Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

A new tetranuclear copper(II) complex with oximate bridges: structure, magnetic properties and DFT study

A new tetranuclear complex, [Cu4L4](ClO4)4·2H2O (1), has been synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligand (2E,3E)-3-(2-aminopropylimino) butan-2-one oxime (HL). Single-crystal X-ray diffraction studies reveal that complex 1 consists of a Cu4(NO)4 core where the four copper(II) centers having square pyramidal environment are arranged in a distorted tetrahedral geometry. They are linked together by a rare bridging mode (μ3-η1,η2,η1) of oximato ligands. Analysis of magnetic susceptibility data indicates moderate antiferromagnetic (J1 = −48 cm−1, J2 = −40 cm−1 and J3 = −52 cm−1) exchange interaction through σ-superexchange pathways (in-plane bridging) of the oxime group. Theoretical calculations based on DFT technique have been used to obtain the energy states of different spin configurations and estimate the coupling constants and to understand the exact magnetic exchange pathways.

Four novel mononuclear and polynuclear Cu(I) thiosaccharinates with triphenylphosphane and bis(diphenylposphino)methane. Synthesis and structural study of Cu(4)(tsac)(4)(PPh(3))(3), Cu(tsac)(PPh(3))(2), Cu(4)(tsac)(4)(dppm)(2), and Cu(2)(tsac)(2)(dppm)(2)

Four new ternary complexes of copper(I) with thiosaccharin and phosphanes were prepared. The reaction of [Cu(4)(tsac)(4)(CH(3)CN)(2)] (1) (tsac: thiosaccharinate anion) with PPh(3) in molar ratios Cu(I)/PPh(3) 1:075 and 1:2 gave the complexes [Cu(4)(tsac)(4)(PPh(3))(3)] center dot CH(3)CN (2) and Cu(tsac)(PPh(3))(2) (3), respectively. The reaction of 1 with Ph(2)PCH(2)PPh(2) (dppm) in molar ratios Cu(I)/dppm 2:1 and 1:1 gave the complexes [Cu(4) (tsac)(4)(dppm)(2)] center dot 2CH(2)Cl(2) (4) and [Cu(2)(tsac)(2)(dppm)(2)] center dot CH(2)Cl(2) (5), respectively. All the compounds have been characterized by spectroscopic and X-ray crystallographic methods. Complex 2 presents a tetra-nuclear arrangement with three metal centers in distorted tetrahedral S(2)NP environments, the fourth one with the Cu(I) ion in a distorted trigonal S(2)N coordination sphere, and the tsac anions acting as six electron donor ligands in mu(3)-S(2)N coordination forms. Complex 3 shows mononuclear molecular units with copper(I) in a distorted trigonal planar coordination sphere, built with the exocyclic S atom of a mono-coordinated thiosaccharinate anion and two P-atoms of triphenylphosphane molecules. With dppm as secondary ligand the structures of the complexes depends strongly on the stoicheometry of the preparation reaction. Complex 4 has a centrosymmetric structure. Two triply bridged Cu(2)(tsac)(2)(dppm) units are joined together by the exocyclic S-atoms of two tsac anions acting effectively as bridging tridentate ligands. Complex 5 is conformed by asymmetric dinuclear moieties where the two dppm and one tsac ligands bridge two Cu(I) atoms and the second tsac anion binds one of the metal centers through its exocyclic S-atom. (C) 2009 Elsevier B.V. All rights reserved.

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Errors in nonword repetition: bridging short- and long-term memory

According to the working memory model, the phonological loop is the component of working memory specialized in processing and manipulating limited amounts of speech-based information. The Children's Test of Nonword Repetition (CNRep) is a suitable measure of phonological short-term memory for English-speaking children, which was validated by the Brazilian Children's Test of Pseudoword Repetition (BCPR) as a Portuguese-language version. The objectives of the present study were: i) to investigate developmental aspects of the phonological memory processing by error analysis in the nonword repetition task, and ii) to examine phoneme (substitution, omission and addition) and order (migration) errors made in the BCPR by 180 normal Brazilian children of both sexes aged 4-10, from preschool to 4th grade. The dominant error was substitution [F(3,525) = 180.47; P < 0.0001]. The performance was age-related [F(4,175) = 14.53; P < 0.0001]. The length effect, i.e., more errors in long than in short items, was observed [F(3,519) = 108.36; P < 0.0001]. In 5-syllable pseudowords, errors occurred mainly in the middle of the stimuli, before the syllabic stress [F(4,16) = 6.03; P = 0.003]; substitutions appeared more at the end of the stimuli, after the stress [F(12,48) = 2.27; P = 0.02]. In conclusion, the BCPR error analysis supports the idea that phonological loop capacity is relatively constant during development, although school learning increases the efficiency of this system. Moreover, there are indications that long-term memory contributes to holding memory trace. The findings were discussed in terms of distinctiveness, clustering and redintegration hypotheses.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (&GE; 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Thermal Behavior and Spectroscopic Study of Neutral and Cationic Mononuclear Cyclopalladated Compounds

