Alveolar bone defects (ABDs) were a perennial problem, especially in the aged. Bisphosphonates, especially etidronate sodium (ET), were frequently used in clinical treatment of ABD. However, the oral administration of ET had poor absorption (<1%). Therefore, optimization of a suitable dosage form substituted with ET to locally repair the ABD was a straightforward approach. Polylactide-co-glycolide (PLGA) is a biodegradable material and had been used in locally implanted medical devices. Therefore, an ET-PLGA microcapsule may help local delivery and prolong the activity of healing ABD. In this paper, a preparation method of ET-PLGA microcapsule was optimized by the single-factor investigation and response surface method. Subsequently, the rat ABD model was used to evaluate the enhancement effect of these microcapsules. Finally, the optimum parameters were determined as follows: 40% dichloromethane, 160 mg/mL PLGA, 10% internal aqua/oil phase, 4% PVA, and emulsifying for 10 min. These microcapsules were spherical in shape and fairly monodisperse in a particle size of 27,51 μm (PDI = 0.3), encapsulation rate 96.6%, and drug loading 4.58%. Compared with the ET groups, the total healing volume of ABD in ET-PLGA groups was significantly increased (P < 0.05). ET-PLGA microcapsules significantly enhanced the effect of ET on ABD. This study provided important technical support for the treatment of ABD with bisphosphonates by local administration. This paper has an exploratory significance for the development of water-soluble bioactive components with low bioavailability for ABD.

In recent years, particular attention has been paid to the natural antioxidants. Bee products, especially propolis, are characterized by multifunctional (antioxidant, anti-inflammatory, antibacterial, antiviral, and food preservative) effects and can be used for the development of functional food or food preservatives. Propolis extracts that are commonly produced are ethanolic; therefore, to certain groups of consumers, for example, children and alcohol sensitive group, their applicability is limited. The aim of this study was to develop alternative propolis from aqueous-polyethylenglycolic propolis extract (AQUA-PEG) and compare the chemical composition as well as antioxidant (radical-scavenging and reduction properties) activities to those of ethanolic propolis extract (EEP). Polyethylene glycol is quite a good solvent, which can be successfully used for the preparation of NEP. The total quantity of phenolic compounds identified in AQUA-PEG (400.36 µg/mL), prepared according to our technology, is very similar to that of EEP (433.53 µg/mL), whereas the amount of phenolic acids was greater by 1.31-fold in AQUA-PEG and of flavonoids was greater by 2.38-fold in EEP. The antioxidant activity depends on the method used: by applying the ABTS and CUPRAC methods, both extracts demonstrate similar antioxidant (antiradical and reducing) activity, whereas in the case of the DPPH and FRAP method, significantly higher antioxidant activity was detected in EEP. This should be taken by researchers into account especially when interpreting the results and drawing conclusions about the antioxidant activity of propolis extracts. On the basis of the results, AQUA-PEG, prepared by the developed technology, can be used as an alternative form to ethanolic propolis extract, since it contains a large quantity of antioxidants, namely, flavonoids and phenolic acids. We believe that nonethanolic propolis extract has the prospect of being applied for the development of functional foods in order to alleviate certain symptoms of oxidative stress or for the prevention of some oxidative-stress-related diseases.

The demand for healthier foods with high nutritional value has resulted in intensive fish farming. In this production system, high-frequency infections occur, and antibiotics are administrated for control. Only two antibiotics are allowed for use in Brazilian aquaculture, one of which is florfenicol. In this work, a bioconcentration assay was performed to assess the accumulation of florfenicol in the muscle of Nile tilapia (Oreochromis niloticus). Tilapia was evaluated as it is the most produced fish species in Brazil. The fish were exposed to florfenicol at a nominal concentration of 10 mg/L, through the water. Muscle and water were collected at 0, 1.5, 3, 6, 24, and 48 h during the exposure phase and at 1.5, 3, 6, 24, 48, and 120 h during the depuration phase. Quantification was performed using an LC-MS/MS. The results showed rapid absorption and elimination of the antibiotic (half-life, t1/2 = 5 h), with low potential for accumulation of florfenicol in tilapia muscles. The study was performed to determine the bioconcentration factor (BCF) and withdrawal period of florfenicol, being 0.05 mL/μg and 1.8 h, respectively. The results contribute to set protocols for the safe use of florfenicol in tilapia transport, avoiding residues in fish that may pose risks to human health.

