Preassembly refers to an evolutionary mechanism that complements current theory. It proposes that genes and gene fragments, formed over the eons among libraries of noncoding genes, ultimately contributed to coding sequences. Previous publications of ours on preassembly have helped explain many enigmas that beset modern biology; for example, the Cambrian explosion (“one of the most remarkable and puzzling events in the history of life,” S. J. Gould), and the appearance of flowering plants with their sparsity of precursors (an “abominable mystery,” C. R. Darwin). The rapid evolutionary development of the domestic cat and human intelligence is also viewed as evidence for a mechanism supplementing neo-Darwinism. The current account centers on convergent evolution as interpreted via DNA preassembly. Convergent evolution refers to the development of near-identical traits in organisms that lack a common ancestor. A prime example is the remarkable similarity between the eyes of humans and octopuses. When early ancestors of these species split apart on the evolution tree, hundreds of millions of years ago, only eyespots existed. Clearly, convergent eyes in the two organisms evolved independently. Current evolutionary belief says that the eyes appeared after Nature had first screened hundreds of mutations, one at a time, and that this multistep and random process produced, fortuitously, two near identical structures. Preassembly, on the other hand, proposes primeval genes, or DNA segments, that had been collected over vast time periods within huge libraries of noncoding DNA (i.e., “preassembled genes”). Ultimately, these DNA units were incorporated into functional genes, a process possibly aided by genetic site-scanning.

An extension of neo-Darwinism, termed preassembly, states that genetic material required for many complex traits, such as echolocation, was present long before emergence of the traits. Assembly of genes and gene segments had occurred over protracted time-periods within large libraries of non-coding genes. Epigenetic factors ultimately promoted transfers from noncoding to coding genes, leading to abrupt formation of the trait via de novo genes. This preassembly model explains many observations that to this present day still puzzle biologists: formation of super-complexity in the absence of multiple fossil precursors, as with bat echolocation and flowering plants; major genetic and physical alterations occurring in just a few thousand years, as with housecat evolution; lack of precursors preceding lush periods of species expansion, as in the Cambrian explosion; and evolution of costly traits that exceed their need during evolutionary times, as with human intelligence. What follows in this paper is a mechanism that is not meant to supplant neo-Darwinism; instead, preassembly aims to supplement current ideas when complexity issues leave them struggling.

Four natural phenomena are cited for their defiance of conventional neo-Darwinian analysis: human intelligence; cat domesticity; the Cambrian explosion; and convergent evolution. 1. Humans are now far more intelligent than needed in their hunting–gathering days >10,000 years ago. 2. Domestic cats evolved from wildcats via major genetic and physical changes, all occurring in less than 12,000 years. 3. The Cambrian explosion refers to the remarkable expansion of species that mystifies evolutionists, as there is a total lack of fossil evidence for precursors of this abundant new life. 4. Convergent evolution often involves formation of complex, multigene traits in two or more species that have no common ancestor. These four evolutionary riddles are discussed in terms of a proposed “preassembly” mechanism in which genes and gene precursors are collected silently and randomly over extensive time periods within huge non-coding sections of DNA. This is followed by epigenetic release of the genes, when the environment so allows, and by natural selection. In neo-Darwinism, macroevolution of complex traits involves multiple mutation/selections, with each of the resulting intermediates being more favorable to the species than the previous one. Preassembly, in contrast, invokes natural selection only after a partially or fully formed trait is already in place. Preassembly does not supplant neo-Darwinism but, instead, supplements neo-Darwinism in those important instances where the classical theory is wanting.

A density functional theory (DFT) computational analysis, using the ωB97X-D functional, of a rapid amide cleavage in 2-carboxyphthalanilic acid (2CPA), where the amide group is flanked by two catalytic carboxyls, reveals key mechanistic information: (a) General base catalysis by a carboxylate coupled to general acid catalysis by a carboxyl is not operative. (b) Nucleophilic attack by a carboxylate on the amide carbonyl coupled to general acid catalysis at the amide oxygen can also be ruled out. (c) A mechanistic pathway that remains viable involves general acid proton delivery to the amide nitrogen by a carboxyl, while the other carboxylate engages in nucleophilic attack upon the amide carbonyl; a substantially unchanged amide carbonyl in the transition state; two concurrent bond-forming events; and a spatiotemporal-base rate acceleration. This mechanism is supported by molecular dynamic simulations which confirm a persistent key intramolecular hydrogen bonding. These theoretical conclusions, although not easily verified by experiment, are consistent with a bell-shaped pH/rate profile but are at odds with hydrolysis mechanisms in the classic literature.

