Identification of potential lockdown areas during COVID-19 transmission in Punjab, Pakistan.

OBJECTIVES: Real-time COVID-19 spread mapping and monitoring to identify lockdown and semi-lockdown areas using hotspot analysis and geographic information systems and also near future prediction modeling for risk of COVID-19 in Punjab, Pakistan. STUDY DESIGN: Data for all COVID-19 cases were collected until 20 October 2020 in Punjab Province. METHODS: The methodology included geotagging COVID-19 cases to understand the trans-mobility areas for COVID-19 and characterize risk. The hotspot analysis technique was used to identify the number of areas in danger zones and the number of people affected by COVID-19. The complete lockdown areas were marked down geographically to be selected by the government of Pakistan based on increased numbers of cases. RESULTS: As per predictive model estimates, almost 9.2 million people are COVID-19 infected by 20 October 2020 in Punjab Province. The compound growth rate of COVID-19 decreased to 0.012% per day and doubling rate increased to 364.5 days in Punjab Province. Based on Pueyo model predictions from past temporal data, it is more likely that Punjab and Pakistan entered into peak around the first week of July 2020, and the decline of growth rate (and doubling rate) of reported cases started afterward. Hospital load was also measured through the Pueyo model, and mostly, people in the 60+ years age group are expected to dominate the hospitalized population. CONCLUSIONS: Pakistan is experiencing a high number of COVID-19 cases, with the maximum share from Punjab, Pakistan. Statistical modeling and compound growth estimation formulation were done through the Pueyo model, which was applied in Pakistan to identify the compound growth of COVID-19 patients and predicting numbers of patients shortly by slightly modifying it as per the local context.

Elastic wave propagation in smooth and wrinkled stratified polymer films.

Periodic materials with sub-micrometer characteristic length scale can provide means for control of propagation of hypersonic phonons. In addition to propagation stopbands for the acoustic phonons, distinct dispersive modes can reveal specific thermal and mechanical behavior under confinement. Here, we employ both experimental and theoretical methods to characterize the phonon dispersion relation (frequency versus wave vector). We employed Brillouin light scattering (BLS) spectroscopy to record the phonon dispersion in stratified multilayer polymer films. These films consist of 4-128 alternate polycarbonate (PC) and poly (methyl methacrylate) (PMMA) layers along and normal to the periodicity direction. The distinct direction-dependent phonon propagation was theoretically accounted for, by considering the polarization, frequency and intensity of the observed modes in the BLS spectra. Layer-guiding was also supported by the glass transition temperatures of the PC and PMMA layers. The number of phonon dispersion branches increased with the number of layers but only a few branches were observable by BLS. Introduction of an additional in-plane periodicity, through a permanent wrinkling of the smooth PC/PMMA films, had only subtle consequences in the phonon propagation. Using the frequencies of the periodicity induced modes and momentum conservation equation we were able to precisely back calculate the wrinkle periodicity. However, a wrinkling-induced acoustic stopband utilizing flexible layered materials is still a challenge.

Solvent-Dependent Light-Induced Structures in Gem-Dichlorocyclopropanated Polybutadiene Solutions.

The formation of permanent structures upon mild red laser illumination in transparent polydiene solutions is examined in the case of gem-dichlorocyclopropanated polybutadiene ( gDCC-PB) polymers bearing 15% functional units of the dichlorocyclopropane groups. The response was found to be distinct from the precursor PB. Whereas fiber-like patterns were clearly observed in both precursor and gDCC-PB solutions in cyclohexane, these were absent in the case of gDCC-PB/chloroform but were present in the precursor PB/chloroform solutions. The involved mechanical stresses were not sufficient for the gDCC activation to be detected by NMR spectroscopy. Remarkably, addition of even 10 wt % gDCC-PB into the latter solution sufficed to suppress the light-induced patterning. The importance of the chemical environment on the response to light irradiation was further checked and confirmed by use of other PB copolymers. Different diameter patterns and kinetics were observed. The strong solvent and comonomer mediated effect was reflected neither in solvency nor in optical polarizability differences of the polymers solvent couples.

