent crystal is fractured impulsively by dropping a load on it, then initially the ML intensity increases linearly with time, attains a maximum value I_m at a particular time t_m and later on it decreases initially at a fast rate and then at a slow rate. For low impact velocity the value of t_m is constant, however, for higher impact velocity t_m decreases logarithmally with the increasing impact velocity. Whereas the peak ML intensity I_m increases linearly with the impact velocity, the total ML intensity I_T, initially increases linearly with the impact velocity and then it tends to attain a saturation value for higher values of the impact velocity. The value of t_m increases logarithmally with the thickness of crystals, I_m increases linearly with the area of cross-section of crystals and I_T increases linearly with the volume of crystals. Generally, the ML of non-irradiated crystals decreases with increasing temperature of crystals. Depending on the prevailing conditions the ML spectra consist of either gas discharge spectra or solid state luminescence spectra or combination of the both. On the basis of the rate of generation of cracks and the rate of creation of new surface area of crystals, expressions are derived for the ML intensity and they are found to explain satisfactorily the temporal, spectral, thermal, crystal-size, impact velocity, surface area, and other characteristics of ML. The present investigation may be useful in designing of damage sensors, fracture sensors, ML-based safety management monitoring system, fuse-system for army warheads, milling machine, etc. The present study may be helpful in understanding the processes involved in earthquakes, earthquake lights and mine-failure as they basically involve fracture of solids.