The reactions of the precursor [Pd(N,C-dmba)(MeCN)2](NO 3) (1) (dmba = N,N-dimethylbenzylamine), with the proligands 3,5-dimethylpyrazole (Hdmpz), 2-quinolinethiol (qnSH) and 1,1′- bis(diphenylphosphine)ferrocene (dppf) afforded the compounds [Pd(N,C-dmba)(Hdmpz)(ONO2)]0.5CH2Cl2 (2), [Pd(N,C-dmba)(qnSH)(ONO2)] 0.5CH2Cl2 (3) and [Pd(N,C-dmba)(dppf)](NO3) (4), respectively. The mononuclear species 2,3 and 4 were characterized by elemental analysis, infrared spectroscopy, NMR and thermogravimetric analysis. The IR spectra show bands which are consistent with terminal monodentate nitrate group for 2-3 and ionic nitrate for 4. The 1H and 13C NMR data confirm that coordination of the organic ligands has occurred and the 31P{1H} NMR data for 4 clearly evidences the occurrence in solution of three cyclopalladated species with the dppf acting as a bridging ligand in two cases and as a chelate in one. The thermal behavior of compounds 1-4 suggests that complex 2 is the most stable. The X-ray diffractometry results show the formation of PdO from 1 and 2, Pd2OSO4 from 3, and of a mixture of PdO and Fe 2(PO4)3 from 4, as final decomposition products.

Synthesis and characterization of a diruthenium(II,III)-ketoprofen compound and study of the in vitro effects on CRC cells in comparison to the naproxen and ibuprofen derivatives

A new diruthenium(II,III) complex, of formula [Ru2Cl(ket)(4)], Ruket, containing the non-steroidal anti-inflammatory drug ketoprofen was synthesized and mainly characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis-IR electronic spectroscopy and FTIR and Raman vibrational spectroscopies. The four drug-carboxylato bridging ligands stabilize a Ru-2(II,III) mixed valent core in a paddlewheel type structure as confirmed by ESI mass spectra, electronic and vibrational spectroscopies and magnetic measurements. Ruket and the analogous compounds containing ibuprofen, Ruibp, and naproxen, Runpx, were tested for the biological effects in the human colon carcinoma cells HT-29 and Caco-2 expressing high and low levels of COX-2 respectively. All compounds only weakly affected the proliferation of the colorectal cancer cells HT-29 and Caco-2, and similarly only partially inhibited the production/activity of MMP-2 and MMP-9 by HT-29 cells, suggesting that COX-2 inhibition by these drugs can only partially be involved in the pharmacological effects of these derivatives. (c) 2012 Elsevier Ltd. All rights reserved.

Transformations of bridging ligands in diiron complexes: unconventional routes to new functionalized multisite bound organic frames

