Publications by authors named "Valentina Colombo"

31 Publications

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne-Functionalized Nickel(II)-Pyrazolate-Based MOFs.

Chemistry 2021 Jun 11. Epub 2021 Jun 11.

Departamento de Química, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain.

C H /CO separation is a highly challenging process as a consequence of their similar physicochemical properties. In this work we have explored, by static and dynamic gas sorption techniques and computational modelling, the suitability of a series of two isoreticular robust Ni(II)pyrazolate-based MOFs, bearing alkyne moieties on the ligand backbones, for C H /CO separation. The results are consistent with high adsorption capacity and selectivity of the essayed systems towards C H molecules. Furthermore, a post-synthetic treatment with KOH ethanolic solution gives rise to linker vacancy defects and incorporation of extraframework potassium ions. Creation of defects is responsible for increased adsorption capacity for both gases, however, strong interactions of the cluster basic sites and extraframework potassium cations with CO molecules are responsible for a lowering of C H over CO selectivity.
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http://dx.doi.org/10.1002/chem.202100821DOI Listing
June 2021

Robotic-assisted gait rehabilitation following stroke: a systematic review of current guidelines and practical clinical recommendations.

Eur J Phys Rehabil Med 2021 Jun 5;57(3):460-471. Epub 2021 May 5.

Unit of Rehabilitation, ULSS (Local Health Authority) Euganea, Camposampiero Hospital, Padua, Italy.

Introduction: Stroke is the third leading cause of adult disability worldwide, and lower extremity motor impairment is one of the major determinants of long-term disability. Although robotic therapy is becoming more and more utilized in research protocols for lower limb stroke rehabilitation, the gap between research evidence and its use in clinical practice is still significant. The aim of this study was to determine the scope, quality, and consistency of guidelines for robotic lower limb rehabilitation after stroke, in order to provide clinical recommendations.

Evidence Acquisition: We systematically reviewed stroke rehabilitation guideline recommendations between January 1, 2010 and October 31, 2020. We explored electronic databases (N.=4), guideline repositories and professional rehabilitation networks (N.=12). Two independent reviewers used the Appraisal of Guidelines for Research and Evaluation (AGREE) II instrument, and brief syntheses were used to evaluate and compare the different recommendations, considering only the most recent version.

Evidence Synthesis: From the 1219 papers screened, ten eligible guidelines were identified from seven different regions/countries. Four of the included guidelines focused on stroke management, the other six on stroke rehabilitation. Robotic rehabilitation is generally recommended to improve lower limb motor function, including gait and strength. Unfortunately, there is still no consensus about the timing, frequency, training session duration and the exact characteristics of subjects who could benefit from robotics.

Conclusions: Our systematic review shows that the introduction of robotic rehabilitation in standard treatment protocols seems to be the future of stroke rehabilitation. However, robot assisted gait training (RAGT) for stroke needs to be improved with new solutions and in clinical practice guidelines, especially in terms of applicability.
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http://dx.doi.org/10.23736/S1973-9087.21.06887-8DOI Listing
June 2021

Sleeping Beauty-engineered CAR T cells achieve antileukemic activity without severe toxicities.

J Clin Invest 2020 11;130(11):6021-6033

Tettamanti Research Center, Department of Pediatrics, University of Milano-Bicocca/Fondazione MBBM, Monza, Italy.

BACKGROUNDChimeric antigen receptor (CAR) T cell immunotherapy has resulted in complete remission (CR) and durable response in highly refractory patients. However, logistical complexity and high costs of manufacturing autologous viral products limit CAR T cell availability.METHODSWe report the early results of a phase I/II trial in B cell acute lymphoblastic leukemia (B-ALL) patients relapsed after allogeneic hematopoietic stem cell transplantation (HSCT) using donor-derived CD19 CAR T cells generated with the Sleeping Beauty (SB) transposon and differentiated into cytokine-induced killer (CIK) cells.RESULTSThe cellular product was produced successfully for all patients from the donor peripheral blood (PB) and consisted mostly of CD3+ lymphocytes with 43% CAR expression. Four pediatric and 9 adult patients were infused with a single dose of CAR T cells. Toxicities reported were 2 grade I and 1 grade II cytokine-release syndrome (CRS) cases at the highest dose in the absence of graft-versus-host disease (GVHD), neurotoxicity, or dose-limiting toxicities. Six out of 7 patients receiving the highest doses achieved CR and CR with incomplete blood count recovery (CRi) at day 28. Five out of 6 patients in CR were also minimal residual disease negative (MRD-). Robust expansion was achieved in the majority of the patients. CAR T cells were measurable by transgene copy PCR up to 10 months. Integration site analysis showed a positive safety profile and highly polyclonal repertoire in vitro and at early time points after infusion.CONCLUSIONSB-engineered CAR T cells expand and persist in pediatric and adult B-ALL patients relapsed after HSCT. Antileukemic activity was achieved without severe toxicities.TRIAL REGISTRATIONClinicalTrials.gov NCT03389035.FUNDINGThis study was supported by grants from the Fondazione AIRC per la Ricerca sul Cancro (AIRC); Cancer Research UK (CRUK); the Fundación Científica de la Asociación Española Contra el Cáncer (FC AECC); Ministero Della Salute; Fondazione Regionale per la Ricerca Biomedica (FRRB).
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http://dx.doi.org/10.1172/JCI138473DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7598053PMC
November 2020

Binaural Beats Reduce Postoperative Morphine Consumption in Older adults After Total Knee Replacement Surgery.

