Molecular streaming and its voltage control in ångström-scale channels.

Over the past decade, the ability to reduce the dimensions of fluidic devices to the nanometre scale (by using nanotubes1-5 or nanopores6-11, for example) has led to the discovery of unexpected water- and ion-transport phenomena12-14. More recently, van der Waals assembly of two-dimensional materials15 has allowed the creation of artificial channels with ångström-scale precision16. Such channels push fluid confinement to the molecular scale, wherein the limits of continuum transport equations17 are challenged. Water films on this scale can rearrange into one or two layers with strongly suppressed dielectric permittivity18,19 or form a room-temperature ice phase20. Ionic motion in such confined channels21 is affected by direct interactions between the channel walls and the hydration shells of the ions, and water transport becomes strongly dependent on the channel wall material22. We explore how water and ionic transport are coupled in such confinement. Here we report measurements of ionic fluid transport through molecular-sized slit-like channels. The transport, driven by pressure and by an applied electric field, reveals a transistor-like electrohydrodynamic effect. An applied bias of a fraction of a volt increases the measured pressure-driven ionic transport (characterized by streaming mobilities) by up to 20 times. This gating effect is observed in both graphite and hexagonal boron nitride channels but exhibits marked material-dependent differences. We use a modified continuum framework accounting for the material-dependent frictional interaction of water molecules, ions and the confining surfaces to explain the differences observed between channels made of graphene and hexagonal boron nitride. This highly nonlinear gating of fluid transport under molecular-scale confinement may offer new routes to control molecular and ion transport, and to explore electromechanical couplings that may have a role in recently discovered mechanosensitive ionic channels23.

Ballistic molecular transport through two-dimensional channels.

Gas permeation through nanoscale pores is ubiquitous in nature and has an important role in many technologies1,2. Because the pore size is typically smaller than the mean free path of gas molecules, the flow of the gas molecules is conventionally described by Knudsen theory, which assumes diffuse reflection (random-angle scattering) at confining walls3-7. This assumption holds surprisingly well in experiments, with only a few cases of partially specular (mirror-like) reflection known5,8-11. Here we report gas transport through ångström-scale channels with atomically flat walls12,13 and show that surface scattering can be either diffuse or specular, depending on the fine details of the atomic landscape of the surface, and that quantum effects contribute to the specularity at room temperature. The channels, made from graphene or boron nitride, allow helium gas flow that is orders of magnitude faster than expected from theory. This is explained by specular surface scattering, which leads to ballistic transport and frictionless gas flow. Similar channels, but with molybdenum disulfide walls, exhibit much slower permeation that remains well described by Knudsen diffusion. We attribute the difference to the larger atomic corrugations at molybdenum disulfide surfaces, which are similar in height to the size of the atoms being transported and their de Broglie wavelength. The importance of this matter-wave contribution is corroborated by the observation of a reversed isotope effect, whereby the mass flow of hydrogen is notably higher than that of deuterium, in contrast to the relation expected for classical flows. Our results provide insights into the atomistic details of molecular permeation, which previously could be accessed only in simulations10,14, and demonstrate the possibility of studying gas transport under controlled confinement comparable in size to the quantum-mechanical size of atoms.

Molecular transport through capillaries made with atomic-scale precision.

Nanometre-scale pores and capillaries have long been studied because of their importance in many natural phenomena and their use in numerous applications. A more recent development is the ability to fabricate artificial capillaries with nanometre dimensions, which has enabled new research on molecular transport and led to the emergence of nanofluidics. But surface roughness in particular makes it challenging to produce capillaries with precisely controlled dimensions at this spatial scale. Here we report the fabrication of narrow and smooth capillaries through van der Waals assembly, with atomically flat sheets at the top and bottom separated by spacers made of two-dimensional crystals with a precisely controlled number of layers. We use graphene and its multilayers as archetypal two-dimensional materials to demonstrate this technology, which produces structures that can be viewed as if individual atomic planes had been removed from a bulk crystal to leave behind flat voids of a height chosen with atomic-scale precision. Water transport through the channels, ranging in height from one to several dozen atomic planes, is characterized by unexpectedly fast flow (up to 1 metre per second) that we attribute to high capillary pressures (about 1,000 bar) and large slip lengths. For channels that accommodate only a few layers of water, the flow exhibits a marked enhancement that we associate with an increased structural order in nanoconfined water. Our work opens up an avenue to making capillaries and cavities with sizes tunable to ångström precision, and with permeation properties further controlled through a wide choice of atomically flat materials available for channel walls.