The main scope of this Ph.D. thesis has concerned the possible transformations of bridging ligands in diiron complexes, in order to explore unconventional routes to the synthesis of new functionalized multisite bound organic frames. The results achieved during the Ph.D. can be summarized in the following points: 1) We have extended the assembling between small unsaturated molecules and bridging carbyne ligands in diiron complexes to other species. In particular, we have investigated the coupling between olefins and thiocarbyne, leading to the synthesis of thioallylidene bridging diiron complexes. Then, we have extended the study to the coupling between olefins and aminocarbyne. This result shows that the coupling between activated olefins and heteroatom substituted bridging carbynes has a general character. 2) As we have shown, the coupling of bridging alkylidyne ligands with alkynes and alkenes provides excellent routes to the synthesis of bridging C3 hydrocarbyl ligands. As a possible extension of these results we have examined the synthesis of C4 bridging frames through the combination of bridging alkylidynes with allenes. Also in this case the reaction has a general character. 3) Diiron complexes bearing bridging functionalized C3 organic frames display the presence of donor atoms, such as N and S, potentially able to coordinate unsaturated metal fragments. Thus, we have studied the possibility for these systems to act as ‘organometallic ligands’, in particular towards Pd and Rh. 4) The possibility of releasing the organic frame from the bridging coordination appears particularly appealing in the direction of a metal-assisted organic synthesis. Within this field, we have investigated the possibility of involving the C3 bridging ligand in cycloaddition reactions with alkynes, with the aim of generating variously functionalized five-membered cycles. The [3+2] cyclization does not lead to the complete release of the organic fragment but rather it produces its transformation into a cyclopentadienyl ring, which remains coordinated to one Fe atom. This result introduces a new approach to the formation of polyfunctionalised ferrocenes. 5) Furthermore, I have spent a research period of about six months at the Department of Inorganic Chemistry of the Barcelona University, under the supervision of Prof. Concepción López, with the aim of studying the chemistry of polydentate ferrocenyl ligands and their use in organometallic synthesis.

Tail bridging vs. patchiness

The subject of this thesis are the interactions between nucleosome core particles (NCPs). NCPs are the primary storage units of DNA in eucaryotic cells. Each NCP consists of a core of eight histone proteins and a strand of DNA, which is wrapped around about two times. Each histone protein has a terminal tail passing over and between the superhelix of the wrapped DNA. Special emphasis was placed on the role of the histone tails, since experimental ndings suggest that the tails have a great in uence on the mutual attraction of the NCPs. In those experiments Mangenot et al. observe a dramatic change in the con guration of the tails, which is accompanied by evidence of mutual attraction between NCPs, when a certain salt concentration is reached. Existing models used in the theoretical approaches and in simulations focus on the description of the histone core and the wrapped DNA, but neglect the histone tails. We introduce the multi chain complex as a new simulation model. Here the histone core and the wrapping DNA are modelled via a charged sphere, while the histone tails are represented by oppositely charged chains grafted on the sphere surface. We start by investigating the parameter space describing a single NCP. The Debye-Huckel potential is used to model the electrostatic interactions and to determine the e ective charge of the NCP core. This value is subsequently used for a study of the pairinteraction of two NCPs via an extensive Molecular Dynamics study. The monomer distribution of the full chain model is investigated. The existence of tail bridges between the cores is demonstrated. Finally, by discriminating between bridging and non-bridging con gurations, we can show that the effect of tail bridging between the spheres does indeed account for the observed attraction. The full chain model can serve as a model to study the acetylation of the histone tails of the nucleosome. The reduction of the charge fraction of the tails, that corresponds to the process of acetylation, leads to a reduction or even the disappearance of the attraction. A recent MC study links this e ect to the unfolding of the chromatin ber in the case of acetylated histone tails. In this case the acetylation of the histone tails leads to the formation of heterochromatin, and one could understand how larger regions of the genetic information could be inactivated through this mechanism.

Bridging innovation, nature and tradition: assessment of strategies for rural tourism development in Maramureş (Romania)

In the frame of EU rural policy, always more oriented towards environmental concerns and green livelihoods, Romania stands out for the predominance of rural areas and high nature value farming. The country has to face the challenge of joining the modernization process of rural farming systems with the valorization of local assets. Tourism has emerged as one of the main drivers of change and contributors for a sustainable exploitation of local resources. Rural tourism (RT) can foster the enhancement of the territorial capital (TC), the preservation of public goods (PGs) and the promotion of a more environmental oriented livelihood. The research focuses on a case study area, two valleys from Maramureş, where environmental approaches as diversification strategies are partially explored. The work investigates the role of tourism initiatives for the promotion of green oriented practices. The first part of the work is based on a literature review and interdisciplinary analysis of secondary data to identify the key issues: from rural development policy, to the concept of TC, of PGs and RT. The Romanian development programmes and related strategies are investigated; afterwards the characteristics of the County and the role of RT as diversification and valorisation policies is considered. The second part is based on the collection of primary data through interviews to different local stakeholders (farmers owners of rural guesthouses, local administrators, networks and artisans). The main frequencies are analyzed, a cluster analysis is computed to evaluate the similarities within the most representative groups and a comparative analysis is carried out between the two Valleys. The frame of the analysis is based on a set of indicators following the dimensions of the TC, to assess the characteristics of the local stakeholders and to outline the perception about the local PGs and on the adopted strategies to manage the territory. Final considerations are elaborated and few scenarios are outlined, giving relevance to the importance of improving awareness and creating embeddedness among public-private local stakeholders and resources as a tool for a socio-economic and environmental development of the area.