Altern Ther Health Med 2021 Mar;27(2):27-30

Context: A reduction in the use of opioids by older adult patients could reduce unpleasant side effects for them. During general anesthesia, binaural beat (BB) listening has been found to reduce intraoperative fentanyl consumption as well as postoperative pain scores and discharge time. Auditory BBs are a perceptual phenomenon occurring when tones of 2 slightly different frequencies are presented simultaneously and separately to each ear.

Objective: The study intended to evaluate the ability of BBs, as a nonpharmacological premedication, to reduce postoperative morphine consumption in older adults undergoing total knee replacement surgery and to modify the levels of anxiety and feelings of pain that patients experience.

Design: The research team designed a prospective, single-center, randomized controlled study.

Setting: The study was conducted in the Orthopedic Department of the Santa Maria Maddalena Hospital (Volterra [Pisa], Italy).

Participants: Forty older adults at the hospital who were undergoing total knee joint replacement with spinal anesthesia participated in the study.

Intervention: The study included 2 groups (n = 20 each), one receiving BBs stimulation with frequencies of 256 Hz in one ear and 260 Hz in the opposite ear producing a BB of 4 Hz (intervention group), and the other receiving acoustical stimulation at 256 Hz in both ears (control group). BBs, or acoustical stimulation, were administered before the surgical procedure. Both acoustical stimuli, generated with the Gnaural program, were delivered through stereo headphones connected to a laptop in the preoperative holding area.

Outcome Measures: The study measured postoperative, cumulative, self-administered morphine consumption, in mg, through a patient-controlled analgesia device. Feelings of anxiety were also assessed using the State-Trait Anxiety Inventory, and feelings of pain were measured every 8 h during the first postoperative day using a numerical rating scale.

Results: Patients who received the intervention, consumed almost half of the dosage of morphine during the first postoperative day when compared with the control group's consumption, 5.75 mg ± 5.25 vs 11.85 mg ± 7.71, respectively. The consumption did not correlate to anxiety measures. Regarding pain perception, no differences between the groups were captured.

Conclusions: BB stimulation before surgery can be successfully used as a nonpharmacological treatment to reduce morphine consumption in older adults who undergo knee replacement. The use of a noninvasive, safe, and inexpensive BB intervention can result in a positive effect on patients' postoperative recovery.
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March 2021

Stabilization by Configurational Entropy of the Cu(II) Active Site during CO Oxidation on MgCoNiCuZnO.

J Phys Chem Lett 2020 May 23;11(9):3589-3593. Epub 2020 Apr 23.

CNR - Istituto Officina dei Materiali, TASC, I-34149 Trieste, Italy.

The mechanisms of CO oxidation on the MgCoNiCuZnO high-entropy oxide were studied by means of operando soft X-ray absorption spectroscopy. We found that Cu is the active metal and that Cu(II) can be rapidly reduced to Cu(I) by CO when the temperature is higher than 130 °C. Co and Ni do not have any role in this respect. The Cu(II) oxidation state can be easily but slowly recovered by treatment of the sample with O at ca. 250 °C. However, it should be noted that CuO is readily and irreversibly reduced to Cu(I) when it is treated with CO at > 100 °C. Thus, the main conclusion of this work is that the high configurational entropy of MgCoNiCuZnO stabilizes the rock-salt structure and permits the oxidation/reduction of Cu to be reversible, thus permitting the catalytic cycle to take place.
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http://dx.doi.org/10.1021/acs.jpclett.0c00602DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8007101PMC
May 2020

Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites.

Nat Mater 2020 05 3;19(5):517-521. Epub 2020 Feb 3.

Department of Chemistry, University of California, Berkeley, CA, USA.

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N, through backbonding interactions, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates. Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N capacities and selectivities for the removal of N from mixtures with CH, while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents.
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http://dx.doi.org/10.1038/s41563-019-0597-8DOI Listing
May 2020

Different Metallophilic Attitudes Revealed by Compression.

Inorg Chem 2020 Feb 30;59(4):2223-2227. Epub 2020 Jan 30.

Dipartimento di Chimica, Materiali e Ingegneria Chimica , Politecnico di Milano , Via Mancinelli, 7 , 20131 Milano , Italy.

Two isostructural coordination polymers with coinage metal(I) cations were compressed with the purpose of testing interactions between chains, which may trigger metallophilic interactions or otherwise expand the metal coordination. DFT calculations and X-ray diffraction studies reveal an extraordinary difference between Ag(I) and Cu(I) in homologous compounds. Argentophilic interactions are favored by a mild compression, and at = 7.94 GPa, the Ag-Ag distance matches the value of metallic silver. On the other hand, no cuprophilic interaction is activated even by compression up to 8 GPa, and Cu-Cu distances remain outside the van der Waals spheres.
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http://dx.doi.org/10.1021/acs.inorgchem.9b02852DOI Listing
February 2020

Crystal structure of pirfenidone (5-methyl-1-phenyl-1-pyridin-2-one): an active pharmaceutical ingredient (API).

Acta Crystallogr E Crystallogr Commun 2019 Jul 11;75(Pt 7):984-986. Epub 2019 Jun 11.

Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, I-20133 Milano, Italy.

