The synthesis and X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone

Regiospecific bromination of 2,4,4-trimethyl-cyclohex-2-enone was achieved and the X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone is presented.

The synthesis and X-ray crystal structure of 9-carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one

9-Carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one (1) was prepared and examined by X-ray crystallography to probe its potential as a new peptide scaffold/template. The crystal structure of the anhydride precursor 7-(2-acetoxyethyl)-4-methoxy-3a,4,7,7a-tetrahydro-4,7-ethanoisobenzofuran-1,3-dione (6) is also reported.

Ambient assisted living technology: comparative perspectives of users and caregivers

Developed societies are currently facing severe demographic changes: the world population is ageing at an unprecedented rate. This demographic trend will be also followed by an increase of people with physical limitations. New challenges are being raised to the traditional health care systems, not only in Portugal, but also in all other European states. There is an urgent need to find solutions that allow extending the time people can live in their preferred environment by increasing their autonomy, self-confidence and mobility. AAL4ALL is a project currently being developed in cooperation with 34 Portuguese interdisciplinary partners, from industry to academia, R&D and social disciplines, which employs a novel conceptual approach through the development of an ecosystem of products and services for Ambient Assisted Living (AAL) associated to a business model and validated through large scale trial. This paper presents a comparative perspective of the needs and attitudes towards technology of the AAL users and caregivers identified in the analysis of a set of three different surveys: a users survey targeted at the Portuguese seniors and pre-seniors; an informal caregivers survey targeted at the family, friends and neighbours who provide care without any financial compensation; and a formal caregivers survey targeted at physicians, nurses,psychologists, social workers, and direct-care workers providing care to elders. The first results indicate that AAL solutions must be affordable,user friendly and have a true perceived benefit to their users.

A Platform to Emulate Ambient Assisted Living Environments

According to the opinion of clinicians, emerging medical conditions can be timely detected by observing changes in the activities of daily living and/or in the physiological signals of a person. To accomplish such purpose, it is necessary to properly monitor both the person’s physiological signals as well as the home environment with sensing technology. Wireless sensor networks (WSNs) are a promising technology for this support. After receiving the data from the sensor nodes, a computer processes the data and extracts information to detect any abnormality. The computer runs algorithms that should have been previously developed and tested in real homes or in living-labs. However, these installations (and volunteers) may not be easily available. In order to get around that difficulty, this paper suggests the making of a physical model to emulate basic actions of a user at home, thus giving autonomy to researchers wanting to test the performance of their algorithms. This paper also studies some data communication issues in mobile WSNs namely how the orientation of the sensor nodes in the body affects the received signal strength, as well as retransmission aspects of a TDMA-based MAC protocol in the data recovery process.

Needs and Opportunities in Ambient Assisted Living in Portugal

The exponential raise in the age dependency rate together with the difficulties in having conventional care solutions opens the space for the appearance and development of innovative Ambient Assisted Living (AAL) solutions.However, the development of these solutions requires a thorough understanding of user needs and wills. In this paper we present the scenarios being adopted in the context of AAL projects, as well as the products and services current available in each of the considered utilization scenarios. The needs of the Portuguese AAL users are analyzed through the discussion of some preliminary results from a survey targeted at the Portuguese population over 55 years old. These results will be used to characterize the needs and establish the readiness and willingness of elder Portuguese population in using AAL solutions.

A Caregiver Support Platform within the Scope of an Ambient Assisted Living Ecosystem

The Ambient Assisted Living (AAL) area is in constant evolution, providing new technologies to users and enhancing the level of security and comfort that is ensured by house platforms. The Ambient Assisted Living for All (AAL4ALL) project aims to develop a new AAL concept, supported on a unified ecosystem and certification process that enables a heterogeneous environment. The concepts of Intelligent Environments, Ambient Intelligence, and the foundations of the Ambient Assisted Living are all presented in the framework of this project. In this work, we consider a specific platform developed in the scope of AAL4ALL, called UserAccess. The architecture of the platform and its role within the overall AAL4ALL concept, the implementation of the platform, and the available interfaces are presented. In addition, its feasibility is validated through a series of tests.

Robosonic: Randomness-Based Manipulation of Sounds Assisted by Robots

In this text, we intend to explore the possibilities of sound manipulation in a context of augmented reality (AR) through the use of robots. We use the random behaviour of robots in a limited space for the real-time modulation of two sound characteristics: amplitude and frequency. We add the possibility of interaction with these robots, providing the user the opportunity to manipulate the physical interface by placing markers in the action space, which alter the behaviour of the robots and, consequently, the audible result produced. We intend to demonstrate through the agents, programming of random processes and direct manipulation of this application, that it is possible to generate empathy in interaction and obtain specific audible results, which would be difficult to otherwise reproduce due to the infinite loops that the interaction promotes.

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

Field effect and light-assisted a-Si:H sensors for detection of ions in solution

In this paper we present an amorphous silicon device that can be used in two operation modes to measure the concentration of ions in solution. While crystalline devices present a higher sensitivity, their amorphous counterpart present a much lower fabrication cost, thus enabling the production of cheap disposable sensors for use, for example, in the food industry. The devices were fabricated on glass substrates by the PECVD technique in the top gate configuration, where the metallic gate is replaced by an electrolytic solution with an immersed Ag/AgCl reference electrode. Silicon nitride is used as gate dielectric enhancing the sensitivity and passivation layer used to avoid leakage and electrochemical reactions. In this article we report on the semiconductor unit, showing that the device can be operated in a light-assisted mode, where changes in the pH produce changes on the measured ac photocurrent. In alternative the device can be operated as a conventional ion selective field effect device where changes in the pH induce changes in the transistor's threshold voltage.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

A dramatic effect of double bond configuration in N-oxy-3-aza Cope rearrangements: a simple synthesis of functionalised allenes

The first examples of low temperature N-oxy-3-aza Cope rearrangements, leading to functionalised allenes are described, where the Z-configuration of the enaminic double bond in the rearranging system proves critical.

Asymmetric synthesis of N-aryl aziridines

The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (−)-8-phenylmenthol, (−)-quinine and (−)-Oppolzer’s sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer’s auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantioselection and a mechanism is proposed for the aziridination reaction.

Studies in 3-oxy-assisted 3-aza Cope rearrangements

On thermolysis appropriately substituted N-silyloxy-N-allyl enamines undergo smooth 3,3-sigmatropic rearrangments to the corresponding N-silyloxy imino ethers.