A cross-linked polymer inclusion membrane (CL-PIM) incorporating the extractant trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate (Cyphos® IL 104) was developed for the first time for the enhanced Au(III) recovery from aqua regia digests of electronic waste (discarded mobile phones). Cellulose triacetate (CTA), poly(vinyl chloride) (PVC) and poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) were examined as base polymers. The suitability of poly(ethylene glycol) dimethylacrylate (PEGDMA), poly(ethylene glycol) divinyl ether (PEGDVE) and N-ethylmaleimide (NEM) as cross-linking agents, and the possibility of using triarylsulfonium hexafluorophosphate (TASHFP) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as initiators were investigated. It was demonstrated that the CL-PIMs composed of Cyphos® IL 104 (30 wt%), PVDF-HFP, PEGDMA (base polymer to cross-linking agent ratio 6:4) and DMPA (1 wt%) or TASHFP (2 wt%) transported Au(III) from 2.5 mol L-1 hydrochloric acid solutions twice as fast as their non-CL-PIM counterpart, showing excellent stability over five successive transport experiments. However, in aqua regia feed solutions (6 mol L-1 acidity) only the CL-PIM containing TASHFP was able to achieve complete Au(III) recovery. AFM studies revealed that the PVDF-HFP-based CL-PIMs had a much higher surface contact area when compared to their non-CL counterpart, and this is proposed to be the reason for their superior transport performance. The CL-PIM that showed good transport efficiency in aqua regia was also applied to aqua regia digests of electronic waste from two mobile phones, and Au(III) was selectively recovered in less than 24 h, while other metals present in significantly higher concentrations were not transported.

Due to fast nasal mucociliary clearance, only the dissolved drug content can effectively permeate the mucosa and be pharmaceutically active after intranasal application of suspensions. Therefore, the aim of this study was to increase the budesonide concentration in solution of a nasal spray formulation. Budesonide, a highly water-insoluble corticosteroid, was successfully solubilized using a micellar formulation comprising escin, propylene glycol and dexpanthenol in an aqueous buffered environment ("Budesolv"). A formulation based on this micellar system was well-tolerated in the nasal cavity as shown in a good laboratory practice (GLP) local tolerance study in rabbits. Ex vivo permeation studies into porcine nasal mucosa revealed a faster and more efficient absorption. Budesolv with 300 µg/mL solubilized budesonide resulted in a budesonide concentration of 42 µg/g tissue after only 15 min incubation. In comparison, incubation with the marketed product Rhinocort® aqua 64 (1.28 mg/mL budesonide as suspension) led to 15 µg/g tissue. The in vivo tumor-necrosis-factor (TNF)-α secretion in an acute lung inflammation mouse model was significantly reduced (p < 0.001) following a prophylactic treatment with Budesolv compared to Rhinocort® aqua 64. Successful treatment 15 min after the challenge was only possible with Budesolv (40% reduction of TNF-α, p = 0.0012) suggesting a faster onset of action. The data reveal that solubilization based on saponin micelles presents an opportunity for the development of products containing hardly soluble substances that result in a faster onset and a better topical treatment effect.

The purpose of this study was to evaluate the influence of various polishing protocols on the surface roughness of polyetheretherketone (PEEK) and identify an effective polishing method of dental prostheses at the chairside. The PEEK specimens were assigned to seven groups with different protocols: no additional polishing (NT); polishing using a rubber point (C); polishing using "silky shine" (S); polishing using "aqua blue paste" (A); protocol C followed by protocol S (CS); protocol C followed by protocol A (CA); and protocol C followed by protocols S and A (CSA). The surface roughness (Sa and Ra) of the polished surfaces was measured. The surface roughness decreased in the following order of groups: NT, C, S, CS, CSA, CA, and A. In Groups C and S, wide deep pits formed by abrasive grains of SiC paper were observed, whereas only fine linear structures were observed on the surface in other groups. With respect to the polishing protocol of PEEK, clinically acceptable surface roughness was obtained using a soft polishing brush and agent for more than 3 min.