The crystal structure of pirfenidone, CHNO [alternative name: 5-methyl-1-phenyl-pyridin-2(1)-one], an active pharmaceutical ingredient (API) approved in Europe and Japan for the treatment of Idiopathic pulmonary fibrosis (IPF), is reported here for the first time. It was crystallized from toluene by the temperature gradient technique, and crystallizes in the chiral monoclinic space group 2. The phenyl and pyridone rings are inclined to each other by 50.30 (11)°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds involving the same acceptor atom, forming undulating layers lying parallel to the plane.
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http://dx.doi.org/10.1107/S2056989019006418DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6659322PMC
July 2019

PIDAZTA: Structurally Constrained Chelators for the Efficient Formation of Stable Gallium-68 Complexes at Physiological pH.

Chemistry 2019 Aug 11;25(45):10698-10709. Epub 2019 Jul 11.

Dip. di Scienze del Farmaco, Università del Piemonte Orientale, Largo Donegani 2/3, 28100, Novara, Italy.

Two structurally constrained chelators based on a fused bicyclic scaffold, 4-amino-4-methylperhydro-pyrido[1,2-a][1,4]diazepin-N,N',N'-triacetic acids [(4R*,10aS*)-PIDAZTA (L1) and (4R*,10aR*)-PIDAZTA (L2)], were designed for the preparation of Ga -based radiopharmaceuticals. The stereochemistry of the ligand scaffold has a deep impact on the properties of the complexes, with unexpected [Ga(L2)OH] species being superior in terms of both thermodynamic stability and inertness. This peculiar behavior was rationalized on the basis of molecular modeling and appears to be related to a better fit in size of Ga into the cavity of L2. Fast and efficient formation of the Ga chelates at room temperature was observed at pH values between 7 and 8, which enables Ga radiolabeling under truly physiological conditions (pH 7.4).
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http://dx.doi.org/10.1002/chem.201901512DOI Listing
August 2019

The influence of potential stressors on oviposition site selection and subsequent growth, survival and emergence of the non-biting midge ().

Ecol Evol 2019 May 10;9(9):5512-5522. Epub 2019 Apr 10.

School of BioSciences University of Melbourne Parkville Victoria Australia.

Theory predicts that animals should prefer habitats where their fitness is maximized but some mistakenly select habitats where their fitness is compromised, that is, ecological traps. Understanding why this happens requires knowledge of the habitat selection cues animals use, the habitats they prefer and why, and the fitness costs of habitat selection decisions. We conducted experiments with a freshwater insect, the non-biting midge to ask: (a) whether females respond to potential oviposition cues, (b) to explore whether oviposition is adaptive in relation to metal pollution and conductivity, and (c) whether individuals raised in poor quality sites are more likely to breed in similarly poor locations. We found the following: (a) females responded to some cues, especially conductivity and conspecifics, (b) females preferred sites with higher concentrations of bioavailable metals but suffered no consequences to egg/larval survival, (c) females showed some avoidance of high conductivities, but they still laid eggs resulting in reduced egg hatching, larval survival, and adult emergence, and (d) preferences were independent of natal environment. Our results show that is susceptible to ecological traps, depending on life stage and the relative differences in conductivities among potential oviposition sites. Our results highlight that (a) the fitness outcomes of habitat selection need to be assessed across the life cycle and (b) the relative differences in preference/suitability of habitats need to be considered in ecological trap research. This information can help determine why habitat preferences and their fitness consequences differ among species, which is critical for determining which species are susceptible to ecological traps.
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http://dx.doi.org/10.1002/ece3.5148DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6509373PMC
May 2019

Tailor-Made Microporous Metal-Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion.

Adv Mater 2018 Dec 15;30(49):e1805088. Epub 2018 Oct 15.

Department of Chemistry and Chemical Biology, Rutgers University, 610 Taylor Road, Piscataway, NJ, 08854, USA.

Adsorptive separation of olefin/paraffin mixtures by porous solids can greatly reduce the energy consumption associated with the currently employed cryogenic distillation technique. Here, the complete separation of propane and propylene by a designer microporous metal-organic framework material is reported. The compound, Y (OH) (abtc) (H O) (DMA) (Y-abtc, abtc = 3,3',5,5'-azobenzene-tetracarboxylates; DMA = dimethylammonium), is rationally designed through topology-guided replacement of inorganic building units. Y-abtc is both thermally and hydrothermally robust, and possesses optimal pore window size for propane/propylene separation. It adsorbs propylene with fast kinetics under ambient temperature and pressure, but fully excludes propane, as a result of selective size exclusion. Multicomponent column breakthrough experiments confirm that polymer-grade propylene (99.5%) can be obtained by this process, demonstrating its true potential as an alternative sorbent for efficient separation of propane/propylene mixtures.
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http://dx.doi.org/10.1002/adma.201805088DOI Listing
December 2018

Sol-gel TiO colloidal suspensions and nanostructured thin films: structural and biological assessments.

Nanotechnology 2018 Feb;29(5):055704

Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy.