Solution-processed soldering of carbon nanotubes for flexible electronics.

We report a simple lithography-free, solution-based method of soldering of carbon nanotubes with Ohmic contacts, by taking specific examples of multi-walled carbon nanotubes (MWNTs). This is achieved by self-assembling a monolayer of soldering precursor, Pd(2+) anchored to 1,10 decanedithiol, onto which MWNTs could be aligned across the gap electrodes via solvent evaporation. The nanosoldering was realized by thermal/electrical activation or by both in sequence. Electrical activation and the following step of washing ensure selective retention of MWNTs spanning across the gap electrodes. The soldered joints were robust enough to sustain strain caused during the bending of flexible substrates as well as during ultrasonication. The estimated temperature generated at the MWNT-Au interface using an electro-thermal model is ∼150 °C, suggesting Joule heating as the primary mechanism of electrical activation. Further, the specific contact resistance is estimated from the transmission line model.

Long-term memory and synapse-like dynamics in two-dimensional nanofluidic channels.

Fine-tuned ion transport across nanoscale pores is key to many biological processes, including neurotransmission. Recent advances have enabled the confinement of water and ions to two dimensions, unveiling transport properties inaccessible at larger scales and triggering hopes of reproducing the ionic machinery of biological systems. Here we report experiments demonstrating the emergence of memory in the transport of aqueous electrolytes across (sub)nanoscale channels. We unveil two types of nanofluidic memristors depending on channel material and confinement, with memory ranging from minutes to hours. We explain how large time scales could emerge from interfacial processes such as ionic self-assembly or surface adsorption. Such behavior allowed us to implement Hebbian learning with nanofluidic systems. This result lays the foundation for biomimetic computations on aqueous electrolytic chips.

Evaluation of potable groundwater quality in some villages of Adilabad in Andhra Pradesh, India.

Reconnaissance hydrochemical survey was conducted in some villages of Adilabad district, Andhra Pradesh to assess the quality of groundwater, which is mainly used for drinking purpose. The study consists of the determination of physico-chemical properties, trace metals, heavy metals and rare earth elements in water samples. The data showed the variation of the investigated parameters in samples as follows: pH 6.92 to 8.32, EC 192 to 2706 microS cm(-1), TDS 129.18 to 1813.02 ppm. The pH of the waters was within the permissible limits whereas EC and TDS were above the permissible limits of World Health Organization (WHO). Total 27 elements (Li, Be, B, Na, Mg, Al, Si, K, Ca, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Ba and Pb) were analyzed using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). The concentration of elements in water samples ranged between 0.063 to 0.611 mg l(-1) for B, 11.273 to 392 mg l(-)1 for Na, 5.871 to 77.475 mg l(-1) for Mg, 0.035 to 1.905 mg l(-1) for Al, 0.752 to 227.893 mg l(-1) for K, 11.556 to 121.655 mg l(-1) for Ca and 0.076 to 0.669 mg l(-1) for Fe respectively. The concentrations of Na, Mg, Al, K, Ca, and Fe exceeded the permissible limits of WHO and BIS guidelines for drinking water quality. In the present study, Bhimavaram, Kazipalli, Kannepalli and Chennur areas of the Adilabad are especially prone to geogenic contamination. Overall water quality was found unsatisfactory for drinking purposes.

Clogging and Unclogging of Hydrocarbon-Contaminated Nanochannels.

The recent advantages of the fabrication of artificial nanochannels enabled new research on the molecular transport, permeance, and selectivity of various gases and molecules. However, the physisorption/chemisorption of the unwanted molecules (usually hydrocarbons) inside nanochannels results in the alteration of the functionality of the nanochannels. We investigated contamination due to hydrocarbon molecules, nanochannels made of graphene, hexagonal boron nitride, BC2N, and molybdenum disulfide using molecular dynamics simulations. We found that for a certain size of nanochannel (i.e., h = 0.7 nm), as a result of the anomalous hydrophilic nature of nanochannels made of graphene, the hydrocarbons are fully adsorbed in the nanochannel, giving rise to full uptake. An increasing temperature plays an important role in unclogging, while pressure does not have a significant role. The results of our pioneering work contribute to a better understanding and highlight the important factors in alleviating the contamination and unclogging of nanochannels, which are in good agreement with the results of recent experiments.