Osseointegration of hollow cylinder based spinal implants in normal and osteoporotic vertebrae: a sheep study

INTRODUCTION: Osteoporosis is not only responsible for an increased number of metaphyseal and spinal fractures but it also complicates their treatment. To prevent the initial loosening, we developed a new implant with an enlarged implant/bone interface based on the concept of perforated, hollow cylinders. We evaluated whether osseointegration of a hollow cylinder based implant takes place in normal or osteoporotic bone of sheep under functional loading conditions during anterior stabilization of the lumbar spine. MATERIALS AND METHODS: Osseointegration of the cylinders and status of the fused segments (ventral corpectomy, replacement with iliac strut, and fixation with testing implant) were investigated in six osteoporotic (age 6.9 +/- 0.8 years, mean body weight 61.1 +/- 5.2 kg) and seven control sheep (age 6.1 +/- 0.2 years, mean body weight 64.9 +/- 5.7 kg). Osteoporosis was introduced using a combination protocol of ovariectomy, high-dose prednisone, calcium and phosphor reduced diet and movement restriction. Osseointegration was quantified using fluorescence and conventional histology; fusion status was determined using biomechanical testing of the stabilized segment in a six-degree-of-freedom loading device as well as with radiological and histological staging. RESULTS: Intact bone trabeculae were found in 70% of all perforations without differences between the two groups (P = 0.26). Inside the cylinders, bone volume/total volume was significantly higher than in the control vertebra (50 +/- 16 vs. 28 +/- 13%) of the same animal (P<0.01), but significantly less (P<0.01) than in the near surrounding (60 +/- 21%). After biomechanical testing as described in Sect. "Materials and methods", seven spines (three healthy and four osteoporotic) were classified as completely fused and six (four healthy and two osteoporotic) as not fused after a 4-month observation time. All endplates were bridged with intact trabeculae in the histological slices. CONCLUSIONS: The high number of perforations, filled with intact trabeculae, indicates an adequate fixation; bridging trabeculae between adjacent endplates and tricortical iliac struts in all vertebrae indicates that the anchorage is adequate to promote fusion in this animal model, even in the osteoporotic sheep.

High molecular weight kininogen regulates platelet-leukocyte interactions by bridging Mac-1 and glycoprotein Ib

Leukocyte-platelet interaction is important in mediating leukocyte adhesion to a thrombus and leukocyte recruitment to a site of vascular injury. This interaction is mediated at least in part by the beta2-integrin Mac-1 (CD11b/CD18) and its counter-receptor on platelets, glycoprotein Ibalpha (GPIbalpha). High molecular weight kininogen (HK) was previously shown to interact with both GPIbalpha and Mac-1 through its domains 3 and 5, respectively. In this study we investigated the ability of HK to interfere with the leukocyte-platelet interaction. In a purified system, HK binding to GPIbalpha was inhibited by HK domain 3 and the monoclonal antibody (mAb) SZ2, directed against the epitope 269-282 of GPIbalpha, whereas mAb AP1, directed to the region 201-268 of GPIbalpha had no effect. In contrast, mAb AP1 inhibited the Mac-1-GPIbalpha interaction. Binding of GPIbalpha to Mac-1 was enhanced 2-fold by HK. This effect of HK was abrogated in the presence of HK domains 3 or 5 or peptides from the 475-497 region of the carboxyl terminus of domain 5 as well as in the presence of mAb SZ2 but not mAb AP1. Whereas no difference in the affinity of the Mac-1-GPIbalpha interaction was observed in the absence or presence of HK, maximal binding of GPIbalpha to Mac-1 doubled in the presence of HK. Moreover, HK/HKa increased the Mac-1-dependent adhesion of myelomonocytic U937 cells and K562 cells transfected with Mac-1 to immobilized GPIbalpha or to GPIbalpha-transfected Chinese hamster ovary cells. Finally, Mac-1-dependent adhesion of neutrophils to surface-adherent platelets was enhanced by HK. Thus, HK can bridge leukocytes with platelets by interacting via its domain 3 with GPIbalpha and via its domain 5 with Mac-1 thereby augmenting the Mac-1-GPIbalpha interaction. These distinct molecular interactions of HK with leukocytes and platelets contribute to the regulation of the adhesive behavior of vascular cells and provide novel molecular targets for reducing atherothrombotic pathologies.