The role of substrate topography in phenotype expression of in vitro cultured cells has been widely assessed. However, the production of the nanostructured interface via the deposition of sol-gel synthesized nanoparticles (NPs) has not yet been fully exploited. This is also evidenced by the limited number of studies correlating the morphological, structural and chemical properties of the grown thin films with those of the sol-gel 'brick' within the framework of the bottom-up approach. Our work intends to go beyond this drawback presenting an accurate investigation of sol-gel TiO NPs shaped as spheres and rods. They have been fully characterized by complementary analytical techniques both suspended in apolar solvents, by dynamic light scattering (DLS) and nuclear magnetic resonance (NMR) and after deposition on substrates (solid state configuration) by transmission electron microscopy (TEM) and powder x-ray diffraction (PXRD). In the case of suspended anisotropic rods, the experimental DLS data, analyzed by the Tirado-Garcia de la Torre model, present the following ranges of dimensions: 4-5 nm diameter (∅) and 11-15 nm length (L). These results are in good agreement with that obtained by the two solid state techniques, namely 3.8(9) nm ∅ and 13.8(2.5) nm L from TEM and 5.6(1) ∅ and 13.3(1) nm L from PXRD data. To prove the suitability of the supported sol-gel NPs for biological issues, spheres and rods have been separately deposited on coverslips. The cell response has been ascertained by evaluating the adhesion of the epithelial cell line Madin-Darby canine kidney. The cellular analysis showed that titania films promote cell adhesion as well clustering organization, which is a distinguishing feature of this type of cell line. Thus, the use of nanostructured substrates via sol-gel could be considered a good candidate for cell culture with the further advantages of likely scalability and interfaceability with many different materials usable as supports.
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http://dx.doi.org/10.1088/1361-6528/aa9ca0DOI Listing
February 2018

Intravenous infusion of human bone marrow mesenchymal stromal cells promotes functional recovery and neuroplasticity after ischemic stroke in mice.

Sci Rep 2017 07 31;7(1):6962. Epub 2017 Jul 31.

Department of Neuroscience, IRCCS - Istituto di Ricerche Farmacologiche Mario Negri, Via La Masa,19, 20156, Milano, Italy.

Transplantation of human bone marrow mesenchymal stromal cells (hBM-MSC) promotes functional recovery after stroke in animal models, but the mechanisms underlying these effects remain incompletely understood. We tested the efficacy of Good Manufacturing Practices (GMP) compliant hBM-MSC, injected intravenously 3.5 hours after injury in mice subjected to transient middle cerebral artery occlusion (tMCAo). We addressed whether hBM-MSC are efficacious and if this efficacy is associated with cortical circuit reorganization using neuroanatomical analysis of GABAergic neurons (parvalbumin; PV-positive cells) and perineuronal nets (PNN), a specialized extracellular matrix structure which acts as an inhibitor of neural plasticity. tMCAo mice receiving hBM-MSC, showed early and lasting improvement of sensorimotor and cognitive functions compared to control tMCAo mice. Furthermore, 5 weeks post-tMCAo, hBM-MSC induced a significant rescue of ipsilateral cortical neurons; an increased proportion of PV-positive neurons in the perilesional cortex, suggesting GABAergic interneurons preservation; and a lower percentage of PV-positive cells surrounded by PNN, indicating an enhanced plastic potential of the perilesional cortex. These results show that hBM-MSC improve functional recovery and stimulate neuroprotection after stroke. Moreover, the downregulation of "plasticity brakes" such as PNN suggests that hBM-MSC treatment stimulates plasticity and formation of new connections in the perilesional cortex.
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http://dx.doi.org/10.1038/s41598-017-07274-wDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5537246PMC
July 2017

Bifenthrin Causes Toxicity in Urban Stormwater Wetlands: Field and Laboratory Assessment Using Austrochiltonia (Amphipoda).

Environ Sci Technol 2017 Jun 30;51(12):7254-7262. Epub 2017 May 30.

Centre for Aquatic Pollution Identification and Management (CAPIM), School of BioSciences, The University of Melbourne , Royal Parade, Parkville, Australia 3010.

Stormwater wetlands are engineered to accumulate sediment and pollutants from stormwater and provide environmental value to urban environments. Therefore, contaminated sediment risks causing toxicity to aquatic fauna. This research identifies contaminants of concern in urban wetland sediments by assessing sediment toxicity using the amphipod Austrochiltonia subtenuis. Sediments from 98 wetlands were analyzed for contaminants, and laboratory bioassays were performed with A. subtenuis. Wild Austrochiltonia spp. were also collected from wetlands to assess field populations. Random forest modeling was used to identify the most important variables predicting survival, growth, and field absence of Austrochiltonia spp. Bifenthrin was the most frequently detected pesticide and also the most important predictor of Austrochiltonia spp. responses. Copper, permethrin, chromium, triclosan, and lead were also important. The median lethal effect concentration (LC50) of bifenthrin to laboratory-based A. subtenuis (1.09 (±0.08) μg/gOC) exposed to wetland sediments was supported by a bifenthrin-spiked sediment experiment, indicating A. subtenuis is a suitable test species. Furthermore, Austrochiltonia spp. were absent from all sites that exceeded the calculated bifenthrin LC50, demonstrating the impact of this contaminant on wild populations. This research demonstrates the sensitivity of Austrochiltonia spp. to urban sediment contamination and identifies bifenthrin as a contaminant of concern in urban wetlands.
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http://dx.doi.org/10.1021/acs.est.7b01472DOI Listing
June 2017

Municipal wastewater effluent licensing: A global perspective and recommendations for best practice.

Sci Total Environ 2017 Feb 22;580:1327-1339. Epub 2016 Dec 22.

Centre for Aquatic Pollution Identification and Management CAPIM, Building 147 (BioSciences 4), Faculty of Science, University of Melbourne, Victoria 3010, Australia.