Metal anion-alkyl ammonium complexes as direct write precursors to produce nanopatterns of metals, nitrides, oxides, sulfides, and alloys.

The study explores the possibility of using metal anions complexed with tetraoctylammonium bromide (ToABr) as single-source direct write precursors in e-beam and soft lithography processes to obtain micro- and nanoscale patterns of various metals, i.e., Au, Pd, Pt, Ag, Pb and Cu, as well as of their alloys (AuCu), oxides (Co(3)O(4), ZnO), nitrides (CoN, InN, GaN), and sulfides (Ag(2)S). The extraction efficiency of ToABr for different metal anions is found to be varied (40-90%), but the obtained precursors are easily processable as they have reasonable solubility in common solvents and are obtainable as smooth films, both being important for high-resolution patterning. The e-resist action of the precursors originates from the extreme e-beam sensitivity of the hydrocarbon chain present in ToABr, while direct micromolding has been possible due to easy flow of the precursor solutions in capillaries. The interaction of the anion and ToABr being mainly electrostatic enables easy removal of the hydrocarbon from patterned regions by thermolysis on a hot plate in the ambient or in controlled atmosphere to form the desired product. This method can be easily generalized.

Direct micromolding of Pd micro-stripes for electronic applications.

A simple, one-step direct micromolding process has been realised to produce highly conducting Pd micro-stripes over large areas on various substrates including flexible polyimide. Under a PDMS micromold, Pd octanethiolate served as a precursor at 250 degrees C, a temperature at which the precursor gets neatly metallised. Thus produced micro-stripes are robust under bending and can be utilised for flexible electronics. Hydrogen sensing by Pd micro-stripes is demonstrated. By electrolessly depositing Cu on the stripes, they can be made to peel off to form free standing Cu-Pd micro-ribbons.

Fulminant hepatitis and glomerulonephritis--a rare presentation of hepatitis A virus infection.

AIM: We report a case of fulminant hepatitis and glomerulonephritis by Hepatitis A virus infection. METHODS: We observed the patient's clinical course and analyzed his data retrospectively. RESULTS: The three-year-old boy presented with features of acute renal failure and stage 2 hepatic encephalopathy. Renal biopsy showed diffuse mesangioproliferative glomerulonephritis with immunoglobulin M and complement 3 deposition. After receiving supportive treatment for over 6 weeks, the hepatic and renal function became normal. Renal biopsy after 3 months was normal. CONCLUSION: Acute renal failure is a rare complication of Hepatitis A virus infection. Physicians should be aware of the potential renal involvement of Hepatitis A virus infection as the prognosis is not always favourable.

Clinical course of children with a depressive spectrum disorder and transient manic symptoms.

OBJECTIVE: To assess rates of conversion to bipolar spectrum disorder (BPSD) and risk factors associated with conversion in children with depressive spectrum disorders (DSD) and transient manic symptoms (TMS) over 18 months. TMS are manic-like symptoms of insufficient duration or number to warrant a diagnosis of BPSD. METHODS: Participants were 165 children (mean = 9.9 years, SD = 1.3) with mood disorders from the Multi-Family Psychoeducational Psychotherapy (MF-PEP) treatment study: 37 with DSD+TMS, 13 with DSD, and 115 with BPSD. All were assessed with standardized instruments on four occasions over 18 months, with half receiving MF-PEP after their baseline assessment and half receiving MF-PEP after a one-year wait-list condition. RESULTS: At baseline, the Children's Global Assessment Scale scores did not differ significantly between the DSD+TMS, DSD, and BPSD groups. Conversion rates to BPSD were significantly higher for the DSD+TMS group (48.0%) compared to the DSD group (12.5%). Conversion was significantly more frequent for participants in the one-year wait-list control group (60%) compared to the immediate treatment group (16%). Clinical presentation, family environment, and family history did not differ significantly between the small subset of DSD+TMS participants who did convert to BPSD at follow-up and those who did not convert. Baseline functional impairment was greater for the converted group than the non-converted group. CONCLUSIONS: Transient manic symptoms are a risk factor for eventual conversion to BPSD; psychoeducational psychotherapy may be protective. As this exploratory study had a small sample size and did not correct for multiple comparisons, additional studies with larger sample sizes are needed.