Most robust functional organic materials are currently based on polymers. These materials exhibit high stability, but once formed they are difficult to modify, adapt to their environment, and recycle. Materials based on small molecules that are held together by noncovalent interactions can offer an alternative to conventional polymer materials for applications that require adaptive and stimuli-responsive features. However, it is challenging to engineer macroscopic noncovalent materials that are sufficiently robust for practical applications. This Account summarizes progress made by our group towards the development of noncovalent "aqua materials" based on well-defined organic molecules. These materials are uniquely assembled in aqueous media, where they harness the strength of hydrophobic and π-π interactions between large aromatic groups to achieve robustness. Despite their high stability, these supramolecular systems can dynamically respond to external stimuli. We discuss design principles, fundamental properties, and applications of two classes of aqua materials: (1) supramolecular gels and (2) nanocrystalline arrays. The materials were characterized by a combination of steady-state and time-resolved spectroscopic techniques, electrical measurements, molecular modeling, and high-resolution microscopic imaging, in particular cryogenic transmission electron microscopy (cryo-TEM) and cryogenic scanning electron microscopy (cryo-SEM). All investigated aqua materials are based on one key building block, perylene diimide (PDI). PDI exhibits remarkably stable intermolecular bonds, together with useful chemical and optoelectronic properties. PDI-based amphiphiles carrying poly(ethylene glycol) (PEG) were designed to form linear supramolecular polymers in aqueous media. These one-dimensional arrays of noncovalently linked molecules can entangle and form three-dimensional supramolecular networks, leading to soft gel-like materials. Tuning the strength of interactions between fibers enables dynamic adjustment of viscoelastic properties and functional characteristics. Besides supramolecular gels, we show that simple PDI-based molecules can self-assemble in aqueous medium to form robust organic nanocrystals (ONCs). The mechanical and optoelectronic properties of ONCs are distinctly different from gel-phase materials. ONCs are excellent building blocks for macroscopic free-standing materials that can be used in dry state, unlike hydrogels. Being constructed from small molecules, ONC materials are easy to fabricate and recycle. High thermal robustness, good mechanical properties, and modular design render ONC materials versatile and suitable for a variety of applications. In the future, noncovalent aqua materials can become a sustainable alternative to conventional polymer materials. Examples from our research include stimuli-responsive and recyclable filtration membranes for preparative nanoparticle separation, water purification and catalysis, light-harvesting hydrogels for solar energy conversion, and nanocrystalline films for switchable surface coatings and electronic devices.

This study focused on the quality of sperm obtained from spermatophores of cadaveric shrimp after long-term storage. Spermatophores were collected using the stripping method, which has resulted in maximum sperm viability when this approach was previously used. Cryoprotectants toxicity assessment of samples was conducted using dimethyl sulfoxide (DMSO), methanol (MeOH), ethylene glycol (EG), glycerol (Gly), dimethyl acetamide (DMA) and propylene glycol (PG) at different concentrations (5%, 10% and 30% v/v), prepared in Ca-F saline. Based on the results from the cryoprotectant toxicity assay, DMSO and MeOH were used individually as well as in combination for the subsequent study. Samples along with cryoprotectants were subjected to slow and fast freezing protocols (i.e. -0.5, and -10 °C/min to a final temperature of -80 °C) and were subsequently stored in LN2 (196 °C). Similarly, vitrification was performed by plunging the samples directly in to LN2. Samples of control and cryopreserved spermatophores that were stored for 45 days had sperm viabilities of 91.4 ± 3.6% and 53.9 ± 4.7%, respectively. Further observations with HOST and DNA integrity analyses of the cryopreserved sperm, resulted in percentages of 45.6 ± 4.2%; 58.1 ± 1.7% compared to control values of 82.3 ± 4.8%; 94.3 ± 1.9%, respectively. Use of the one-step slow freezing protocol at the rate of -0.5 °C/min between 4 °C and -80 °C in LN2 with DMSO (5%) + MeOH (5%) was a desirable preservation strategy of spermatophores, compared to other freezing protocols. Unlike sperm viability, the HOST results affirm the fertility potential of the sperm that have the capacity to participate in the fertilization process. Thus, the results of this study demonstrate that long term storage of sperm in spermatophores of Fenneropenaeus indicus collected from cadaveric specimens can result in viable sperm after cryopreservation if extender (Ca-F saline) containing DMSO and MeOH are used.

This work presents a numerical-experimental framework for assessment of stiffness of nanofibres in a fibrous hydrogel - bacterial cellulose (BC) hydrogel - based on a combination of in-aqua mechanical testing, microstructural analysis and finite-element (FE) modelling. Fibrous hydrogels attracted growing interest as potential replacements to some tissues. To assess their applicability, a comprehensive understanding of their mechanical response under relevant conditions is desirable; a lack of such knowledge is mainly due to changes at microscale caused by deformation that are hard to evaluate in-situ because of the dimensions of nanofibres and aqueous environment. So, discontinuous FE simulations could provide a feasible solution; thus, properties of nanofibres could be characterised with a good accuracy. An alternative - direct tests with commercial testing systems - is cumbersome at best. Hence, in this work, a numerical-experimental framework with advantages of convenience and relative easiness in implementation is suggested to determine the stiffness of BC nanofibres. The obtained magnitudes of 53.7-64.9GPa were assessed by calibrating modelling results with the original experimental data.

