10 research outputs found
Finishing the euchromatic sequence of the human genome
The sequence of the human genome encodes the genetic instructions for human physiology, as well as rich information about human evolution. In 2001, the International Human Genome Sequencing Consortium reported a draft sequence of the euchromatic portion of the human genome. Since then, the international collaboration has worked to convert this draft into a genome sequence with high accuracy and nearly complete coverage. Here, we report the result of this finishing process. The current genome sequence (Build 35) contains 2.85 billion nucleotides interrupted by only 341 gaps. It covers ∼99% of the euchromatic genome and is accurate to an error rate of ∼1 event per 100,000 bases. Many of the remaining euchromatic gaps are associated with segmental duplications and will require focused work with new methods. The near-complete sequence, the first for a vertebrate, greatly improves the precision of biological analyses of the human genome including studies of gene number, birth and death. Notably, the human enome seems to encode only 20,000-25,000 protein-coding genes. The genome sequence reported here should serve as a firm foundation for biomedical research in the decades ahead
Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule
Chirality-selective functionalization
of semiconducting single-walled
carbon nanotubes (SWCNTs) has been a difficult synthetic goal for
more than a decade. Here we describe an on-demand covalent chemistry
to address this intriguing challenge. Our approach involves the synthesis
and isolation of a chemically inert diazoether isomer that can be
switched to its reactive form <i>in situ</i> by modulation
of the thermodynamic barrier to isomerization with pH and visible
light that resonates with the optical frequency of the nanotube. We
found that it is possible to completely inhibit the reaction in the
absence of light, as determined by the limit of sensitive defect photoluminescence
(less than 0.01% of the carbon atoms are bonded to a functional group).
This optically driven diazoether chemistry makes it possible to selectively
functionalize a specific SWCNT chirality within a mixture. Even for
two chiralities that are nearly identical in diameter and electronic
structure, (6,5)- and (7,3)-SWCNTs, we are able to activate the diazoether
compound to functionalize the less reactive (7,3)-SWCNTs, driving
the chemical reaction to near exclusion of the (6,5)-SWCNTs. This
work opens opportunities to chemically tailor SWCNTs at the single
chirality level for nanotube sorting, on-chip passivation, and nanoscale
lithography
Channeling Excitons to Emissive Defect Sites in Carbon Nanotube Semiconductors beyond the Dilute Regime
The exciton photoluminescence
of carbon nanotube semiconductors
has been intensively exploited for bioimaging, anticounterfeiting,
photodetection, and quantum information science. However, at high
concentrations, photoluminescence is lost to self-quenching because
of the nearly complete overlap of the absorption and emissive states
(∼10 meV Stokes shift). Here we show that by introducing sparse
fluorescent quantum defects via covalent chemistry, self-quenching
can be efficiently bypassed by means of the new emission route. The
defect photoluminescence is significantly red-shifted by 190 meV for <i>p</i>-nitroaryl tailored (6,5)-single-walled carbon nanotubes
(SWCNTs) from the native emission of the nanotube. Notably, the defect
photoluminescence is more than 34 times brighter than the native photoluminescence
of unfunctionalized SWCNTs in the most concentrated nanotube solution
tested (2.7 × 10<sup>14</sup> nanotubes/mL). Moreover, we show
that defect photoluminescence is more resistant to self-quenching
than the native state in a dense film, which is the upper limit of
concentration. Our findings open opportunities to harness nanotube
excitons in highly concentrated systems for applications where photoluminescence
brightness and light-collecting efficiency are mutually important
Optical Probing of Local pH and Temperature in Complex Fluids with Covalently Functionalized, Semiconducting Carbon Nanotubes
We
show that local pH can be optically probed through defect photoluminescence
from semiconducting carbon nanotubes covalently functionalized with
aminoaryl groups. Switching between protonated and deprotonated forms
of the amino moiety produces an energy shift in the defect state of
the functionalized nanotube by as much as 33 meV in the near-infrared
region. This unexpected observation enables a new optical pH sensor
that features ultrabright near-infrared II (1.1–1.4 μm)
photoluminescence, a sensitivity for pH changes as small as 0.2 pH
units over a wide working window that covers the entire physiologic
pH range, and potentially molecular resolution. Independent of pH,
this nanoprobe can simultaneously act as a nanothermometer by monitoring
temperature-modulated changes in photoluminescence intensity, which
follows the van’t Hoff equation. This work opens new opportunities
for quantitative probing of local pH and temperature changes in complex
biological systems
Fluorescent Carbon Nanotube Defects Manifest Substantial Vibrational Reorganization
Fluorescent defects have opened up
exciting new opportunities to
chemically tailor semiconducting carbon nanotubes for imaging, sensing,
and photonics needs such as lasing, single photon emission, and photon
upconversion. However, experimental measurements on the trap depths
of these defects show a puzzling energy mismatch between the optical
gap (difference in emission energies between the native exciton and
defect trap states) and the thermal detrapping energy determined by
application of the van ’t Hoff equation. To resolve this
fundamentally important problem, here we synthetically incorporated
a series of fluorescent aryl defects into semiconducting single-walled
carbon nanotubes and experimentally determined their energy levels
by temperature-dependent and chemically correlated evolution of exciton
population and photoluminescence. We found that depending on the chemical
nature and density of defects, the exciton detrapping energy is 14–77%
smaller than the optical gap determined from photoluminescence. For
the same type of defect, the detrapping energy increases with defect
density from 76 to 131 meV for 4-nitroaryl defects in (6,5) single-walled
carbon nanotubes, whereas the optical gap remains nearly unchanged
(<5 meV). These experimental findings are corroborated by quantum-chemical
simulations of the chemically functionalized carbon nanotubes. Our
results suggest that the energy mismatch arises from vibrational reorganization
due to significant deformation of the nanotube geometry upon exciton
trapping at the defect site. An unexpectedly large reorganization
energy (on the order of 100 meV) is found between ground and excited
states of the defect tailored nanostructures. This finding reveals
a molecular picture for description of these synthetic defects and
suggests significant potential for tailoring the electronic properties
of carbon nanostructures through chemical engineering