Direct Micromolding of Bimetals and Transparent Conducting Oxide Using Metal-TOABr Complexes as Single-Source Precursors.

Patterning of metals, alloys, and conducting oxides is vitally important for many industrial applications pertaining to many technological devices. In this report, we have used the metal anion alkyl ammonium complex (M-TOABr) as a single-source precursor to obtain thin films as well as micro (µ)-patterns of bimetals (Au-Pd, Au-Pt, Au-Cu, and Pt-Pd) and conducting oxides (ITO). This complex can be easily filled inside the soft mold and converted to the desired material in a single step known as direct patterning. The as-obtained µ-pattern comprises a well-connected network of nanocrystals giving rise to metallic conductivity. These periodically aligned bimetals and transparent conducting oxide (TCO) microwires could effectively serve as electrodes as well as an electrocatalyst with the prudence of providing passage for light transmission for many functional photoelectrochemical devices. In addition, the electrochemical stability of the bimetallic film was examined by fabricating a supercapacitor device and by studying its performance.

Complete steric exclusion of ions and proton transport through confined monolayer water.

It has long been an aspirational goal to create artificial structures that allow fast permeation of water but reject even the smallest hydrated ions, replicating the feat achieved by nature in protein channels (e.g., aquaporins). Despite recent progress in creating nanoscale pores and capillaries, these structures still remain distinctly larger than protein channels. We report capillaries made by effectively extracting one atomic plane from bulk crystals, which leaves a two-dimensional slit of a few angstroms in height. Water moves through these capillaries with little resistance, whereas no permeation could be detected even for such small ions as Na+ and Cl- Only protons (H+) can diffuse through monolayer water inside the capillaries. These observations improve our understanding of molecular transport at the atomic scale.

Anomalously low dielectric constant of confined water.

The dielectric constant ε of interfacial water has been predicted to be smaller than that of bulk water (ε ≈ 80) because the rotational freedom of water dipoles is expected to decrease near surfaces, yet experimental evidence is lacking. We report local capacitance measurements for water confined between two atomically flat walls separated by various distances down to 1 nanometer. Our experiments reveal the presence of an interfacial layer with vanishingly small polarization such that its out-of-plane ε is only ~2. The electrically dead layer is found to be two to three molecules thick. These results provide much-needed feedback for theories describing water-mediated surface interactions and the behavior of interfacial water, and show a way to investigate the dielectric properties of other fluids and solids under extreme confinement.

Size effect in ion transport through angstrom-scale slits.

In the field of nanofluidics, it has been an ultimate but seemingly distant goal to controllably fabricate capillaries with dimensions approaching the size of small ions and water molecules. We report ion transport through ultimately narrow slits that are fabricated by effectively removing a single atomic plane from a bulk crystal. The atomically flat angstrom-scale slits exhibit little surface charge, allowing elucidation of the role of steric effects. We find that ions with hydrated diameters larger than the slit size can still permeate through, albeit with reduced mobility. The confinement also leads to a notable asymmetry between anions and cations of the same diameter. Our results provide a platform for studying the effects of angstrom-scale confinement, which is important for the development of nanofluidics, molecular separation, and other nanoscale technologies.

Role of HLA-B51 and HLA-B52 in susceptibility to pulmonary tuberculosis.