A major concern in aquaculture is the use of chemical therapeutics, such as antibiotics, because of their impact on the environment as well as on the fish product. As a potential tool for reducing antibiotic use, we tested the application of low-frequency ultrasound as a method for enhancing antibiotic uptake. Rainbow trout juveniles (Oncorhynchus mykiss) were exposed to two different concentrations of oxytetracycline (OTC), flumequine (FLU) and florfenicol (FLO), administered by bath after the application of ultrasound. After exposure, concentrations of these substances were measured in the liver and blood of treated fish. Results showed that the ultrasound treatment can significantly increase the uptake for all three antibiotics. The uptake of OTC for example, in fish exposed to an OTC concentration of 20 mg L[-1] after prior treatment with ultrasound, was similar to the OTC concentrations in their liver and blood to fish exposed to 100 mg L[-1] without sonication. For FLU and FLO, the use of ultrasound caused significant differences of uptake in the liver at high antibiotic concentrations. This suggests that the use of ultrasound as a technique to deliver antibiotics to fish can ultimately reduce the amount of antibiotics discharged into the aquatic environment.

In this paper, we have developed a one-step thermal treatment of polydimethylsiloxane (PDMS) liquid to create transparent super-repellent surface (TSS) and super-repellent powder. They are super-repellent toward water and ethylene glycol. During the one-step thermal treatment, PDMS soot is generated and deposited onto a glass slide (GS) surface to fabricate the TSS without fluorosilane modification. The facilely obtained TSS presented superhydrophobicity and self-cleaning property when immersed into very low surface tension oils such as petroleum ether, hexadecane, peanut oil, and dodecane. Interestingly, by controlling heating time and temperature, wettability of the treated GS surface and the remained white powder can be regulated. The mechanism of tunable wettability was revealed and analyzed by investigating the variations of surface morphology and chemical composition. More importantly, TSS was able to repel highly corrosive aqua regia and saturated NaOH solutions. TSS maintained excellent superhydrophobicity even after chemical and mechanical damages. This simple thermal deposition method was also applicable for other thermally stable substrates to achieve super-repellency, which are believed to find very promising applications.

Florfenicol (FF) and thiamphenicol (TAP) are two typical pharmaceuticals used widely as therapeutica antibiotic agents in aquaculture. However, little is known about the potential adverse effects of these two antibiotics on non-target organisms in the aquatic ecosystem. In this study we investigated the effects of FF and TAP on photosynthesis and the antioxidant system of the cyanobacteria Microcystis flos-aquae. Over a concentration range of 0.001-1μg/L, the results showed that both FF and TAP significantly increased the chlorophyll a content of M. flos-aquae, while the superoxide dismutase (SOD) activity, catalase (CAT) activity and the levels of malondialdehyde (MDA) changed slightly. In contrast, the chlorophyll a content of M. flos-aqua was significantly inhibited (p<0.01) at high concentrations (>1μg/L) of FF and TAP, reaching a 46% inhibition level at 50μg/L FF and 56% inhibition at 100μg/L TAP. At the same time, the activities of SOD and CAT along with MDA content also increased significantly (p<0.01), indicating that the high concentrations of both FF and TAP led to oxidative stress in the algae. In addition, the M. flos-aquae fluorescence parameters (Fv/Fm, Fv/Fo, alpha, ETRmax and Ik) increased with increasing concentration of both FF and TAP, which may be the result of the increasing photoprotection capacity.

