Solid-state mechanochemical synthesis of chitosan from mud crab (Scylla serrata) chitin.

This study presents a method for solvent-free mechanochemical synthesis of chitosan from chitin, sourced from the shells of mud crabs (Scylla serrata). The procedure involves a sequence of demineralization and deproteinization to extract chitin from the crab shells, followed by mechanochemical deacetylation. The chitin was deacetylated by grinding it as a solid blend with sodium hydroxide (NaOH) using a stainless steel mortar and pestle. After grinding, chitosan is isolated from the blend by repetitive washing and centrifugation. The chitosan product is then characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis. These characterization techniques confirm the successful deacetylation of chitin to form chitosan. A high degree of deacetylation (DD) is achieved when the weight ratio of NaOH to chitin is 1:1 or higher, implying that the DD value can be enhanced by increasing this weight ratio. The mechanochemical reaction mechanism involves the hydroxyl groups on the NaOH particles reacting with the acetamide groups of the chitin strands, yielding solid chitosan and sodium acetate. This mechanochemical deacetylation approach is more practical than the conventional heterogeneous deacetylation in strong basic solutions, since it could suppress depolymerization of the resulting chitosan and requires significantly less base. This makes it a promising method for large-scale industrial applications.

Dynamics and thermodynamics for competitive adsorptive removal of methylene blue and rhodamine B from binary aqueous solution onto durian rind.

Concurrent adsorptive removal of methylene blue (MB) and rhodamine B (RhB) onto durian rind (DR) agricultural waste, from an aqueous binary solution as a model of wastewater containing multiple synthetic dyes, was investigated. The concurrent adsorption of the dyes followed pseudo-second-order kinetics. The adsorption isotherm was well simulated by the Langmuir model, implying a monolayer adsorption to the surface with a homogeneous binding energy. The adsorption process was governed by external mass transfer through two-step intraparticle diffusion of the dyes onto the adsorbent surface. The adsorption efficiency of MB (96.4%) is much higher than that of RhB (56.3%). This is attributed to the higher rate constant for the adsorption of MB (0.348 g mg-1 min-1) as compared to that of RhB (0.151 g mg-1 min-1). The adsorption behavior suggested that the two cationic dyes in the binary solution diffused and adsorbed independently and randomly onto the DR surface. The adsorption capacity of MB and RhB in the binary solution (47.4 mg g-1 and 32.9 mg g-1, respectively) is lower than those of their single solute solutions (93.3 mg g-1 and 62.8 mg g-1, respectively), suggesting a competitive effect in their concurrent adsorption. This was confirmed based on the adsorption characteristics of the binary solution with different molar ratios. The competitive effect was attributed to either non-interactive or repulsive electrostatic interactions between the positively charged dyes in the binary system. The domination of MB is attributed to its smaller molecular size, higher planarity, and faster adsorption kinetics compared with RhB.

Antimicrobial activity of silver sulfide quantum dots functionalized with highly conjugated Schiff bases in a one-step synthesis.

In the present paper, low-dimensional Ag2S QDs were fabricated for the first time, with four different dithiocarbazate derivative Schiff bases (SB) as capping agents in a one-pot synthesis. These SB-capped Ag2S QDs were almost spherical with an average size range of 4.0 to 5.6 nm, which is slightly smaller than conventional thioglycolic acid (TGA)-capped Ag2S QDs. We demonstrate that the growth of Gram-positive bacteria (Bacillus subtillus and Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), and a prevalent fungal pathogen (Candida albicans) are inhibited more when the bacterial and fungal cells were nurtured with the synthesized SB-Ag2S QDs, compared with TGA-Ag2S QDs or free unbound Schiff bases. The minimum inhibitory concentration (MIC) results confirmed that even low concentrations of SB-Ag2S QDs were able to inhibit bacterial (MIC 5-75 µg mL-1) and fungal growth (MIC 80-310 µg mL-1), and in some cases they performed better than streptomycin (8-25 µg mL-1). Lethality bioassay results confirmed that SB-Ag2S QDs were not toxic to brine shrimp (Artemia salina). The results show that capping agents are essential in the design of functional Ag2S QDs, and highlight that Schiff bases provide an excellent opportunity to optimize the biological activities of silver based QDs.