MHC class I-restricted CD8+ T cells are important for the generation of protective immune responses in MTB infection. CD8+ CTL (cytotoxic T-lymphocyte)-derived IFN-g may be especially important both for cells lacking MHC class II molecules, e.g. in the lung and for macrophages where mycobacteria can evade recognition during chronic infection by sequestering their antigens away from sensitized CD4+ T cells. This study was designed to detect any association of MHC class I (HLA-B) molecules with pulmonary tuberculosis. A total of 75 individuals, comprising of 33 patients with pulmonary tuberculosis; 12 HIV patients who developed tuberculosis and 30 healthy controls, were included in the study. They were typed for HLA-B by the PCR-SSP method. The results of only HLA-B alleles, which are highly significant, are presented here. The number of healthy individuals with HLA-B52 was significantly high when compared to the patient groups (healthy versus TB: 21.2% versus 0.0%, OR=0.0, P<0.0001, P(c)=0.003; healthy versus HIV-TB: 21.2% versus 16.7%; OR=0.74; P<0.001; P(c)=0.003). In contrast, the number of patients, both TB- and HIV-TB-positive, with HLA-B51 was significantly high when compared to the healthy group of individuals (TB versus healthy: 36.7% versus 3%; OR=18.53; P<0.0001; P(c)=0.001; HIV-TB versus healthy: 41.7% versus 3%; OR=22.86; P<0.0001; P(c)=0.001). Only one healthy control was positive to HLA-B51; however this individual also had HLA-B52. The results of this study suggest that HLA-B52(5) has a negative, i.e. a protective association and HLA-B51(5) has a positive (susceptible) association, for pulmonary tuberculosis. Studies on HLA-B51 and HLA-B52 in a larger population to assess their role in tuberculosis may be useful for TB-vaccination strategies, since HLA profiles are likely to be related to vaccine efficacy.

Sieving hydrogen isotopes through two-dimensional crystals.

One-atom-thick crystals are impermeable to atoms and molecules, but hydrogen ions (thermal protons) penetrate through them. We show that monolayers of graphene and boron nitride can be used to separate hydrogen ion isotopes. Using electrical measurements and mass spectrometry, we found that deuterons permeate through these crystals much slower than protons, resulting in a separation factor of ≈10 at room temperature. The isotope effect is attributed to a difference of ≈60 milli-electron volts between zero-point energies of incident protons and deuterons, which translates into the equivalent difference in the activation barriers posed by two-dimensional crystals. In addition to providing insight into the proton transport mechanism, the demonstrated approach offers a competitive and scalable way for hydrogen isotope enrichment.

Large-area ohmic top contact to vertically grown nanowires using a free-standing Au microplate electrode.

A method of electrically contacting vertically grown nanowires of uneven heights, a common scenario among as-grown nanowires, is reported here using a chemically synthesized single-crystalline Au microplate as top electrode. The contact is electrically activated and the contact formation is predominantly due to electromigration. With this approach, the electrode could ohmically contact several thousand nanowires at once.

Flexible and semitransparent strain sensors based on micromolded Pd nanoparticle-carbon µ-stripes.

Flexible resistive strain sensors have been fabricated by micromolding Pd alkanethiolate on polyimide substrates and subjecting to thermolysis in air. Thus produced stripes were ∼1 µm wide with spacing of ∼0.5 µm and contained Pd nanoparticles in carbon matrix. The nanoparticle size and the nature of carbon are much dependent on the thermolysis temperature as is also the resistance of the microstripes. Generally, lower thermolysis temperatures (<230 °C) produced stripes containing small Pd nanoparticles with significant fraction of carbon from the precursor decomposition. The stripes were poorly conducting yet interestingly, exhibited change of resistance under tensile and compressive strain. Particularly noteworthy are the stripes produced from 195 °C thermolysis, which showed a high gauge factor of ∼390 with strain sensitivity, 0.09%. With molding at 230 °C, the stripes obtained were highly conducting, and amazingly did not change the resistance with strain even after several bending cycles. The latter are ideal as flexible conduits and interconnects. Thus, the article reports a method of producing flexible sensitive strain sensors on one hand and on the other, flexible conduits with unchanging resistance, merely by fine-tuning the precursor decomposition under the molding conditions.

Metal nanowire grating patterns.

Metal nanowire patterning in the form of grating structures has been carried out using a wide range of lithography techniques, and many hybrid methods derived from them. The challenge is to achieve sub-100 nm linewidths with controllable spacing and thickness over large areas of substrates with high throughput. In particular, the patterns with linewidth and spacing of a few tens of nm offer properties of great interest in optoelectronics and plasmonics. Crossbar grating structures--two gratings patterned perpendicular to each other--will play an important role as ultra-high density electrode grids in memristive devices for non-volatile memory.