Advances in wastewater treatment have greatly improved the quality of municipal wastewater effluents in many parts of the world, but despite this, treated wastewaters can still pose a risk to the environment. Licensing plays a crucial role in the regulation of municipal wastewater effluents by setting standards or limits designed to protect the economic, environmental and societal values of waterbodies. Traditionally these standards have focused on physical and chemical water quality parameters within the discharge itself, however these approaches do not adequately account for emerging contaminants, potential effects of chemical mixtures, or variations in the sensitivity and resilience of receiving environments. In this review we focus on a number of industrialised countries and their approach to licensing. We consider how we can ensure licensing is effective, particularly when considering the rapid changes in our understanding of the impacts of discharges, the technical advances in our ability to detect chemicals at low concentrations and the progress in wastewater treatment technology. In order to meet the challenges required to protect the values of our waterways, licensing of effluents will need to ensure that there is no disconnect between the core values to be protected and the monitoring system designed to scrutinise performance of the WWTP. In many cases this may mean an expansion in the monitoring approaches used for both the effluent itself and the receiving waterbody.
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http://dx.doi.org/10.1016/j.scitotenv.2016.12.096DOI Listing
February 2017

Effects of Lumbriculus variegatus (Annelida, Oligochaete) bioturbation on zinc sediment chemistry and toxicity to the epi-benthic invertebrate Chironomus tepperi (Diptera: Chironomidae).

Environ Pollut 2016 Sep 1;216:198-207. Epub 2016 Jun 1.

CSIRO Land and Water, Lucas Heights, Sydney, NSW, 2234, Australia. Electronic address:

Classical laboratory-based single-species sediment bioassays do not account for modifications to toxicity from bioturbation by benthic organisms which may impact predictions of contaminated sediment risk to biota in the field. This study aims to determine the effects of bioturbation on the toxicity of zinc measured in a standard laboratory bioassay conducted with chironomid larvae (Chironomus tepperi). The epi-benthic chironomid larvae were exposed to two different levels of sediment contamination (1600 and 1980 mg/kg of dry weight zinc) in the presence or absence of annelid worms (Lumbriculus variegatus) which are known to be tolerant to metal and to have a large impact on sediment properties through bioturbation. Chironomids had 5-6x higher survival in the presence of L. variegatus which shows that bioturbation had a beneficial effect on the chironomid larvae. Chemical analyses showed that bioturbation induced a flux of zinc from the pore water into the water column, thereby reducing the bioavailability of zinc in pore water to the chironomid larvae. This also suggested that pore water was the major exposure path for the chironomids to metals in sediment. During the study, annelid worms (Oligochaetes) produced a thin layer of faecal pellets at the sediment surface, a process known to: (i) create additional adsorption sites for zinc, thus reducing its availability, (ii) increase the microbial abundance that in turn could represent an additional food source for opportunistic C. tepperi larvae, and (iii) modify the microbial community's structure and alter the biogeochemical processes it governs thus indirectly impact zinc toxicity. This study represents a contribution in recognising bioturbating organisms as "ecological engineers" as they directly and indirectly influence metal bioavailability and impact other sediment-inhabiting species. This is significant and should be considered in risk assessment of zinc levels (and other metals) in contaminated sediment when extrapolating from laboratory studies to the field.
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http://dx.doi.org/10.1016/j.envpol.2016.05.063DOI Listing
September 2016

Pain control with ultrasound-guided inguinal field block compared with spinal anesthesia after hernia surgery: a randomized trial.

Surgery 2015 Feb;157(2):304-11

Department of Emergency and Intensive Care, San Gerardo University Hospital, Monza, Italy; Department of Health Sciences, University of Milan-Bicocca, Monza, Italy. Electronic address:

Background: Inguinal field block (IFB) is a recommended technique for pain control after inguinal hernia repair but is also underused by surgeons. Currently, there is no decisive evidence on which technique, IFB or spinal anesthesia block (SAB), provides better pain control during the first day after hernia repair. In this study, we compared ultrasound-guided IFB performed by anesthesiologists and SAB for pain control during the first day after hernia repair.

Methods: We compared static and dynamic pain scores measured with a numerical rating scale in 86 male patients scheduled for elective unilateral inguinal hernia repair with either ultrasound-guided IFB (n = 42) or SAB (n = 44).

Results: Dynamic and static pain at 4 hours (P < .01, r > 0.34, "large effect size"), and dynamic pain the morning after operation (P = .04, r > 0.20, "medium effect size") were less in the field block group compared with the SAB group. Postoperative analgesic consumption was reduced during hospital stay (P = .005, r > 0.34, "large effect size") and for 7 postoperative days in the field block group (P = .03, r > 0.20, "medium effect size").

Conclusion: In this study, ultrasound-guided IFB provided lesser dynamic pain scores during the first postoperative day and reduced use of analgesics for 1 week compared with spinal anesthesia after inguinal hernia repair. Our technique could become a substitute performed by anesthesiologists in settings in which IFB is not performed routinely by surgeons.
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http://dx.doi.org/10.1016/j.surg.2014.09.002DOI Listing
February 2015

Crystal chemistry of the antibiotic doripenem.

J Pharm Sci 2014 Nov 17;103(11):3641-3647. Epub 2014 Sep 17.

Dipartimento di Scienza ed Alta Tecnologia, Università dell'Insubria, Como 22100, Italy.