Synergistic effect in concurrent removal of toxic methylene blue and acid red-1 dyes from aqueous solution by durian rind: kinetics, isotherm, thermodynamics, and mechanism.

In the present study, a synergistic effect between cationic methylene blue (MB) and anionic acid red 1 (AR1) on their concurrent adsorptive removal from aqueous binary solution onto durian rind (DR) was systematically investigated in batch mode across different parameters. The concurrent adsorption was pseudo-second-order kinetics and followed the Langmuir isotherm model, similar to their respective single component. The kinetics and intraparticle diffusion analyses demonstrated that the adsorption rate of MB was a 15-fold faster than AR1, and mass transports were governed by a combination of intraparticle and film diffusion. The synergistic effect was evidenced by an enhanced adsorption efficiency of AR1 from 27 to 42%, while that of MB was almost unchanged (97-98%). By changing the molar ratios of MB and AR1, it was found that the maximum adsorption capacity of MB and AR1 was 249 and 200 mg g-1, respectively, in the binary system higher compared with those in their respective single system (108 and 16 mg g-1). Overall data indicated that the synergistic effect was due to electrostatic interactions between cationic and anionic synthetic dyes, supported by negatively charged DR surface, leading to the formation of their stacking layers on the adsorbent surface. Novelty statement: A synergistic effect in concurrent adsorptive removal of synthetic dyes from multicomponent wastewater remains a critical research challenge. We believed that electrostatic interaction between ionic dyes could be explored to enhance their removal efficiency. This report is the first time that such a synergistic effect between cationic methylene blue (MB) and anionic acid red 1 (AR1) on their concurrent adsorption from aqueous binary system is systematically investigated. The kinetics, isotherm, thermodynamics, and mechanism of the concurrent adsorption of MB and AR1 attributed to the synergistic effect are elucidated in detail.

Binary Pectin-Chitosan Composites for the Uptake of Lanthanum and Yttrium Species in Aqueous Media.

Rare-earth elements such as lanthanum and yttrium have wide utility in high-tech applications such as permanent magnets and batteries. The use of biopolymers and their composites as adsorbents for La (III) and Y (III) ions were investigated as a means to increase the uptake capacity. Previous work has revealed that composite materials with covalent frameworks that contain biopolymers such as pectin and chitosan have secondary adsorption sites for enhanced adsorption. Herein, the maximum adsorption capacity of a 5:1 Pectin-Chitosan composite with La (III) and Y (III) was 22 mg/g and 23 mg/g, respectively. Pectin-Chitosan composites of variable composition were characterized by complementary methods: spectroscopy (FTIR, 13C solids NMR), TGA, and zeta potential. This work contributes to the design of covalent Pectin-Chitosan biopolymer frameworks for the controlled removal of La (III) and Y (III) from aqueous media.

Biocompatible chitin-encapsulated CdS quantum dots: Fabrication and antibacterial screening.

Chitin-encapsulated cadmium sulfide quantum dots (CdS@CTN QDs) were successfully synthesized from chitin and Cd(NO3)2 precursor using the colloidal chemistry method, toward the development of biocompatible and biodegradable QDs for biomedical applications. CdS@CTN QDs exhibited the nanocrystalline cubic CdS encapsulated by α-chitin. The average particle size of CdS@CTN QDs was estimated using empirical Henglein model to be 3.9 nm, while their crystallite size was predicted using Scherrer equation to be 4.3 nm, slightly larger compared to 3-mercaptopropionic acid-capped CdS QDs (3.2 and 3.6 nm, respectively). The mechanism of formation was interpreted based on the spectroscopic data and X-ray crystal structures of CdS@CTN QDs fabricated at different pH values and mass ratios of chitin to Cd(NO3)2 precursor. As an important step to explore potential biomolecular and biological applications of CdS@CTN QDs, their antibacterial activities were tested against four different bacterial strains; i.e. Escherichia coli, Bacillus subtillus, Staphylococcus aureus and Pseudomonas aeruginosa.

Design, synthesis and antiamoebic activity of dysprosium-based nanoparticles using contact lenses as carriers against Acanthamoeba sp.