Effects of pH on the structure and mechanical properties of dried pH-responsive latex particles.

Micrometer-sized monodisperse polystyrene (PS) particles carrying a pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) colloidal stabilizer were synthesized via free radical dispersion polymerization. X-ray photoelectron spectroscopy and electrophoretic measurements verified that PDEA covered the PS particle surface. At pH 3.0 and 6.3, where the PDEA is protonated and cationically charged, the PDEA-PS particles were well dispersed in aqueous media thanks to the water soluble PDEA stabilizer and slowly sedimented due to gravity and enriched at the bottom of the glass vials. At pH 10.0, where the PDEA is non-protonated and neutral, the PDEA-PS particles weakly aggregated due to non-hydrated and collapsed PDEA. These PDEA-PS particles and aggregates sedimented to the bottom. The sediment height observed at pH 10.0 was higher than those observed at pH 3.0 and 6.3 in both wet and dry systems, which indicated that a larger porosity was formed at pH 10.0. Mechanical testing experiments confirmed that the fracture toughness of the dried materials decreased with an increase of pH. The fracture toughness was found to be correlated with the degree of particle ordering in the dried particulate materials: more ordered, dense packings lead to a higher fracture toughness compared to amorphous, less dense packings. Thus, we could tune fracture toughness and degree of particle ordering by controlling the pH.

Kinetics of Light-Induced Concentration Patterns in Transparent Polymer Solutions.

When exposed to weak visible laser light, solutions of common polymers like poly(isoprene) and poly(butadiene) respond by local concentration variations, which in turn lead to refractive index changes. Various micropatterns have been recently reported, depending mostly on the solvent environment and the irradiation conditions. Here, we focused on the simpler case of single polymer-rich filaments and we employed phase contrast microscopy to systematically investigate the influence of laser illumination and material parameters on the kinetics of the optically induced local concentration increase in the polydiene solutions. The refractive index contrast of the formed filaments increased exponentially with the laser illumination time. The growth rate exhibited linear dependence on the laser power and increased with polymer chain length in semidilute solutions in good solvents. On the contrary, the kinetics of the formed filaments appeared to be rather insensitive to the polymer concentration. Albeit the origin of the peculiar light field-polymer concentration coupling remains yet elusive, the new phenomenology is considered necessary for the elucidation of its mechanism.

Surface forces between colloidal particles at high hydrostatic pressure.

It was recently suggested that the electrostatic double-layer force between colloidal particles might weaken at high hydrostatic pressure encountered, for example, in deep seas or during oil recovery. We have addressed this issue by means of a specially designed optical trapping setup that allowed us to explore the interaction of a micrometer-sized glass bead and a solid glass wall in water at hydrostatic pressures of up to 1 kbar. The setup allowed us to measure the distance between bead and wall with a subnanometer resolution. We have determined the Debye lengths in water for salt concentrations of 0.1 and 1 mM. We found that in the pressure range from 1 bar to 1 kbar the maximum variation of the Debye lengths was <1 nm for both salt concentrations. Furthermore, the magnitude of the zeta potentials of the glass surfaces in water showed no dependency on pressure.

Measuring contact angle and meniscus shape with a reflected laser beam.

Side-view imaging of the contact angle between an extended planar solid surface and a liquid is problematic. Even when aligning the view perfectly parallel to the contact line, focusing one point of the contact line is not possible. We describe a new measurement technique for determining contact angles with the reflection of a widened laser sheet on a moving contact line. We verified this new technique measuring the contact angle on a cylinder, rotating partially immersed in a liquid. A laser sheet is inclined under an angle φ to the unperturbed liquid surface and is reflected off the meniscus. Collected on a screen, the reflection image contains information to determine the contact angle. When dividing the laser sheet into an array of laser rays by placing a mesh into the beam path, the shape of the meniscus can be reconstructed from the reflection image. We verified the method by measuring the receding contact angle versus speed for aqueous cetyltrimethyl ammonium bromide solutions on a smooth hydrophobized as well as on a rough polystyrene surface.