Doripenem, an ultrabroad spectrum-injectable antibiotic belonging to the wide class of carbapenem beta-lactams, is commonly marketed as powders of a pure monohydrate phase. Here, we have selectively prepared another hydrated phase (a dihydrate) and determined the crystal structure of both forms by state-of-the art powder diffraction methods. Both phases crystallize in the monoclinic P21 space group, and, to some extent, are structurally related. Moreover, by using variable temperature diffractometric analyses, we also discovered a crystalline anhydrous form of doripenem, the structure of which (with two crystallographically independent molecules in the monoclinic P21 space group) remains so far unknown. The thermal interconversion among these phases was further studied by thermogravimetry, differential scanning calorimetry, and thermodiffractometric analyses, and their (metric or stereochemical) mutual relations fully analyzed. The complete structural characterization of the two hydrated phases allows the use of accurate whole pattern profile-fitting procedures for quantitative analyses of these drugs in polycrystalline, or even amorphous, matrices, opening the way to industrial process control and legal protection. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:3641-3647, 2014.
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http://dx.doi.org/10.1002/jps.24166DOI Listing
November 2014

Transgenerational effects of parental nutritional status on offspring development time, survival, fecundity, and sensitivity to zinc in Chironomus tepperi midges.

Ecotoxicol Environ Saf 2014 Dec 29;110:1-7. Epub 2014 Aug 29.

CAPIM (Centre for Aquatic Pollution Identification and Management), Department of Zoology, The University of Melbourne, Melbourne, VIC 3010, Australia.

Environmental stimuli can induce plastic changes in life history traits, and stimuli experienced by parents can be transmitted to the next generation ("transgenerational") through the inheritance of factors unrelated to changes in DNA sequences. Transgenerational effects are common in species living in habitats subjected to recurrent stressful events, such as fluctuating resource availability. In a previous study, the nutritional status of the midge Chironomus tepperi has been reported to influence life history traits of the offspring. In this study we investigated whether they also alter sensitivity of offspring to zinc. Offspring of parents reared under low food conditions had a shorter development time and lower reproductive output compared to offspring of parents raised under excess food. While zinc exposure decreased the survival of offspring generally, the interaction between parental food level and zinc exposure did not influence the relative sensitivity of offspring toward zinc. Parental nutritional stress therefore triggered transgenerational effects, potentially acting as confounding factors in ecotoxicological studies, but they did not directly affect the susceptibility of offspring to zinc.
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http://dx.doi.org/10.1016/j.ecoenv.2014.07.037DOI Listing
December 2014

Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach.

Inorg Chem 2014 Jan 16;53(1):139-46. Epub 2013 Dec 16.

Department of Chemistry and NIS Centre of Excellence, University of Torino , Via P. Giuria 7, 10125 Torino, Italy.

The hydrogen bond network of three polymorphs (1α, 1β, and 1γ) and one solvate form (1·H2O) arising from the hydration-dehydration process of the Ru(II) complex [(p-cymene)Ru(κN-INA)Cl2] (where INA is isonicotinic acid), has been ascertained by means of one-dimensional (1D) and two-dimensional (2D) double quantum (1)H CRAMPS (Combined Rotation and Multiple Pulses Sequences) and (13)C CPMAS solid-state NMR experiments. The resolution improvement provided by homonuclear decoupling pulse sequences, with respect to fast MAS experiments, has been highlighted. The solid-state structure of 1γ has been fully characterized by combining X-ray powder diffraction (XRPD), solid-state NMR, and periodic plane-wave first-principles calculations. None of the forms show the expected supramolecular cyclic dimerization of the carboxylic functions of INA, because of the presence of Cl atoms as strong hydrogen bond (HB) acceptors. The hydration-dehydration process of the complex has been discussed in terms of structure and HB rearrangements.
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http://dx.doi.org/10.1021/ic401762zDOI Listing
January 2014

Dynamic rendering of the heterogeneous cell response to anticancer treatments.

PLoS Comput Biol 2013 17;9(10):e1003293. Epub 2013 Oct 17.

Biophysics Unit, Laboratory of Anticancer Pharmacology, Department of Oncology, IRCCS - Istituto di Ricerche Farmacologiche "Mario Negri," Milano, Italy.

The antiproliferative response to anticancer treatment is the result of concurrent responses in all cell cycle phases, extending over several cell generations, whose complexity is not captured by current methods. In the proposed experimental/computational approach, the contemporary use of time-lapse live cell microscopy and flow cytometric data supported the computer rendering of the proliferative process through the cell cycle and subsequent generations during/after treatment. The effects of treatments were modelled with modules describing the functional activity of the main pathways causing arrest, repair and cell death in each phase. A framework modelling environment was created, enabling us to apply different types of modules in each phase and test models at the complexity level justified by the available data. We challenged the method with time-course measures taken in parallel with flow cytometry and time-lapse live cell microscopy in X-ray-treated human ovarian cancer cells, spanning a wide range of doses. The most suitable model of the treatment, including the dose-response of each effect, was progressively built, combining modules with a rational strategy and fitting simultaneously all data of different doses and platforms. The final model gave for the first time the complete rendering in silico of the cycling process following X-ray exposure, providing separate and quantitative measures of the dose-dependence of G1, S and G2M checkpoint activities in subsequent generations, reconciling known effects of ionizing radiations and new insights in a unique scenario.
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http://dx.doi.org/10.1371/journal.pcbi.1003293DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3798276PMC
May 2014

Structural changes in a macrozoobenthos assemblage after imidacloprid pulses in aquatic field-based microcosms.