PURPOSE: Contact lenses have direct contact with the corneal surface and can induce sight-threatening infection of the cornea known as Acanthamoeba keratitis. The objective of this study was to evaluate the dysprosium-based nanoparticles (Dy-based NPs), namely Fe3 O4 -PEG-Dy2 O3 nanocomposites and Dy(OH)3 nanorods, as an active component against Acanthamoeba sp., as well as the possibility of their loading onto contact lenses as the drug administering vehicle to treat Acanthamoeba keratitis (AK). METHODS: The Dy-based NPs were synthesized, and they were loaded onto commercial contact lenses. The loading content of the NPs and their release kinetics was determined based on the absorbance of their colloidal solution before and after soaking the contact lenses. The cytotoxicity of the NPs was evaluated, and the IC50 values of their antiamoebic activity against Acanthamoeba sp. were determined by MTT colorimetric assay, followed by observation on the morphological changes by using light microscopy. The mechanism of action of the Dy-based NPs against Acanthamoeba sp. was evaluated by DNA laddering assays. RESULTS: The loading efficiencies of the Dy-based NPs onto the contact lens were in the range of 30.6-36.1% with respect to their initial concentration (0.5 mg ml-1 ). The Dy NPs were released with the flux approximately 5.5-11 µg cm-2  hr-1 , and the release was completed within 10 hr. The emission of the NPs consistently showed a peak at 575 nm due to Dy3+ ion, offering the possible monitoring and tracking of the NPs. The SEM images indicated the NPs are aggregated on the surface of the contact lenses. The DNA ladder assay suggested that the cells underwent DNA fragmentation, and the cell death was due most probably to necrosis, rather than apoptosis. The cytotoxicity assay of Acanthamoeba sp. suggested that Fe3 O4 -PEG, Fe3 O4 -PEG-Dy2 O3 , Dy(NO3 )3 .6H2 O and Dy(OH)3 NPs have an antiamoebic activity with the IC50 value being 4.5, 5.0, 9.5 and 22.5 µg ml-1 , respectively. CONCLUSIONS: Overall findings in this study suggested that the Dy-based NPs can be considered as active antiamoebic agents and possess the potential as drugs against Acanthamoeba sp. The NPs could be loaded onto the contact lenses; thus, they can be potentially utilized to treat Acanthamoeba keratitis (AK).

Correlation of Pediatric Palliative Screening Scale and Quality of Life in Pediatric Cancer Patients.

CONTEXT: Palliative care in children is used to be only intended for those in near end-of-life phase. Ideally, palliative intervention should be given since the first time of cancer diagnosis. Palliative care is introduced from the beginning of the treatment by acknowledging that it helps to ensure an ongoing focus on the quality of life (QOL) so that children still can enjoy their life. Several approaches have been used to identify children with the need of palliative care. AIMS: The aim was to describe the use of Paediatric Palliative Screening Scale (PaPaS Scale) and its depiction to the QOL of children with malignancies. SETTINGS AND DESIGN: A cross-sectional study was conducted in sixty children age 2-18 years with malignancies, who were consulted to the palliative team. SUBJECTS AND METHODS: Sixty participants were recruited randomly during the study. PaPaS Scale and QOL (using PedsQL™ cancer module 3.0) were assessed at the same time. Cutoff points of 67 for parent-proxy report and 68.9 for self-report were used, those who have scores <67 and <68.9 were grouped as low QOL group. PaPaS scale was divided into three groups: (1) no palliative care needs (score 10-14), (2) considered palliative care (15-24), and (3) need for palliative (≥25). STATISTICAL ANALYSIS: Differences between palliative score and QOL were analyzed using Chi-square and Fisher test. RESULTS: Children who have lower QOL based on parent-proxy report (<67) included 25 children; they consist of 16 children (64%) with score 10-14, four children (16%) with score 15-24, and five children (20%) with score ≥25. Children with higher QOL (16 children) consist of ten children (62.5%) with score 10-14, four children (25%) scores 15-24, and two children (12.5%) with score ≥25. In the self-report, children with low QOL (eight children) consist of four children (50%) with score 10-14, four children (50%) with score 15-24, and no children with score ≥ 25. Children with higher QOL (11 children) consist of eight children (72.2%) with score 10-14, two children (18.2%) with scores 15-24, and one child (9.1%) with score ≥25. Statistical analysis showed no correlation between PaPaS score and QOL of children with malignancies in parent-proxy report (P = 0.89) and self-report (P = 0.37). CONCLUSIONS: This study showed that children with malignancies already had lower QOL despite the low PaPaS scale they had. The results of this study support the provision of early palliative intervention, starting with a small proportion of intervention to improve the QOL of cancer child.

