Nanoscale Control of DNA-Linked MoS2-Quantum Dot Heterostructures.

The ability to control the assembly of mixed-dimensional heterostructures with nanoscale control is key for the fabrication of novel nanohybrid systems with new functionalities, particularly for optoelectronics applications. Herein we report a strategy to control the assembly of heterostructures and tune their electronic coupling employing DNA as a linker. We functionalized MoS2 nanosheets (NSs) with biotin-terminated dsDNA employing three different chemical strategies, namely, thiol, maleimide, and aryl diazonium. This allowed us to then tether streptavidinated quantum dots (QDs) to the DNA functionalized MoS2 surface via biotin-avidin recognition. Nanoscale control over the separation between QDs and NSs was achieved by varying the number of base pairs (bp) constituting the DNA linker, between 10, 20, and 30 bp, corresponding to separations of 3.4, 6.8, and 13.6 nm, respectively. Spectroscopic data confirmed the successful functionalization, while atomic force and transmission electron microscopy were employed to image the nanohybrids. In solution steady-state and time-resolved photoluminescence demonstrated the electronic coupling between the two nanostructures, that in turn was observed to progressively scale as a function of DNA linker employed and hence distance between the two nanomoieties in the hybrids.

Eumelanin Precursor 2-Carboxy-5,6-Dihydroxyindole (DHICA) as Doping Factor in Ternary (PEDOT:PSS/Eumelanin) Thin Films for Conductivity Enhancement.

The integration of the pristine not-doped commercial poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) PH1000 with eumelanin, the brown to black kind of melanin pigment, was achieved by dissolving the melanogenic precursors 2-carboxy-5,6-dihydroxyindole (DHICA) in the PH1000 suspension. Solid state oxidative polymerization of the catecholic indole allowed obtaining the ternary blend PEDOT:PSS/eumelanin. The introduction of DHICA into PH1000 produced a noticeable increase in the conductivity of PEDOT thin films akin to that produced by dimethyl sulfoxide (DMSO) treatment, opening up novel strategies for the simultaneous integration of eumelanin polymer and conductivity enhancement of PEDOT containing coatings, as well as the long term goal of replacing PSS by DHICA eumelanin for PEDOT pairing.

A multi-scale time-resolved study of photoactivated dynamics in 5-benzyl uracil, a model for DNA/protein interactions.

We combine fluorescence up-conversion and time correlated single photon counting experiments to investigate the 5-benzyl uracil excited state dynamics in methanol from 100 fs up to several ns. This molecule has been proposed as a model for DNA/protein interactions. Our results show emission bands at about 310 and 350 nm that exhibit bi-exponential sub-ps decays. Calculations, including solvent effects by a mixed discrete-continuum model, indicate that the Franck Condon region is characterized by significant coupling between the excited states of the benzyl and the uracil moieties, mirrored by the short-lived emission at 310 nm. Two main ground state recovery pathways are identified, both contributing to the 350 nm emission. The first 'photophysical' decay path involves a ππ* excited state localized on the uracil and is connected to the ground electronic state by an easily accessible crossing with S0, accounting for the short lifetime component. Simulations indicate that a possible second pathway is characterized by exciplex formation, with partial benzene → uracil charge transfer character, that may lead instead to photocyclization. The relevance of our results is discussed in view of the photoactivated dynamics of DNA/protein complexes, with implications on their interaction mechanisms.

Spontaneous wrinkle emergence in nascent eumelanin thin films.

Self-patterning processes originated by physical stimuli have been extensively documented in thin films, whereas spontaneous wrinkling phenomena due to chemical transformation processes are, to the best of our knowledge, unprecedented. Herein we report a case of spontaneous polymerization-driven surface nano-patterning (∼500 nm) that develops in smooth thin solid films of 5,6-dihydroxyindole (DHI), a major precursor of eumelanin polymers, over a time scale of 30 to 60 days in air at room temperature. The phenomenon can be observed only above a critical film thickness of ∼250 nm and it is affected by exposure to ammonia vapors causing acceleration of the oxidation process. The thickness-dependent onset of wrinkling can be attributed to non-homogeneous rates of oxidation through the film causing slow swelling/expansion of the inner layers followed by fast stiffening and cross-linking in the outer layer exposed to higher oxygen levels.