Metal complexes might become a new type of promising gene delivery systems because of their low cytotoxicity, structural diversity, controllable aqua- and lipo-solubility, and appropriate density and distribution of positive charges. In this study, Zn2+ complexes (1-10) formed with a series of ligands contained benzimidazole(bzim)were prepared and characterized. They were observed to have different affinities for DNA, dependent on their numbers of positive charges, bzim groups, and coordination structures around Zn2+. The binding induced DNA to condensate into spherical nanoparticles with ~ 50 nm in diameter. The cell transfection efficiency of the DNA nanoparticles was poor, although they were low toxic. The sequential addition of the cell-penetrating peptide (CPP) TAT(48-60) and polyethylene glycol (PEG) resulted in the large DNA condensates (~ 100 nm in diameter) and the increased cellular uptake. The clathrin-mediated endocytosis was found to be a key cellular uptake pathway of the nanoparticles formed with or without TAT(48-60) or/and PEG. The DNA nanoparticles with TAT(48-60) and PEG was found to have the cell transfection efficiency up to 20% of the commercial carrier Lipofect. These results indicated that a simple Zn2+-bzim complex-based composite system can be developed for efficient and low toxic gene delivery through the combination with PEG and CPPs such as TAT.

This study is focused on anomalous strain-rate-dependent behaviour of bacterial cellulose (BC) hydrogel that can be strain-rate insensitive, hardening, softening, or strain-rate insensitive in various ranges of strain rate. BC hydrogel consists of randomly distributed nanofibres and a large content of free water; thanks to its ideal biocompatibility, it is suitable for biomedical applications. Motivated by its potential applications in complex loading conditions of body environment, its time-dependent behaviour was studied by means of in-aqua uniaxial tension tests at constant temperature of 37 °C at various strain rates ranging from 0.000 1s(-1) to 0.3s(-1). Experimental results reflect anomalous strain-rate-dependent behaviour that was not documented before. Micro-morphological observations allowed identification of deformation mechanisms at low and high strain rates in relation to microstructural changes. Unlike strain-rate softening behaviours in other materials, reorientation of nanofibres and kinematics of free-water flow dominate the softening behaviour of BC hydrogel at high strain rates.

It is extremely important for emerging applications and still enormously challenging to develop multifunctional stimuli-responsive anisotropic polymeric micelles with integration of potentially targeted therapeutic and diagnostic function. Herein, we report a first example of fluorescent anisotropic micelles (FAMs) with Fe(3+), DTT, H2O2, and thermal responsive fluorescence and morphology. FAMs from direct aqueous self-assembly of amphiphilic diblock copolymer showed reversible "switch off/on" of aqua fluorescent emission and controllable structural change by sequential addition of Fe(3+) and DTT. In addition, the FAMs had reversible dual-thermal responsiveness of fluorescence and morphology. This micelle could serve as a promising candidate for all-in-one application of quantitative detecting, imaging, drug delivery, and targeted release.

The Li, Rb and Cs complexes with the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D), namely poly[[aqua[μ3-(2,4-dichlorophenoxy)acetato-κ(3)O(1):O(1):O(1')]lithium(I)] dihydrate], {[Li(C8H5Cl2O3)(H2O)]·2H2O}n, (I), poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ(4)O(1):O(1'):O(1'),Cl(2)]dirubidium(I)], [Rb2(C8H5Cl2O3)2(H2O)]n, (II), and poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ(5)O(1):O(1'):O(1'),O(2),Cl(2)]dicaesium(I)], [Cs2(C8H5Cl2O3)2(H2O)]n, (III), respectively, have been determined and their two-dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO4 coordination involves three carboxylate O-atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six-membered ring systems generate a one-dimensional coordination polymeric chain which extends along b and interspecies water O-H...O hydrogen-bonding interactions give the overall two-dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO5Cl coordination about Rb(+) comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentate O(carboxy),Cl-chelate interaction and three bridging carboxylate O-atom bonding interactions from the 2,4-D ligand. A two-dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four-membered Rb2O2 ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua-carboxylate O-H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z' = 2) irregular CsO6Cl coordination centres, each comprising two O-atom donors (carboxylate and phenoxy) and a ring-substituted Cl-atom donor from the 2,4-D ligand species in a tridentate chelate mode, two O-atom donors from bridging carboxylate groups and one from a bridging water molecule. However, the two 2,4-D ligands are conformationally very dissimilar, with one phenoxyacetate side chain being synclinal and the other being antiperiplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intralayer water-carboxylate O-H...O hydrogen bonds.