Physicochemical analyses, antioxidant, antibacterial, and toxicity of propolis particles produced by stingless bee Heterotrigona itama found in Brunei Darussalam.

In this study, the physicochemical, antioxidant, antibacterial properties, and the toxicity of propolis particles produced by stingless bee Heterotrigona itama found in Brunei Darussalam were investigated. Propolis particles of different sizes were extracted from raw propolis using various volume fractions of ethanol in water. Spectroscopic analyses were utilized to characterize the chemical structures, functional groups, as well as absorbance and fluorescence properties. The total antioxidant capacity of propolis particles, which was assessed using DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, was found to increase with volume fraction of ethanol. The maximum antioxidant capacity was as high as 317.65 mg ascorbic acid equivalent per gram of propolis particles. All of the propolis particles showed antibacterial activity against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). The diameters of the inhibition zone were either significantly higher or equivalent to those of two standard antibiotics (rifampicin and streptomycin), suggesting strong antibacterial activity. The toxicity studies of propolis particles against Caenorhabditis elegans revealed that they are non-toxic after 24 h exposure. Overall findings suggest that H. itama propolis particles are not only an important source of natural antioxidants that could be beneficial for human health, but they have potentials as antimicrobial against bacteria.

Simultaneous adsorption of lanthanum and yttrium from aqueous solution by durian rind biosorbent.

This paper presents the adsorption capacity of a biosorbent derived from the inner part of durian (Durio zibethinus) rinds, which are a low-cost and abundant agro-waste material. The durian rind sorbent has been successfully utilized to remove lanthanum (La) and yttrium (Y) ions from their binary aqueous solution. The effects of several adsorption parameters including contact time, pH, concentrations of La and Y, and temperature on the removal of La and Y ions were investigated. The adsorption isotherm and kinetics of the metal ions were also evaluated in detail. Both La and Y ions were efficiently adsorbed by the biosorbent with optimum adsorption capacity as high as 71 mg La and 35 mg Y per gram biosorbent, respectively. The simultaneous adsorption of La and Y ions follows Langmuir isotherm model, due to the favorable chelation and strong chemical interactions between the functional groups on the surface of the biosorbent and the metal ions. The addition of oxygen content after adsorption offers an interpretation that the rare-earth metal ions are chelated and incorporated most probably in the form of metal oxides. With such high adsorption capacity of La and Y ions, the durian rind sorbent could potentially be used to treat contaminated wastewater containing La and Y metal ions, as well as for separating and extracting rare-earth metal ions from crude minerals.

Anti-amoebic activity of acyclic and cyclic-samarium complexes on Acanthamoeba.

This work investigated the anti-amoebic activity of two samarium (Sm) complexes, the acyclic complex [bis(picrato)(pentaethylene glycol)samarium(III)] picrate-referred to as [Sm(Pic)2(EO5)](Pic)-and the cyclic complex [bis(picrato)(18-crown-6)samarium(III)] picrate-referred to as [Sm(Pic)2(18C6)](Pic). Both Sm complexes caused morphological transformation of the protozoa Acanthamoeba from its native trophozoite form carrying a spine-like structure called acanthopodia, to round-shaped cells with loss of the acanthopodia structure, a trademark response to environmental stress. Further investigation, however, revealed that the two forms of the Sm complexes exerted unique cytotoxicity characteristics. Firstly, the IC50 of the acyclic complex (0.7 µg/mL) was ~ 10-fold lower than IC50 of the cyclic Sm complex (6.5 µg/mL). Secondly, treatment of the Acanthamoeba with the acyclic complex caused apoptosis of the treated cells, while the treatment with the cyclic complex caused necrosis evident by the leakage of the cell membrane. Both treatments induced DNA damage in Acanthamoeba. Finally, a molecular docking simulation revealed the potential capability of the acyclic complex to form hydrogen bonds with profilin-a membrane protein present in eukaryotes, including Acanthamoeba, that plays important roles in the formation and degradation of actin cytoskeleton. Not found for the cyclic complex, such potential interactions could be the underlying reason, at least in part, for the much higher cytotoxicity of the acyclic complex and also possibly, for the observed differences in the cytotoxicity traits. Nonetheless, with IC50 values of < 10 µg/mL, both the acyclic and cyclic Sm complexes feature a promising potential as cytotoxic agents to fight amoebic infections.