Tuning the Coupling in Single-Molecule Heterostructures: DNA-Programmed and Reconfigurable Carbon Nanotube-Based Nanohybrids.

Herein a strategy is presented for the assembly of both static and stimuli-responsive single-molecule heterostructures, where the distance and electronic coupling between an individual functional nanomoiety and a carbon nanostructure are tuned via the use of DNA linkers. As proof of concept, the formation of 1:1 nanohybrids is controlled, where single quantum dots (QDs) are tethered to the ends of individual carbon nanotubes (CNTs) in solution with DNA interconnects of different lengths. Photoluminescence investigations-both in solution and at the single-hybrid level-demonstrate the electronic coupling between the two nanostructures; notably this is observed to progressively scale, with charge transfer becoming the dominant process as the linkers length is reduced. Additionally, stimuli-responsive CNT-QD nanohybrids are assembled, where the distance and hence the electronic coupling between an individual CNT and a single QD are dynamically modulated via the addition and removal of potassium (K+) cations; the system is further found to be sensitive to K+ concentrations from 1 pM to 25 × 10-3 m. The level of control demonstrated here in modulating the electronic coupling of reconfigurable single-molecule heterostructures, comprising an individual functional nanomoiety and a carbon nanoelectrode, is of importance for the development of tunable molecular optoelectronic systems and devices.

Analysis of nascent silicon phase-change gratings induced by femtosecond laser irradiation in vacuum.

The formation of periodic surface structures is a general effect of femtosecond laser irradiation of solid targets showing promising interest in material science and technology. However, the experiments are typically carried out in air, a condition in which the target surface becomes densely decorated with nanoparticles that can influence the formation of the surface structures in the early stage of the irradiation process. Here we report an investigation of structures generation on a silicon surface irradiated in vacuum (10-5 mbar) with a low number of laser pulses (N ≤ 10) that exploits several microscopy techniques (optical, atomic force, electron and Raman). Our analyses allow identifying the creation of silicon phase-change gratings consisting of alternating amorphous and crystalline periodic lines, with almost no material removal, located at the periphery of a shallow ablation crater. These gratings originate from two different kinds of defects: (i) the first is characterized by a peculiar lobed shape that is produced by the first few laser pulses; (ii) the second is provided by the one-dimensional, linear singularity defined by the ablation edge of the nascent crater. Both kind of defects lead to grating structures extending outwards the amorphous central area of the crater along the direction of the laser polarization. Comparative analysis with the surface formed in air, in the same experimental conditions, evidences the important role played by nanoparticles densely decorating the target in air and the striking variation occurring in vacuum.

Time-resolved analysis of DNA-protein interactions in living cells by UV laser pulses.

Interactions between DNA and proteins are mainly studied through chemical procedures involving bi-functional reagents, mostly formaldehyde. Chromatin immunoprecipitation is used to identify the binding between transcription factors (TFs) and chromatin, and to evaluate the occurrence and impact of histone/DNA modifications. The current bottleneck in probing DNA-protein interactions using these approaches is caused by the fact that chemical crosslinkers do not discriminate direct and indirect bindings or short-lived chromatin occupancy. Here, we describe a novel application of UV laser-induced (L-) crosslinking and demonstrate that a combination of chemical and L-crosslinking is able to distinguish between direct and indirect DNA-protein interactions in a small number of living cells. The spatial and temporal dynamics of TF bindings to chromatin and their role in gene expression regulation may thus be assessed. The combination of chemical and L-crosslinking offers an exciting and unprecedented tool for biomedical applications.

Giant O2-Induced Photoluminescence Modulation in Hierarchical Titanium Dioxide Nanostructures.

We demonstrate exceptionally large modulation of PL intensity in hierarchical titanium dioxide (TiO2) nanostructures exposed to molecular oxygen (O2). Optical responsivities up to about 1100% at 20% O2 concentrations are observed in hyperbranched anatase-phase hierarchical structures, outperforming those obtainable by commercial TiO2 nanopowders (up to a factor of ∼7 for response to synthetic air) and significantly improving the ones typically reported in PL-based opto-chemical gas sensing using MOXs. The improved PL response is discussed in terms of the specific morphology of hierarchical structures, characterized by simultaneous presence of small nanoparticles, large surface areas, and large voids. These characteristics guarantee an optimal interplay between photogenerated charges, PL-active centers, and adsorbed gas molecules. The results highlight the potentialities offered by hierarchical structures based on TiO2 or other MOXs and open interesting scenarios toward the development of all-optical and/or hybrid (opto/electrical) chemical sensors with improved sensitivity.