Myocardial bridging: depiction rate and morphology at CT coronary angiography--comparison with conventional coronary angiography

PURPOSE: To prospectively assess the depiction rate and morphologic features of myocardial bridging (MB) of coronary arteries with 64-section computed tomographic (CT) coronary angiography in comparison to conventional coronary angiography. MATERIALS AND METHODS: Patients were simultaneously enrolled in a prospective study comparing CT and conventional coronary angiography, for which ethics committee approval and informed consent were obtained. One hundred patients (38 women, 62 men; mean age, 63.8 years +/- 11.6 [standard deviation]) underwent 64-section CT and conventional coronary angiography. Fifty additional patients (19 women, 31 men; mean age, 59.2 years +/- 13.2) who underwent CT only were also included. CT images were analyzed for the direct signs length, depth, and degree of systolic compression, while conventional angiograms were analyzed for the indirect signs step down-step up phenomenon, milking effect, and systolic compression of the tunneled segment. Statistical analysis was performed with Pearson correlation analysis, the Wilcoxon two-sample test, and Fisher exact tests. RESULTS: MB was detected with CT in 26 (26%) of 100 patients and with conventional angiography in 12 patients (12%). Mean tunneled segment length and depth at CT (n = 150) were 24.3 mm +/- 10.0 and 2.6 mm +/- 0.8, respectively. Systolic compression in the 12 patients was 31.3% +/- 11.0 at CT and 28.2% +/- 10.5 at conventional angiography (r = 0.72, P < .001). With CT, a significant correlation was not found between systolic compression and length (r = 0.16, P = .25, n = 150) but was found with depth (r = 0.65, P < .01, n = 150) of the tunneled segment. In 14 patients in whom MB was found at CT but not at conventional angiography, length, depth, and systolic compression were significantly lower than in patients in whom both modalities depicted the anomaly (P < .001, P < .01, and P < .001, respectively). CONCLUSION: The depiction rate of MB is greater with 64-section CT coronary angiography than with conventional coronary angiography. The degree of systolic compression of MB significantly correlates with tunneled segment depth but not length.

Cement distribution, volume, and compliance in vertebroplasty: some answers from an anatomy-based nonlinear finite element study

STUDY DESIGN: The biomechanics of vertebral bodies augmented with real distributions of cement were investigated using nonlinear finite element (FE) analysis. OBJECTIVES: To compare stiffness, strength, and stress transfer of augmented versus nonaugmented osteoporotic vertebral bodies under compressive loading. Specifically, to examine how cement distribution, volume, and compliance affect these biomechanical variables. SUMMARY OF BACKGROUND DATA: Previous FE studies suggested that vertebroplasty might alter vertebral stress transfer, leading to adjacent vertebral failure. However, no FE study so far accounted for real cement distributions and bone damage accumulation. METHODS: Twelve vertebral bodies scanned with high-resolution pQCT and tested in compression were augmented with various volumes of cements and scanned again. Nonaugmented and augmented pQCT datasets were converted to FE models, with bone properties modeled with an elastic, plastic and damage constitutive law that was previously calibrated for the nonaugmented models. The cement-bone composite was modeled with a rule of mixture. The nonaugmented and augmented FE models were subjected to compression and their stiffness, strength, and stress map calculated for different cement compliances. RESULTS: Cement distribution dominated the stiffening and strengthening effects of augmentation. Models with cement connecting either the superior or inferior endplate (S/I fillings) were only up to 2 times stiffer than the nonaugmented models with minimal strengthening, whereas those with cement connecting both endplates (S + I fillings) were 1 to 8 times stiffer and 1 to 12 times stronger. Stress increases above and below the cement, which was higher for the S + I cases and was significantly reduced by increasing cement compliance. CONCLUSION: The developed FE approach, which accounts for real cement distributions and bone damage accumulation, provides a refined insight into the mechanics of augmented vertebral bodies. In particular, augmentation with compliant cement bridging both endplates would reduce stress transfer while providing sufficient strengthening.