A novel antiamoebic agent against Acanthamoeba sp.--A causative agent for eye keratitis infection.

The terbium trinitrate.trihydrate.18-crown ether-6, Tb(NO3)3(OH2)3.(18C6) complex has been characterized by elemental analysis, photoluminescence and single X-ray diffraction. The IC50 values were determined based on MTT assay while light and fluorescence microscopy imaging were employed to evaluate the cellular morphological changes. Alkaline comet assay was performed to analyze the DNA damage. The photoluminescence spectrum of the Tb complex excited at 325 nm displayed seven luminescence peaks corresponding to the (5)D4→(7)F(0, 1, 2, 3, 4, 5, 6) transitions. The cytotoxicity and genotoxicity studies indicated that the Tb(NO3)3(OH2)3.(18C6) complex and its salt form as well as the 18C6 molecule have excellent anti-amoebic activity with very low IC50 values are 7, 2.6 and 1.2 µg/mL, respectively, with significant decrease (p<0.05) in Acanthamoeba viability when the concentration was increased from 0 to 30 µg/mL. The mode of cell death in Acanthamoeba cells following treatment with the Tb complex was apoptosis. This is in contrast to the Tb(NO3)3.6H2O salt- and 18C6 molecule-treated Acanthamoeba, which exhibited necrotic type cells. The percentage of DNA damage following treatment with all the compounds at the IC25 values showed high percentage of type 1 with the % nuclei damage are 14.15±2.4; 46.00±4.2; 36.36±2.4; 45.16±0.6%, respectively for untreated, treated with Tb complex, Tb salt and 18C6 molecule. The work features promising potential of Tb(NO3)3(OH2)3.(18C6) complex as anti-amoebic agent, representing a therapeutic option for Acanthamoeba keratitis infection.

Modification of chitosan by using samarium for potential use in drug delivery system.

In the presence of hydroxyl and amine groups, chitosan is highly reactive; therefore, it could be used as a carrier in drug delivery. For this study, chitosan-Sm complexes with different concentrations of samarium from 2.5 to 25 wt.% have been successfully synthesized by the impregnation method. Chitosan combined with Sm3+ ions produced a drug carrier material with fluorescence properties; thus, it could also be used as an indicator of drug release with ibuprofen (IBU) as a model drug. We evaluated the spectroscopic and interaction properties of chitosan and Sm3+ ions, the interaction of chitosan-Sm matrices with IBU as a model drug, and the effect of Sm3+ ions addition on the chitosan ability to adsorb the drug. The result showed that the hypersensitive fluorescence intensity of chitosan-Sm (2.5 wt.%) is higher than the others, even though the adsorption efficiency of chitosan-Sm 2.5wt.% is lower (29.75%) than that of chitosan-Sm 25 wt.% (33.04%). Chitosan-Sm 25 wt.% showed the highest efficiency of adsorption of ibuprofen (33.04%). In the release process of ibuprofen from the chitosan-Sm-IBU matrix, the intensity of orange fluorescent properties in the hypersensitive peak of 4G5/2→6H7/2 transition at 590 nm was observed. Fluorescent intensity increased with the cumulative amount of IBU released; therefore, the release of IBU from the Sm-modified chitosan complex can be monitored by the changes in fluorescent intensity.

Investigation of crystal structure influence on spectroscopic and photoluminescent properties of terbium-picrate triethylene glycol complex.