Properties of amphiphilic oligonucleotide films at the air/water interface and after film transfer.

The self-assembly of amphiphilic hybrid materials containing an oligonucleotide sequence at the air/water interface was investigated by means of pressure-molecular area (Π-A) isotherms. In addition, films were transferred onto solid substrates and imaged using scanning force microscopy. We used oligonucleotide molecules with lipid tails, which consisted of a single stranded oligonucleotide 11 mer containing two hydrophobically modified 5-(dodec-1-ynyl)uracil nucleobases (dU11) at the 5'-end of the oligonucleotide sequence. The air/water interface was used as confinement for the self-assembling process of dU11. Scanning force microscopy of films transferred via Langmuir-Blodgett technique revealed mono-, bi- (Π ≥ 2 mN/m) and multilayer formation (Π ≥ 30 mN/m). The first layer was 1.6 ± 0.1 nm thick. It was oriented with the hydrophilic oligonucleotide moiety facing the hydrophilic substrate while the hydrophobic alkyl chains faced air. In the second layer the oligonucleotide moiety was found to face the air. The second layer was found to cover up to 95% of the sample area. Our measurements indicated that the rearrangement of the molecules into bi- and multiple bilayers happened already at the air/water interface. Similar results were obtained with a second type of oligonucleotide amphiphile, an oligonucleotide block copolymer, which was composed of an oligonucleotide 11 mer covalently attached at the terminus to polypropyleneoxide (PPO).

Dynamic measurement of the force required to move a liquid drop on a solid surface.

We measured the forces required to slide sessile drops over surfaces. The forces were measured by means of a vertical deflectable capillary stuck in the drop. The drop adhesion force instrument (DAFI) allowed the investigation of the dynamic lateral adhesion force of water drops of 0.1 to 2 µL volume at defined velocities. On flat PDMS surfaces, the dynamic lateral adhesion force increases linearly with the diameter of the contact area of the solid-liquid interface and linearly with the sliding velocity. The movement of the drop relative to the surfaces enabled us to resolve the pinning of the three-phase contact line to individual defects. We further investigated a 3D superhydrophobic pillar array. The depinning of the receding part of the rim of the drop occurred almost simultaneously from four to five pillars, giving rise to peaks in the lateral adhesion force.

Dynamics and kinetics of structure formation in molecularly tethered fluorocarbon/hydrocarbon amphiphiles.

Biphasic fluorocarbon/hydrocarbon amphiphiles tethered to cores at distances commensurate with their packing requirement can provide thermodynamic pathways toward equilibrium. This contrasts with the analogous semifluorinated alkanes. The dynamics of a fluorous biphasic hexa(3,5-substituted-phenyl)benzene (HPB) is studied with dielectric spectroscopy as a function of temperature and pressure in comparison to the parent biphasic diphenylacetylene (DPA). Dielectric spectroscopy is a sensitive probe of the fluorocarbon environment through the end C-F dipole. Four dielectrically active processes were observed that associate with the CF(3) environment within the different phases (isotropic, liquid-like lamellar, solid lamellar, glassy state). Pressure facilitates the construction of the equilibrium phase diagram. The kinetic pathways to fluorocarbon organization are explored by pressure-jump experiments. A highly cooperative process was found that is atypical of a nucleation and growth process expected for first-order transitions.

Studying flow close to an interface by total internal reflection fluorescence cross-correlation spectroscopy: quantitative data analysis.

