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1.
Chem Sci ; 13(38): 11368-11375, 2022 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-36320581

RESUMEN

Maintaining close spatial proximity of functional moieties within molecular systems can result in fascinating emergent properties. Whilst much work has been done on covalent tethering of functional units for myriad applications, investigations into mechanically linked systems are relatively rare. Formation of the mechanical bond is usually the final step in the synthesis of interlocked molecules, placing limits on the throughput of functionalised architectures. Herein we present the synthesis of a bis-azide [2]catenane scaffold that can be post-synthetically modified using CuAAC 'click' chemistry. In this manner we have been able to access functionalised catenanes from a common precursor and study the properties of electrochemically active, emissive and photodimerisable units within the mechanically interlocked system in comparison to non-interlocked analogues. Our data demonstrates that the greater (co-)conformational flexibility that can be obtained with mechanically interlocked systems compared to traditional covalent tethers paves the way for developing new functional molecules with exciting properties.

2.
Chem Commun (Camb) ; 56(72): 10453-10456, 2020 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-32748902

RESUMEN

A mechanically interlocked [2]rotaxane is reported incorporating a ditopic ligand moiety as one of the stoppers. Upon complexation with palladium(ii) ions a metallo-[5]rotaxane was formed with a porous Pd2L4 metal-organic cage at the core of the structure. This proof-of-principle system precedes work towards the construction of metal organic polyhedra with switchable mechano-chemical properties.

3.
Org Biomol Chem ; 18(35): 6757-6780, 2020 09 21.
Artículo en Inglés | MEDLINE | ID: mdl-32840554

RESUMEN

Mechanically interlocked molecules have fascinated chemists for decades. Initially a tantalising synthetic challenge, interlocked molecules have continued to capture the imagination for their aesthetics and, increasingly, for their potential as molecular machines and use in materials applications. Whilst preliminary statistical attempts to prepare these molecules were exceedingly inefficient, a raft of template-directed strategies have now been realised, providing a vast toolbox from which chemists can access interlocked structures in excellent yields. For many envisaged applications it is desirable to move away from small, discrete interlocked molecules and turn to oligomers and polymers instead, either due to the need for multiple mechanical bonds within the desired material, or to exploit an extended scaffold for the organisation and arrangement of individual mechanically interlocked units. In this tutorial-style review we outline the synthetic strategies that have been employed for the synthesis of mechanically interlocked oligomers and polymers, including oligo-/polymerisation of (pseudo)interlocked precursors, metal-organic self-assembly, the use of orthogonal template motifs, iterative approaches and grafting onto polymer backbones.

4.
MethodsX ; 6: 464-468, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-30923683

RESUMEN

In the present work, we describe and evaluate an additional step to the standard western blot protocol to increase signal strength after revealing. Weak or absence of signal is a common issue in western blot protocol leading to unexpected results. In our Antigen Retrieval for Western Blot Method (ARWB method), after transfer, the membrane was incubated in a citrate buffer following normal antigen retrieval procedure used for immunohistochemistry. Later, standard protocol was performed in order to reveal and compare with unexposed membranes to this antigen retrieval step. Signal in bands obtained by the modified protocol resulted significantly higher (in all 13 antibodies analyzed) compared to standard protocol. Some bands were only visible after citrate incubation. This method is a simple and economical way to improve results in western blot analysis. •The ARWB method significantly increases band's density in all antibodies analyzed.•Protein localization does not influence the efficacy of the ARWB method since membrane and citoplasmatic proteins bands increase their signal in a similar way after the protocol is performed.•This ARWB method is simple, safe, economical and undoubtedly helpful in immunoblotting for proteins with weak signal.

5.
Physiol Meas ; 35(6): 931-41, 2014 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-24846525

RESUMEN

Breast cancer (BC) is the leading cause of cancer death in women worldwide, with a higher mortality reported in undeveloped countries. Ideal adjuvant therapeutic strategies require the continuous monitoring of patients by regular blood tests to detect circulating cancer cells, in order to determine whether additional treatment is necessary to prevent cancer dissemination. This circumstance requires a non-complex design of tumor cell biosensor in whole blood with feasibility for use in poor regions. In this work we have evaluated an inexpensive and simple technique of relative bioimpedance measurement, assisted by magnetic nanoparticles, as a potential biosensor of BC cells in suspension. Measurements represent the relative impedance changes caused by the magnetic holding of an interphase of tumor cells versus a homogenous condition in the frequency range of 10-100 kHz. The results indicate that use of a magnet to separate tumor cells in suspension, coupled to magnetic nanoparticles, is a feasible technique to fix an interphase of tumor cells in close proximity to gold electrodes. Relative impedance changes were shown to have potential value as a biosensor method for BC cells in whole blood, at frequencies around 20 kHz. Additional studies are warranted with respect to electrode design and sensitivity at micro-scale levels, according to the proposed technique.