The [Tb(Pic)(2)(H(2)O)(EO3)](Pic)·0.5(EO3) complex, for which EO3 and Pic stand for triethylene glycol and picrate anion, respectively, was successfully prepared and characterized. The Tb(III) complex was crystallized in triclinic structure with space group P1¯. The Tb(III) ion was coordinated to nine oxygen atoms from one EO3 ligand, one water molecule, and two Pic anions. The photoluminescent (PL) spectrum of the complex displayed characteristic narrow bands arising from intraconfigurational transitions of the Tb(III) ion. The strongest emission was centred at 544 nm ((5)D(4)→(7)F(5)), which was responsible for the green emission. The short acyclic chain length of the EO3 ligand, lanthanide contraction, and a bulky picrate anion affected the PL intensity, coordination environment around the Tb(III) ion, and crystal structure of the inner-sphere [Tb(Pic)(2)(H(2)O)(EO3)](+) moiety. The unique crystal structure in the Tb complex contained a half mole of triethylene glycol solvated. The complex had a high thermal stability due to the role of π-π stacking interactions of the Pic anions. The appearance of an emission from the ligands suggests that the photoluminescence of ligands cannot be quenched by coordination to the Tb(III) ion in its complex, so the intramolecular energy transfer process from the triplet state of the ligands (T(1)(L)) to the resonant emissive energy level of Tb(III) is not effective.

Study and fabrication of europium picrate triethylene glycol complex.

A mononuclear of [Eu(NO3)(Pic)(H2O)2(EO3)](Pic)·(0.73)H2O complex, where EO3=trietraethylene glycol and Pic=picrate anion, shows a red emission when used as an active layer in a single layer of ITO/EO3-Eu-Pic/Al configuration. The crystal structure of the complex consists of [Eu(NO3)(Pic)(H2O)2(EO3)]+ cation and [Pic]- anion. The Eu(III) ion is coordinated to the 10 oxygen atoms from one EO3 ligand, one Pic anion, one nitrate anion, and two water molecules. The complex is crystallized in triclinic with space group P-1. The hybrids in thin films I and II were prepared in the respective order solution concentrations of 15 and 20 mg/mL the emissive center. Comparing the photoluminescence (PL) and electroluminescence (EL) spectra, we can find that all emissions come from the characteristic transitions of the Eu(III) ion. The EL spectra of both thin films showed the occurrence of the most intense red-light emission around at 612 nm. Comparison of organic light-emitting device (OLED) current intensity characteristics as a function of voltage (I-V) show that the thin film I is better than those found for the thin film II. The thickness of the emitting layer is an important factor to control the current-voltage curve. The sharp and intense emission of the complex at low voltage indicates that the complex is a suitable and promising candidate for red-emitting materials.

The manganese(III) complex with chelating Schiff base ligand: X-ray structure, spectroscopic and computational studies.

A new Mn(III) complex, [MnCl(H(2)O)(L)].H(2)O.C(2)H(5)OH, where L=2,2'-[1,2-phenylenebis[nitrilomethylylidene]]bis(6-methoxyphenolate), has been synthesized and characterized by single-crystal X-ray diffraction. There is a good agreement between calculated and experimental structural data. The complex is crystallized in orthorhombic with space group Pbca. The Mn1 atom is coordinated with one Schiff base ligand, one water molecule and one chloride anion, forming a six-coordination number. The electronic and fluorescence spectra of the complex were also studied.

Coordination of Ce(III) and Nd(III) with pentaethylene glycol in the presence of picrate anion: spectroscopic and X-ray structural studies.

(1)H NMR evidence for direct coordination between the Ln(III) ion and the oxygen atoms of the pentaethylene glycol (EO5) ligand and the picrate anion (Pic) in [Ln(Pic)(2)(EO5)][Pic] {Ln=Ce and Nd} complexes are confirmed by single X-ray diffraction. No dissociation of Ln-O bonds in dimethyl sulfoxide-d solution was observed in NMR studies conducted at different temperatures ranging 25-100 degrees C. The Ln(III) ion was chelated to nine oxygen atoms from the EO5 ligand in a hexadentate manner and the two Pic anions in each bidentate and monodentate modes. Both compounds are isostructural and crystallized in monoclinic with space group P2(1)/c. Coordination environment around the Ce1 and Nd1 atoms can be described as tricapped trigonal prismatic and monocapped square antiprismatic geometries, respectively. The crystal packing of the complexes have stabilized by one dimensional (1D) chains along the [001] direction to form intermolecular O-Hcdots, three dots, centeredO and C-Hcdots, three dots, centeredO hydrogen bonding. The molar conductance of the complexes in DMSO solution indicated that both compounds are ionic. The complexes had a good thermal stability. Under the UV-excitation, these complexes exhibited the red-shift emission.