Carbon Nanotube-Quantum Dot Nanohybrids: Coupling with Single-Particle Control in Aqueous Solution.

A strategy is reported for the controlled assembly of organic-inorganic heterostructures consisting of individual single-walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT-QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD-based optoelectronic and light-energy conversion devices.

Simple and Flexible Model for Laser-Driven Antibody-Gold Surface Interactions: Functionalization and Sensing.

Interactions between biomolecules and between substrates and biomolecules is a crucial issue in physics and applications to topics such as biotechnology and organic electronics. The efficiency of bio- and mechanical sensors, of organic electronics systems, and of a number of other devices critically depends on how molecules are deposited on a surface so that these acquire specific functions. Here, we tackle this vast problem by developing a coarse grained model of biomolecules having a recognition function, such as antibodies, capable to quantitatively describe in a simple manner essential phenomena: antigen-antibody and antibody substrate interactions. The model is experimentally tested to reproduce the results of a benchmark case, such as (1) gold surface functionalization with antibodies and (2) antibody-antigen immune-recognition function. The agreement between experiments and model prediction is excellent, thus unveiling the mechanism for antibody immobilization onto metals at the nanoscale in various functionalization schemes. These results shed light on the geometrical packing properties of the deposited molecules, and may open the way to a novel coarse-grained based approach to describe other processes where molecular packing is a key issue with applications in a huge number of fields from nano- to biosciences.

Femtosecond UV-laser pulses to unveil protein-protein interactions in living cells.

A hallmark to decipher bioprocesses is to characterize protein-protein interactions in living cells. To do this, the development of innovative methodologies, which do not alter proteins and their natural environment, is particularly needed. Here, we report a method (LUCK, Laser UV Cross-linKing) to in vivo cross-link proteins by UV-laser irradiation of living cells. Upon irradiation of HeLa cells under controlled conditions, cross-linked products of glyceraldehyde-3-phosphate dehydrogenase (GAPDH) were detected, whose yield was found to be a linear function of the total irradiation energy. We demonstrated that stable dimers of GAPDH were formed through intersubunit cross-linking, as also observed when the pure protein was irradiated by UV-laser in vitro. We proposed a defined patch of aromatic residues located at the enzyme subunit interface as the cross-linking sites involved in dimer formation. Hence, by this technique, UV-laser is able to photofix protein surfaces that come in direct contact. Due to the ultra-short time scale of UV-laser-induced cross-linking, this technique could be extended to weld even transient protein interactions in their native context.

Detection of parathion and patulin by quartz-crystal microbalance functionalized by the photonics immobilization technique.

Oriented antibodies are tethered on the gold surface of a quartz crystal microbalance through the photonics immobilization technique so that limit of detection as low as 50 nM and 140 nM are achieved for parathion and patulin, respectively. To make these small analytes detectable by the microbalance, they have been weighed down through a "sandwich protocol" with a second antibody. The specificity against the parathion has been tested by checking the immunosensor response to a mixture of compounds similar to parathion, whereas the specificity against the patulin has been tested with a real sample from apple puree. In both cases, the results are more than satisfactory suggesting interesting outlook for the proposed device.

The relationship between childhood parental loss and metabolic syndrome in obese subjects.

The increasing global trend of obesity is a fundamental contributor to the growing prevalence of metabolic syndrome, a cluster of medical abnormalities including impaired glucose and lipid metabolism, obesity and hypertension. Results from animal and human investigations have shown that early life stress can result in weight gain and metabolic changes. Our aim is to investigate whether a particular type of an early adverse event, i.e. parental loss during childhood, is associated with the development of metabolic syndrome in severely obese subjects. One hundred thirty-five consecutive obese patients who were seeking bariatric surgery were assessed for metabolic syndrome according to the Adult Treatment Panel (ATP) III criteria. Information regarding the experience of parental separation or bereavement before the age of 17 was collected with the use of a semi-structured interview. In our population, 31.1% of the subjects met the criteria for metabolic syndrome. No significant differences in demographic factors, health habits or psychiatric diagnosis were found between patients with and without coexisting metabolic syndrome. After adjusting for age and gender, multivariate logistic regression analysis revealed that both childhood loss of a parent and a body mass index (BMI) value greater than 50 were significant predictors of metabolic syndrome. This study provides preliminary evidence linking childhood parental loss to risk factors for the development of metabolic syndrome.