Total internal reflection fluorescence cross-correlation spectroscopy (TIR-FCCS) has recently [S. Yordanov et al., Optics Express 17, 21149 (2009)] been established as an experimental method to probe hydrodynamic flows near surfaces, on length scales of tens of nanometers. Its main advantage is that fluorescence occurs only for tracer particles close to the surface, thus resulting in high sensitivity. However, the measured correlation functions provide only rather indirect information about the flow parameters of interest, such as the shear rate and the slip length. In the present paper, we show how to combine detailed and fairly realistic theoretical modeling of the phenomena by Brownian dynamics simulations with accurate measurements of the correlation functions, in order to establish a quantitative method to retrieve the flow properties from the experiments. First, Brownian dynamics is used to sample highly accurate correlation functions for a fixed set of model parameters. Second, these parameters are varied systematically by means of an importance-sampling Monte Carlo procedure in order to fit the experiments. This provides the optimum parameter values together with their statistical error bars. The approach is well suited for massively parallel computers, which allows us to do the data analysis within moderate computing times. The method is applied to flow near a hydrophilic surface, where the slip length is observed to be smaller than 10nm, and, within the limitations of the experiments and the model, indistinguishable from zero.

One-dimensional hypersonic phononic crystals.

We report experimental observation of a normal incidence phononic band gap in one-dimensional periodic (SiO(2)/poly(methyl methacrylate)) multilayer film at gigahertz frequencies using Brillouin spectroscopy. The band gap to midgap ratio of 0.30 occurs for elastic wave propagation along the periodicity direction, whereas for inplane propagation the system displays an effective medium behavior. The phononic properties are well captured by numerical simulations. The porosity in the silica layers presents a structural scaffold for the introduction of secondary active media for potential coupling between phonons and other excitations, such as photons and electrons.

Effect of chain topology on the self-organization and dynamics of block copolypeptides: from diblock copolymers to stars.

The effect of chain topology on (i) the peptide secondary structure, (ii) the nanophase self-assembly, and (iii) the local segmental and global peptide relaxations has been studied in a series of model diblock and 3-arm star copolypeptides of poly(epsilon-carbobenzyloxy-L-lysine) (PZLL) and poly(gamma-benzyl-L-glutamate) (PBLG) with PZLL forming the core. Diblock copolypeptides are nanophase separated with PBLG and PZLL domains comprising alpha-helices packed in a hexagonal lattice. Star copolypeptides are only weakly phase separated, comprising PBLG and PZLL alpha-helices in a pseudohexagonal lattice. Phase mixing has profound consequences on the local and global dynamics. The relaxation of the peptide secondary structure speeds up, and the helix persistence length is further reduced in the stars, signifying an increased concentration of helical defects.

Impact of atomic force microscopy on interface and colloid science.

Since its invention twenty years ago the atomic force microscope (AFM) has become one of the most important tools in colloid and interface science. The reason for this impact is that the AFM allows doing experiments on length, time, force, and energy scales, which are not accessible by any other technique. These experiments can be carried out under natural conditions, for example in liquid environments. In this paper we specify the length and time scales involved, give examples where by using the AFM relevant questions in colloid and interface science have been solved, and we discuss future perspectives.

Diffusion and conformation of peptide-functionalized polyphenylene dendrimers studied by fluorescence correlation and 13C NMR spectroscopy.

We report on the combined use of fluorescence correlation spectroscopy (FCS) and 1H and 13C NMR spectroscopy to detect the size and type of peptide secondary structures in a series of poly-Z-L-lysine functionalized polyphenylene dendrimers bearing the fluorescent perylenediimide core in solution. In dilute solution, the size of the molecule as detected from FCS and 1H NMR diffusion measurements matches nicely. We show that FCS is a sensitive probe of the core size as well as of the change in the peptide secondary structure. However, FCS is less sensitive to functionality. A change in the peptide secondary conformation from beta-sheets to alpha-helices detected by 13C NMR spectroscopy gives rise to a steep increase in the hydrodynamic radii for number of residues n > or = 16. Nevertheless, helices are objects of low persistence.

Nanowear on polymer films of different architecture.