Synthesis and structure of dimeric anthracene-9-carboxylato bridged dinuclear erbium(III) complex, [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)].

We study the influence of the bulky aromatic rings, e.g. anthracence-9-carboxylic acid (9-ACA) with a large conjugated pi-system on the structure and spectroscopic properties of [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex where 9-AC=anthracence-9-carboxylato and DMF=N,N'-dimethylformamide. The complex has been prepared from the erbium chloride and 9-ACA in the mixture of H(2)O:DMF solution (4:1, v/v) followed by pH adjustment to 6. The complex is crystallized in a monoclinic system with space group P2(1)/n. The two Er(III) ions are double bridged by the deprotonated carboxyl groups of two 9-AC anions (O1 and O1A), forming an eight-coordination number. The chelating bidentate (O,O), chelating-bridging tridentate (O,O,O') and monodentate of 9-AC anions are observed in the dinuclear [Er(2)(9-AC)(6)(DMF)(2)(H(2)O)(2)] complex. The Er-Er distance is 4.015A in the dimeric unit. Intramolecular O-Hcdots, three dots, centeredO and C-Hcdots, three dots, centeredO hydrogen bonds as well as numerous of intermolecular C-Hcdots, three dots, centeredpi interactions between the anthracene rings by edge-to-face interactions linked the dinuclear dimeric units into two-dimensional supramolecular network in a propeller-arrangement. Electronic absorption spectra of the Er(III) complex and its salt were measured. The emission spectrum of the complex is composed of a broad band due to the emission of intraligand pi*-->pi transition from the 9-AC anions and a shoulder peak originating from the 4f-4f emission transition of the Er(III) ions. The complex has a high thermal stability which can be attributed to the effectively increase the rigidity of the 9-AC anions.

Aqua-dipicrato(tetra-ethyl-ene glycol)gadolinium(III) picrate methanol hemisolvate.

THE ASYMMETRIC UNIT OF THE TITLE COMPOUND [SYSTEMATIC NAME: aqua-bis(2,4,6-trinitro-phenolato)(3,6,9-trioxaundecane-1,11-diol)gadolinium(III) 2,4,6-trinitro-phenolate methanol hemi-solvate], [Gd(C(6)H(2)N(3)O(7))(2)(C(8)H(18)O(5))(H(2)O)](C(6)H(2)N(3)O(7))·0.5CH(4)O, contains two crystallographically independent Gd(III) complex cations with two uncoordinated picrate anions and one methanol mol-ecule. Each Gd(III) atom has nine coordination sites occupied by five O atoms of tetra-ethyl-ene glycol as a penta-dentate ligand, one O atom of a water mol-ecule and three O atoms of the two picrate anions as bidentate and monodentate ligands. The geometry is distorted tricapped trigonal prismatic. The mean planes of the two coordinated mono- and bidentate picrate ligands to the Gd(III) center are almost perpendicular to each other, as indicated by the dihedral angles of 89.92 (8) and 86.60 (8)° in the two complex cations. The ions are arranged in a two-dimensional network parallel to the ac plane. Short O⋯O and N⋯O contacts between the nitro groups, intra-molecular C-H⋯O hydrogen bonds, inter-molecular O-H⋯O, O-H⋯N and C-H⋯O hydrogen bonds, and two π-π inter-actions between benzene rings [centroid-centroid distances = 3.8073 (10)-3.9831 (10) Å] are observed. The methanol solvent mol-ecule is disordered over two positions, with site-occupancy factors of ca 0.6 and 0.4.

Dibenzo-18-crown-6-picric acid-water (1/2/3).

In the crown ether ring of the title compound, C(20)H(24)O(6)·2C(6)H(3)N(3)O(7)·3H(2)O, the O-C(H(2))-C(H(2))-O torsion angles indicate a gauche conformation of the ethyl-eneoxy units, while the C-O-C-C torsion angles indicate planarity of these segments; the dihedral angle between the two benzene rings is 44.53 (13)°. In both picric acid mol-ecules, one of the nitro groups is twisted away from the attached ring. The mol-ecules are linked into chains along the b axis via inter-molecular O-H⋯O hydrogen bonds. In addition, the crystal structure is stabilized by C-H⋯O hydrogen bonds and π-π inter-actions [centroid-centroid distance between benzene rings = 3.5697 (16) Å].