Overactive lifestyle in patients with fibromyalgia as a core feature of bipolar spectrum disorder.

OBJECTIVES: To test the hypothesis that the premorbid overactivity previously described in subjects with fibromyalgia is a core feature of the manic/hypomanic symptoms characterising bipolar spectrum disorders. METHODS: 110 consecutive patients with fibromyalgia were assessed for bipolar spectrum disorders using both categorical and dimensional approaches. The first was based on a version of the DSM-IV SCID-CV interview, modified to improve the detection of bipolar spectrum disorders, the second on the hypomania symptom checklist HCL-32, which adopts a dimensional perspective of the manic/hypomanic component of mood by including sub-syndromal hypomania. RESULTS: Both DSM-IV and Zurich criteria diagnosed high rates of bipolar spectrum disorder in patients with fibromyalgia (70% and 86.3%, respectively). Individuals with a major bipolar spectrum disorder (bipolar II disorder) and with a minor bipolar spectrum disorder (subthreshold depression and hypomania) did not differ in their demographic and clinical aspects. Hypomanic symptom counts on the HCL-32 confirmed high estimates of the bipolar spectrum, with 79% of subjects with fibromyalgia scoring 14 (threshold for hypomania) or above. CONCLUSIONS: Overactivity reported in previous studies may be considered a core feature of hypomanic symptoms or syndromes comorbid with bipolar spectrum disorders. Major and minor bipolar spectrum disorders are not associated with differences in demographic or clinical characteristics, suggesting that fibromyalgia rather than being related specifically to depression is related to bipolar spectrum disorders and in particular to the hypomania/overactivity component.

Childhood parental loss and bipolar spectrum in obese bariatric surgery candidates.

BACKGROUND: Early adverse experiences such as sexual, verbal, or physical abuse and parental neglect have been associated with a higher risk of weight or eating problems in adulthood, and death or prolonged separation from parents during childhood has been implicated as a correlate of adult psychiatric disorders that are widely represented in obese subjects seeking bariatric surgery. OBJECTIVE: The aim of this study was to examine the rate of childhood parental loss in obese bariatric surgery candidates and explore its association with a psychiatric diagnosis and clinical and weight/eating-related characteristics. METHODS: The current and lifetime psychiatric diagnoses of 120 consecutive bariatric patients undergoing pre-surgical psychiatric consultation were assessed using a modified version of the Structured Clinical Interview for DSM-IV (SCID-CV), and information relating to parental death or separation before the age of 17 years was collected using a semi-structured interview. The rate of childhood parental loss was compared with that of an always slender population sharing the same psychiatric diagnosis. RESULTS: 91.7% of the obese subjects were diagnosed as having a bipolar spectrum disorder. Overall, 28% of the patients reported a childhood parental death or separation. Early parental loss was not equally distributed in the different diagnostic subgroups, being more frequent in those with bipolar II disorders; the always slender subjects with bipolar II disorders showed a lower rate of early parental loss. CONCLUSIONS: The study findings confirm the association between obesity and bipolar disorders and suggest that early parental loss may play a role in the development of obesity in bipolar II subjects.

Real-space observation of spectral degeneracy breaking in a waveguide-coupled disk microresonator.

We report on the real-space observation of resonant frequency splitting in a high-Q waveguide-coupled silicon-on-insulator microdisk resonator. Phase sensitive near-field analysis reveals the stationary nature of the two resonant states, and spectral investigations clearly show their orthogonality. These measurements emphasize the role of the coupling waveguide in this splitting phenomenon. The symmetry of the two stationary whispering gallery modes is clearly observed and is found to follow the axial symmetry of the waveguide-coupled microdisk as it has been reported by earlier theoretical predictions.