There is increasing evidence that the physicochemical nature of any given material is a dominant factor for the release of cytokines by innate immune cells, specifically of macrophages, and thus majorly influences their interaction with other cell types. Recently, we could show that the 3D structure of star shaped polytheylene oxide-polypropylene oxide co-polymers (sP(EO-stat-PO))-hydrogel coated substrates has a stronger influence on the release pattern of cytokines after 7 days of culture than surface chemistry. Here, we focused on the analysis of cytokine release over time and a more detailed analysis of cell morphology by scanning electron microscopy (SEM). Therefore, we compared different strategies for SEM sample preparation and found that using osmium tetroxide combined with aqua bidest led to best preparation results. For cytokine release we show significant changes from day 3 to day 7 of cell culture. After 3 days, the sP(EO-stat-PO)-coated substrates led to an induction of pro-angiogenic CCL3 and CCL4, and of low amounts of the anti-inflammatory IL10, which declined at day 7. In contrast, pleiotropic IL6 and the pro-inflammatory TNFα and IL1β were expressed stronger at day 7 than at day 3.

In the present study, we reported fabrication and skin benefit of a novel vitamin E (VE)-loaded silk fibroin (SF) nanofibrous mats. RRR-α-Tocopherol polyethylene glycol 1000 succinate (VE TPGS), a water-soluble derivative of VE, was incorporated into SF nanofiber successfully by aqua solution electrospinning for the first time. Morphology of the composite nanofibers changed with the different amount of VE TPGS: a ribbon-like shape for lower loading dose of VE TPGS, while a round shape for higher loading dose (more than 4% (wt/wt) based on the weight of SF). After treated with 75% (v/v) ethanol vapor, the composite nanofibrous mats showed an excellent water-resistant ability. In vitro study disclosed a sustained release behavior of VE TPGS disassociated from the nanofibrous mats. The mouse skin fibroblasts (L929 cells) cultured on the VE-loaded SF nanofibrous mats spread and proliferated much better than on cover slips. Moreover, the incorporation of VE TPGS was found strengthening the ability of SF nanofibrous mats on protecting the cells against oxidation stress induced by tert-butyl hydroperoxide. Our data presented impressive skin benefits of this VE-loaded SF nanofibrous mats, suggesting a promising applicative potential of this novel product on personal skin care, tissue regeneration and other related area.

In the title complex, {[Mn(C(14)H(6)O(6)S)(C(2)H(6)O(2))(H(2)O)(2)]·C(4)H(9)NO}(n), the Mn(II) ion is six-coordinated in a trans-octa-hedral geometry by two carboxyl-ate O atoms from two 5,5-dioxodibenzo[b,d]thio-phene-3,7-dicarboxyl-ate (L) ligands in a monodentate mode, two O atoms from two ethyl-ene glycol (EG) mol-ecules and two aqua O atoms. The metal ions are linked by the EG and L ligands, forming two-dimensional coordination networks, which are associated into the three-dimensional structure through O-H⋯O hydrogen bonds.

The ruthenium aqua complexes [Ru(H(2)O)(2)(bipy)(2)](OTf)(2), [cis-Ru(6,6'-Cl(2)-bipy)(2)(OH(2))(2)](OTf)(2), [Ru(H(2)O)(2)(phen)(2)](OTf)(2), [Ru(H(2)O)(3)(2,2':6',2''-terpy)](OTf)(2) and [Ru(H(2)O)(3)(Phterpy)](OTf)(2) (bipy = 2,2'-bipyridine; OTf(-) = triflate; phen = phenanthroline; terpy = terpyridine; Phterpy = 4'-phenyl-2,2':6',2''-terpyridine) are water- and acid-stable catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOS(O)(2)CF(3) (triflic acid) as a dehydration co-catalyst they directly convert 1,2-hexanediol to n-hexanol and hexane. The terpyridine complexes are stable and active as catalysts at temperatures > or = 250 degrees C and in either aqueous sulfolane solution or pure water convert glycerol into n-propanol and ultimately propane as the final reaction product in up to quantitative yield. For the terpy complexes the active catalyst is postulated to be a carbonyl species [(4'-R-2,2':6',2''-terpy)Ru(CO)(H(2)O)(2)](OTf)(2) (R = H, Ph) formed by the decarbonylation of aldehydes (hexanal for 1,2-hexanediol and 3-hydroxypropanal for glycerol) generated in the reaction mixture through acid-catalyzed dehydration. The structure of the dimeric complex [{(4'-phenyl-2,2':6',2''-terpy)Ru(CO)}(2)(mu-OCH(3))(2)](OTf)(2) has been determined by single crystal X-ray crystallography (Space group P1 (a = 8.2532(17); b = 12.858(3); c = 14.363(3) A; alpha = 64.38(3); beta = 77.26(3); gamma = 87.12(3) degrees, R = 4.36 %).