Asunto(s)
Técnicas Biosensibles , Neoplasias de la Mama/diagnóstico , Espectroscopía Dieléctrica , Nanopartículas de Magnetita , Neoplasias de la Mama/patología , Línea Celular Tumoral , Electricidad , Femenino , Humanos , Microscopía Confocal
6.
Child Abuse Negl ; 38(5): 851-7, 2014 May.
Artículo en Inglés | MEDLINE | ID: mdl-24630439

RESUMEN

The purpose of this study was to describe behavioural and emotional symptoms and to examine the effect of abuse-related factors, family responses to disclosure, and child self-blame on these symptoms in children presenting for medical evaluations after disclosure of sexual abuse. A retrospective review was conducted of 501 children ages 8-17. Trauma symptoms were determined by two sets of qualitative measures. Abstracted data included gender, ethnicity, and age; severity of abuse and abuser relationship to child; child responses regarding difficulty with sleep, school, appetite/weight, sadness, or self-harm, parent belief in abuse disclosure, and abuse-specific self-blame; responses to the Trauma Symptom Checklist in Children-Alternate; and the parent's degree of belief in the child's sexual abuse disclosure. Overall, 83% of the children had at least one trauma symptom; 60% had difficulty sleeping and one-third had thoughts of self-harm. Child age and abuse severity were associated with 3 of 12 trauma symptoms, and abuse-specific self-blame was associated with 10 trauma symptoms, after controlling for other variables. The children of parents who did not completely believe the initial disclosure of abuse were twice as likely to endorse self-blame as children of parents who completely believed the initial disclosure. Screening for behavioural and emotional problems during the medical assessment of suspected sexual abuse should include assessment of self-blame and family responses to the child's disclosures. In addition, parents should be informed of the importance of believing their child during the initial disclosure of abuse and of the impact this has on the child's emotional response to the abuse.


Asunto(s)
Abuso Sexual Infantil/psicología , Culpa , Autoimagen , Adolescente , Niño , Revelación , Femenino , Humanos , Masculino , Relaciones Padres-Hijo , Estudios Retrospectivos , Trastornos de Estrés Traumático/psicología
7.
Electrophoresis ; 32(17): 2331-57, 2011 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-21823133

RESUMEN

Dielectrophoresis (DEP) is the motion of polarizable particles in the presence of nonuniform electric fields. This novel electrokinetic technique has successfully been employed in many miniaturized systems for the manipulation and detection of microbes. This review article depicts the application of dielectrophoresis for the monitoring of microorganisms in microfluidic devices for environmental applications. The research studies described here are mainly conceived for water- and air-monitoring assessments, and are classified considering the target aimed to detect, concentrate, and/or separate, including chemical and toxicant agents, and microorganisms ranging from virus to protozoa. Dielectrophoresis has also played an important role in biofilm formation studies. This review article comprises mainly studies published from 2000 to present. Even in this relatively short time frame, there have been many significant contributions of this powerful and nascent technique related to environmental monitoring; thus, unveiling its great potential for future research directions.


Asunto(s)
Electroforesis/métodos , Microbiología Ambiental , Monitoreo del Ambiente/métodos , Técnicas Analíticas Microfluídicas/métodos , Cryptosporidium parvum/química , Giardia lamblia/química , Esporas Bacterianas/química , Virus/química , Contaminantes del Agua/análisis
8.
Lab Chip ; 10(23): 3235-42, 2010 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-20936247

RESUMEN

Low frequency alternating current insulator-based dielectrophoresis is a novel technique that allows for highly controlled manipulation of particles. By varying the shape of an AC voltage applied across a microchannel containing an array of insulating cylindrical structures it was possible to concentrate and immobilize microparticles in bands; and then, move the bands of particles to a different location. Mathematical modeling was performed to analyze the distribution of the electric field and electric field gradient as function of the shape of the AC applied potential, employing frequencies in the 0.2-1.25 Hz range. Three different signals were tested: sinusoidal, half sinusoidal and sawtooth. Experimental results demonstrated that this novel dielectrophoretic mode allows highly controlled particle manipulation.


Asunto(s)
Campos Electromagnéticos , Microesferas , Algoritmos , Biotecnología/métodos , Simulación por Computador , Suministros de Energía Eléctrica , Diseño de Equipo , Cinética , Microfluídica/instrumentación , Microfluídica/métodos , Miniaturización , Modelos Teóricos , Tamaño de la Partícula , Reproducibilidad de los Resultados , Factores de Tiempo
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