In this paper, we describe atomic force microscope (AFM) friction experiments on different polymers. The aim was to analyze the influence of the physical architecture of the polymer on the degree and mode of wear and on the wear mode. Experiments were carried out with (1) linear polystyrene (PS) and cycloolefinic copolymers of ethylene and norbornene, which are stabilized by entanglements, (2) mechanically stretched PS, (3) polyisoprene-b-polystyrene diblock copolymers, with varying composition, (4) brush polymers consisting of a poly(methyl methacrylate) (PMMA) backbone and PS side chains, (5) PMMA and PS brushes grafted from a silicon wafer, (6) plasma-polymerized PS, and (7) chemically cross-linked polycarbonate. For linear polymers, wear depends critically on the orientation of the chains with respect to the scan direction. With increasing cross-link density, wear was reduced and ripple formation was suppressed. The cross-linking density was the dominating material parameter characterizing wear.

Thermodynamics and rheology of cycloolefin copolymers.

Cycloolefin copolymers of ethylene and norbornene, with norbornene content in the range from 36 to 62 mol %, were studied with respect to the thermal, thermodynamic, and rheological properties using differential scanning calorimetry, pressure-volume-temperature, and dynamic mechanical measurements. All copolymers obey the principle of time-temperature superposition, i.e., they can be considered as thermorheologically simple except for a temperature range in the vicinity of T(g). Despite this, the results on (i) the ratio of activation energies E(V)(*)/H(*) used to quantify the origin of the liquid-to-glass transition, (ii) the pressure coefficient of the glass temperature T(g)(P), and (iii) the dynamic fragility m suggest increasing dynamic heterogeneity with increasing norbornene content that is driven by the structural heterogeneity along the backbone.

Surface forces in a confined polymer melt: self-consistent field analysis of full and restricted equilibrium cases.

In full equilibrium the self-consistent field theory for a homopolymer melt confined between two surfaces predicts pronounced oscillatory interaction forces on the monomer length scale. However, when not all the polymer molecules can reversibly equilibrate with the bulk, the trapped molecules may be squeezed, adding a repulsive contribution to the interaction energy. The classical constrained or restricted equilibrium approach by Scheutjens and Fleer two decades ago to deal with this for polymers adsorbed from dilute solutions, breaks down in semidilute and concentrated polymer solutions. We present a generalized restricted equilibrium ansatz applicable also for concentrated polymer solutions. The key idea is that only the adsorbed polymer molecules, i.e., molecules that touch the surface at least once, are forced to remain inside the gap, whereas the nonadsorbing chains are free to move out of the gap when the surfaces approach each other. As in dilute solutions, the forces found in confined melt with trapped adsorbed chains become repulsive. We analyse the dependence of the interaction forces both in full as well as in restricted equilibrium cases as a function of the chain length and the interactions with the surface for a compressible polymer melt.

Force measurements on myelin basic protein adsorbed to mica and lipid bilayer surfaces done with the atomic force microscope.

The mechanical and adhesion properties of myelin basic protein (MBP) are important for its function, namely the compaction of the myelin sheath. To get more information about these properties we used atomic force microscopy to study tip-sample interaction of mica and mixed dioleoylphosphatidylserine (DOPS) (20%)/egg phosphatidylcholine (EPC) (80%) lipid bilayer surfaces in the absence and presence of bovine MBP. On mica or DOPS/EPC bilayers a short-range repulsive force (decay length 1.0-1.3 nm) was observed during the approach. The presence of MBP always led to an attractive force between tip and sample. When retracting the tip again, force curves on mica and on lipid layers were different. While attached to the mica surface, the MBP molecules exhibited elastic stretching behavior that agreed with the worm-like chain model, yielding a persistence length of 0.5 +/- 0.25 nm and an average contour length of 53 +/- 19 nm. MBP attached to a lipid bilayer did not show elastic stretching behavior. This shows that the protein adopts a different conformation when in contact with lipids. The lipid bilayer is strongly modified by MBP attachment, indicating formation of MBP-lipid complexes and possibly disruption of the original bilayer structure.