Arch Environ Contam Toxicol 2013 Nov 1;65(4):683-92. Epub 2013 Aug 1.

Department of Zoology, Centre for Aquatic Pollution Identification and Management (CAPIM), University of Melbourne, Melbourne, VIC, 3010, Australia,

A field-based microcosm experiment was performed to investigate the effects of repeated pulses of the neonicotinoid insecticide imidacloprid on a lentic benthos assemblage. This specific microcosm method was chosen because it allows for both testing of a wide range of organisms under natural conditions and as well as gaining insight into intraspecific and interspecific interactions. The macrozoobenthos that colonised the microcosms was exposed to three pulses each 1 week apart at nominal concentrations ranging from 0.6 to 40 μg/L. Imidacloprid underwent fast aqueous photolysis due to optimal sunlight conditions during the test phase (half-life = 28 ± 8 h [monitored for 21 days]). Nonetheless, decreased abundance and emergence of Ephemeroptera and decreased survival of chironomid species of the subfamilies Tanypodinae and Orthocladiinae were observed at time-weighted average concentrations of 2.3 μg/L. In contrast, the gastropod Radix sp. became dominant at high imidacloprid concentrations, probably due to decreased competition for food with sensitive species. The results of this study show that repeated short-term contamination of imidacloprid at low concentration levels may affect aquatic ecosystems even under optimal conditions for photodegradation. The microcosm approach, with its simple and field-relevant design, proved to be a useful tool for assessing the effects of imidacloprid contamination.
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http://dx.doi.org/10.1007/s00244-013-9940-2DOI Listing
November 2013

Stability vs. reactivity: understanding the adsorption properties of Ni3(BTP)2 by experimental and computational methods.

Dalton Trans 2013 May;42(18):6450-8

Dipartimento di Chimica, Università di Torino, NIS Centre of Excellence and INSTM Centre of Reference, Torino, Italy.

FTIR spectroscopy and ab initio molecular modelling have been employed to probe the interaction between CO and Ni3(BTP)2, a thermally and chemically stable MOF. A combination of low pressure adsorption isotherms and FTIR spectroscopy has been utilised to study the material for its interaction with CO2 and H2. The experimental results indicate that despite an abundance of Ni(2+) coordination vacancies in the activated sample, the molecular probes considered in this study do not interact with them. These findings are in alignment with the data obtained by molecular modelling, in which it is shown that the unreactive diamagnetic, low spin state is more stable. Due to the strong N-donor character of the pyrazolate ligands on this material, the electrostatic potential map of the optimized low spin structure does not show any evidence of a region of positive potential typical of open metal sites.
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http://dx.doi.org/10.1039/c3dt32944eDOI Listing
May 2013

Tuning the adsorption properties of isoreticular pyrazolate-based metal-organic frameworks through ligand modification.

J Am Chem Soc 2012 Aug 19;134(30):12830-43. Epub 2012 Jul 19.

Dipartimento di Scienza e Alta Tecnologia, Università dell'Insubria, Como, Italy.

Two isoreticular series of pyrazolate-based 3D open metal-organic frameworks, MBDP_X, adopting the NiBDP and ZnBDP structure types [H(2)BDP = 1,4-bis(1H-pyrazol-4-yl)benzene], were synthesized with the new tagged organic linkers H(2)BDP_X (X = -NO(2), -NH(2), -OH). All of the MBDP_X materials have been characterized through a combination of techniques. IR spectroscopy proved the effective presence of tags, while X-ray powder diffraction (XRPD) witnessed their isoreticular nature. Simultaneous TG/DSC analyses (STA) demonstrated their remarkable thermal stability, while variable-temperature XRPD experiments highlighted their high degree of flexibility related to guest-induced fit processes of the solvent molecules included in the channels. A structural isomer of the parent NiBDP was obtained with a sulfonate tagged ligand, H(2)BDP_SO(3)H. Structure solution from powder diffraction data collected at three different temperatures (room temperature, 90, and 250 °C) allowed the determination of its structure and the comprehension of its solvent-related flexible behavior. Finally, the potential application of the tagged MOFs in selective adsorption processes for gas separation and purification purposes was investigated by conventional single component adsorption isotherms, as well as by advanced experiments of pulse gas chromatography and breakthrough curve measurements. Noteworthy, the results show that functionalization does not improve the adsorption selectivity (partition coefficients) for the resolution of gas mixtures characterized by similar high quadrupole moments (e.g., CO(2)/C(2)H(2)); however, the resolution of gas mixtures containing molecules with highly differentiated polarities (i.e., N(2)/CO(2) or CH(4)/CO(2)) is highly improved.
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http://dx.doi.org/10.1021/ja305267mDOI Listing
August 2012

Spectroscopic and adsorptive studies of a thermally robust pyrazolato-based PCP.

Dalton Trans 2012 Apr 1;41(14):4012-9. Epub 2012 Mar 1.

Dipartimento di Chimica, Università di Torino, Centre of Excellence, via Quarello 11/A, 10135 Torino, Italy.

