391 research outputs found
Deep control of linear oligomerization of glycerol using lanthanum catalyst on mesoporous silica gel
The valorization of glycerol (1), a waste of biodiesel production of Fatty Acid Methyl Esters (FAMEs), adopting a âgreenâ approach, represents an important goal of sustainable chemistry. While the polymerization of 1 to hyperbranched oligomers is a well-established process, the linear analogues are difficult to obtain. In this context, we explore the reaction without the solvent of heterogeneous hybrid La(III)O-KIT-6 catalyst (2), which is based on lanthanum oxide on mesoporous silica gel, showing a superior linear selectivity compared to most of the analogous catalysts recently reported
College Studentsâ Use of Communication Technology with Parents: Influences of Distance, Gender, and Social Presence
Information and communication technology (ICT) has significantly affected the way people maintain relationships despite spatial and other social and economic barriers. In the case of college students and their parents, ICT is a means of maintaining this parent-child relationship when students travel far from home to attend school. However, little research has examined college studentsâ use of various types of technology for communicating with their parents and how it may affect their relationship with their parents. This chapter analyzes the socio-spatial aspects of how college students use a variety of communication channels (cell phones, text messaging, email, and social networking sites) to connect with their parents using both quantitative and qualitative methods. Specifically, the study addresses: 1) the impact of geographical distance between a college student and their parent on their use of communication technology and the qualities of their relationship, 2) how the gender of both the students and their parents influences the amount and type of communication technology students use with their parents, and 3) whether or not studentsâ social presence mediates the association between using particular technologies to communicate with their parents and their relationship with their parents. Overall, this chapter contributes to our understanding of the social and spatial aspects of communication technologies within the parent-child relationship and has important implications for universities and families with students transitioning to college
Reversible stretching of homopolymers and random heteropolymers
We have analyzed the equilibrium response of chain molecules to stretching.
For a homogeneous sequence of monomers, the induced transition from compact
globule to extended coil below the -temperature is predicted to be
sharp. For random sequences, however, the transition may be smoothed by a
prevalence of necklace-like structures, in which globular regions and coil
regions coexist in a single chain. As we show in the context of a random
copolymer, preferential solvation of one monomer type lends stability to such
structures. The range of stretching forces over which necklaces are stable is
sensitive to chain length as well as sequence statistics.Comment: 14 pages, 4 figure
Mechanical response of random heteropolymers
We present an analytical theory for heteropolymer deformation, as exemplified
experimentally by stretching of single protein molecules. Using a mean-field
replica theory, we determine phase diagrams for stress-induced unfolding of
typical random sequences. This transition is sharp in the limit of infinitely
long chain molecules. But for chain lengths relevant to biological
macromolecules, partially unfolded conformations prevail over an intermediate
range of stress. These necklace-like structures, comprised of alternating
compact and extended subunits, are stabilized by quenched variations in the
composition of finite chain segments. The most stable arrangements of these
subunits are largely determined by preferential extension of segments rich in
solvophilic monomers. This predicted significance of necklace structures
explains recent observations in protein stretching experiments. We examine the
statistical features of select sequences that give rise to mechanical strength
and may thus have guided the evolution of proteins that carry out mechanical
functions in living cells.Comment: 10 pages, 6 figure
Free induction signal from biexcitons and bound excitons
A theory of the free induction signal from biexcitons and bound excitons is
presented. The simultaneous existence of the exciton continuum and a bound
state is shown to result in a new type of time dependence of the free
induction. The optically detected signal increases in time and oscillates with
increasing amplitude until damped by radiative or dephasing processes.
Radiative decay is anomalously fast and can result in strong picosecond pulses.
The expanding area of a coherent exciton polarization (inflating antenna),
produced by the exciting pulse, is the underlying physical mechanism. The
developed formalism can be applied to different biexciton transients.Comment: RevTeX, 20 p. + 2 ps fig. To appear in Phys. Rev. B1
Theory of mechanical unfolding of homopolymer globule: all-or-none transition in force-clamp mode vs phase coexistence in position-clamp mode
Equilibrium mechanical unfolding of a globule formed by long flexible
homopolymer chain collapsed in a poor solvent and subjected to an extensional
force f (force-clamp mode) or extensional deformation D (position-clamp mode)
is studied theoretically. Our analysis, like all previous analysis of this
problem, shows that the globule behaves essentially differently in two modes of
extension. In the force-clamp mode, mechanical unfolding of the globule with
increasing applied force occurs without intramolecular microphase segregation,
and at certain threshold value of the pulling force the globule unfolds as a
whole ("all-or-none" transition). The value of the threshold force and the
corresponding jump in the distance between the chain ends increase with a
deterioration of the solvent quality and/or with an increase in the degree of
polymerization. In the position-clamp mode, the globule unfolding occurs via
intramolecular microphase coexistence of globular and extended microphases
followed by an abrupt unraveling transition. Reaction force in the microphase
segregation regime demonstrates an "anomalous" decrease with increasing
extension. Comparison of deformation curves in force and position-clamp modes
demonstrates that at weak and strong extensions the curves for two modes
coincide, differences are observed in the intermediate extension range. Another
unfolding scenario is typical for short globules: in both modes of extension
they unfold continuously, without jumps or intramolecular microphase
coexistence, by passing a sequence of uniformly elongated configurations.Comment: 19 pages, 13 figures, 1 tabl
Mechanical Strength of 17 134 Model Proteins and Cysteine Slipknots
A new theoretical survey of proteins' resistance to constant speed stretching
is performed for a set of 17 134 proteins as described by a structure-based
model. The proteins selected have no gaps in their structure determination and
consist of no more than 250 amino acids. Our previous studies have dealt with
7510 proteins of no more than 150 amino acids. The proteins are ranked
according to the strength of the resistance. Most of the predicted top-strength
proteins have not yet been studied experimentally. Architectures and folds
which are likely to yield large forces are identified. New types of potent
force clamps are discovered. They involve disulphide bridges and, in
particular, cysteine slipknots. An effective energy parameter of the model is
estimated by comparing the theoretical data on characteristic forces to the
corresponding experimental values combined with an extrapolation of the
theoretical data to the experimental pulling speeds. These studies provide
guidance for future experiments on single molecule manipulation and should lead
to selection of proteins for applications. A new class of proteins, involving
cystein slipknots, is identified as one that is expected to lead to the
strongest force clamps known. This class is characterized through molecular
dynamics simulations.Comment: 40 pages, 13 PostScript figure
Spatio-temporal dynamics of quantum-well excitons
We investigate the lateral transport of excitons in ZnSe quantum wells by
using time-resolved micro-photoluminescence enhanced by the introduction of a
solid immersion lens. The spatial and temporal resolutions are 200 nm and 5 ps,
respectively. Strong deviation from classical diffusion is observed up to 400
ps. This feature is attributed to the hot-exciton effects, consistent with
previous experiments under cw excitation. The coupled transport-relaxation
process of hot excitons is modelled by Monte Carlo simulation. We prove that
two basic assumptions typically accepted in photoluminescence investigations on
excitonic transport, namely (i) the classical diffusion model as well as (ii)
the equivalence between the temporal and spatial evolution of the exciton
population and of the measured photoluminescence, are not valid for
low-temperature experiments.Comment: 8 pages, 6 figure
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