The pyrazolato-based PCP [Ni(8)(μ(4)-OH)(4)(μ(4)-OH(2))(2)(μ(4)-PBP)(6)] (NiPBP, H(2)PBP = 4,4'-bis(1H-pyrazol-4-yl)biphenyl), whose 3-D architecture is built upon octametallic hydroxo clusters reciprocally connected by organic spacers, is a very promising candidate for gas adsorption applications, owing to its remarkable thermal stability (up to 400 °C in air) and its high void volume (70%). As such, NiPBP was selected as a proof-of-concept material to demonstrate how an optimized set of solid state techniques can concur to create a comprehensive and coherent picture, relating (average and local) structural features to adsorptive properties. To this aim, the response of NiPBP toward different gases, retrieved by gas adsorption measurements (N(2) at 77 K, in the low pressure region; H(2) at 77 K, in the high pressure region), was explained in terms of local-level details, as emerged by coupling electronic, X-ray (absorption and emission), and variable temperature IR spectroscopy.
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http://dx.doi.org/10.1039/c2dt12121bDOI Listing
April 2012

Cation-exchange porosity tuning in anionic metal-organic frameworks for the selective separation of gases and vapors and for catalysis.

Angew Chem Int Ed Engl 2010 Sep;49(40):7308-11

Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071 Granada, Spain.

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http://dx.doi.org/10.1002/anie.201003314DOI Listing
September 2010

Cubic octanuclear Ni(II) clusters in highly porous polypyrazolyl-based materials.

J Am Chem Soc 2010 Jun;132(23):7902-4

Dipartimento di Scienze Chimiche e Ambientali, Università dell'Insubria, via Valleggio 11, I-22100 Como, Italy.

Two highly porous coordination polymers, containing rare octanuclear hydroxo-nickel clusters and long bis-pyrazolyl spacers, are shown to possess, after mild thermal treatment, lattice cavities up to 72% of the total crystal volume.
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http://dx.doi.org/10.1021/ja102862jDOI Listing
June 2010

Chemotherapeutic activity of silymarin combined with doxorubicin or paclitaxel in sensitive and multidrug-resistant colon cancer cells.

Cancer Chemother Pharmacol 2011 Feb 30;67(2):369-79. Epub 2010 Apr 30.

Laboratory of Anticancer Pharmacology, Department of Oncology, Istituto di Ricerche Farmacologiche Mario Negri, Via La Masa 19, 20156 Milan, Italy.

Purpose: The milk thistle extract silymarin, alone or in combined chemotherapy, is now under investigation in anticancer research, with particular interest for its possible employ in the treatment of chemoresistant tumours. So far, the consequences of a silymarin pre-treatment have not been thoroughly investigated. We studied whether silymarin pre-treatment synergized with chemotherapy, exploring the dose-dependence of the interaction in sensitive and multidrug-resistant cells.

Methods: We studied cell cycle perturbations induced by silymarin in two colon carcinoma cell lines, LoVo and the multidrug-resistant isogenic LoVo/DX. Synergism/additivity/antagonism of silymarin-doxorubicin silymarin-paclitaxel combined treatments were evaluated by isobologram/combination index analysis, in the whole spectrum of active and sub-active concentrations of all drugs. The mechanisms of silymarin interaction with the other drugs were investigated by measuring drug uptake and cell cycle perturbations.

Results: Silymarin had similar antiproliferative activity against both cell lines. Pre-treatment with low silymarin concentrations synergised with both doxorubicin and paclitaxel in LoVo but not in LoVo/DX. Higher silymarin concentrations were additive with doxorubicin and paclitaxel in both cell lines. Silymarin favourably interfered with uptake and cell cycle effects of the chemotherapeutics in LoVo but not in LoVo/DX.

Conclusion: These findings confirm activity of silymarin against colon carcinoma, including multidrug-resistant types, at relatively high but clinically achievable concentrations. In view of its low toxicity, two schedules based on low- and high-dose silymarin pre-treatment might offer a valuable option for combined treatment.
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http://dx.doi.org/10.1007/s00280-010-1335-8DOI Listing
February 2011

Quantitative assessment of the complex dynamics of G1, S, and G2-M checkpoint activities.

Cancer Res 2009 Jun 9;69(12):5234-40. Epub 2009 Jun 9.

Biophysics Unit, Laboratory of Anticancer Pharmacology, Department of Oncology, Istituto di Ricerche Farmacologiche Mario Negri, Milan, Italy.

Although studies of cell cycle perturbation and growth inhibition are common practice, they are unable to properly measure the activity of cell cycle checkpoints and frequently convey misinterpretation or incomplete pictures of the response to anticancer treatment. A measure of the strength of the treatment response of all checkpoints, with their time and dose dependence, provides a new way to evaluate the antiproliferative activity of the drugs, fully accounting for variation of the cell fates within a cancer cell line. This is achieved with an interdisciplinary approach, joining information from independent experimental platforms and interpreting all data univocally with a simple mathematical model of cell cycle proliferation. The model connects the dynamics of checkpoint activities at the molecular level with population-based flow cytometric and growth inhibition time course measures. With this method, the response to five drugs, characterized by different molecular mechanisms of action, was studied in a synoptic way, producing a publicly available database of time course measures with different techniques in a range of drug concentrations, from sublethal to frankly cytotoxic. Using the computer simulation program, we were able to closely reproduce all the measures in the experimental database by building for each drug a scenario of the time and dose dependence of G(1), S, and G(2)-M checkpoint activities. We showed that the response to each drug could be described as a combination of a few types of activities, each with its own strength and concentration threshold. The results gained from this method provide a means for exploring new concepts regarding the drug-cell cycle interaction.
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http://dx.doi.org/10.1158/0008-5472.CAN-08-3911DOI Listing
June 2009
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