This essay focuses on the debate between Warshel et al. (proponents of preorganization) and Menger and Nome (proponents of spatiotemporal effects) over the source of fast enzyme catalysis. The Warshel model proposes that the main function of enzymes is to push the solvent coordinate toward the transition state. Other physical-organic factors (e.g., desolvation, entropic effects, ground state destabilization, etc.) do not, ostensibly, contribute substantially to the rate. Indeed, physical organic chemistry in its entirety was claimed to be "irrelevant to an enzyme's active site". Preorganization had been applied by Warshel to his "flagship" enzyme, ketosteroid isomerase, but we discuss troubling issues with their ensuing analysis. For example, the concepts of "general acid" and "general base", known to play a role in this enzyme's mechanism, are ignored in the text. In contrast, the spatiotemporal theory postulates that enzyme-like rates (i.e., accelerations >108) occur when two functionalities are held rigidly at contact distances less than ca. 3 Å. Numerous diverse organic systems are shown to bear this out experimentally. Many of these are intramolecular systems where distances between functionalities are known. Among them are fast intramolecular systems where strain is actually generated during the reaction, thereby excluding steric compression as a source of the observed enzyme-like rates. Finally, the account ends with structural data from four active sites of enzymes, obtained by others, all showing contact distances between substrate analogues and enzyme. To our knowledge, contact distances less than the diameter of water are found universally among enzymes, and it is to this fact that we attribute their extremely fast rates given the assumption that enzymes, whatever their particular mechanism, obey elementary chemical principles.

A review of micelles' quarter century history, no matter how cursory, must not bypass the "double-relaxation" model initiated by N. Muller, experimentally tested by R. Zana and colleagues and theoretically developed by E. A. G. Aniansson and coworkers. In 1920 McBain and Salmon proposed the existence of micelles, while in 1936 G. S. Hartley ventured to guess what the micelle might look like. A good agreement was found between the correlation times for reorientation of trans-decalin in micelles and in hydrocarbon solvents with the same chain length. Engberts used a set of nine related surfactants to show that minor structural variations lead to preferential formation of spherical micelles, rodlike micelles, or vesicles. The solubilization capacity of micelles is a recurrent theme in the micelle literature. Twenty-five years ago, people began grappling with micelles in the hope of catalyzing organic reactions with an efficiency and selectivity rivaling that of enzymes.

Aspartic proteinases, which include HIV-1 proteinase, function with two aspartate carboxy groups at the active site. This relationship has been modeled in a system possessing an otherwise unactivated amide positioned between two carboxy groups. The model amide is cleaved at an enzyme-like rate that renders the amide nonisolable at 35 °C and pH 4 owing to the joint presence of carboxy and carboxylate groups. A currently advanced theory attributing almost the entire catalytic power of enzymes to electrostatic reorganization is shown to be superfluous when suitable interatomic interactions are present. Our kinetic results are consistent with spatiotemporal concepts where embedding the amide group between two carboxylic moieties in proper geometries, at distances less than the diameter of water, leads to enzyme-like rate enhancements. Space and time are the essence of enzyme catalysis.

In modern times, Lamarck's view of evolution, based on inheritance of acquired traits has been superseded by neo-Darwinism, based on random DNA mutations. This article begins with a series of observations suggesting that Lamarckian inheritance is in fact operative throughout Nature. I then launch into a discussion of human intelligence that is the most important feature of human evolution that cannot be easily explained by mutational selection. Thus, we are smarter than demanded by our evolutionary experience as hunter-gatherers. The difficulty lies in the inability of neo-Darwinism to satisfactorily answer the following question: How can a large energy-costly set of genes, each member of which has little apparent benefit when first created individually, all gather into a permanent existence within a short time period in each and every member of a small population (that was dispersed and geographically isolated over a huge planet) who had a low reproductive output, a low rate of beneficial mutations, and a low level of genetic contact? The article concludes with a speculative but far-reaching epigenetic theory of intelligence that does not require DNA mutation as the exclusive source of evolutionary change. Instead, cranial feedback relating brain chemistry, as affected by brain activity including education, with the genome. When it comes to the fast rate of evolution, and the dissemination of the intelligence trait worldwide, cranial feedback could make all the difference.

We present a smart liposome carrier system for stimulated release, consisting of cationic, thermo-responsive microgels. At low temperature, the swollen microgels adsorb about 200 anionic liposomes, 50 nm in diameter, per microgel. When heated from 39 °C to 41 °C, the microgel–liposome complex particles collapse from approx. 370 nm down to approx. 270 nm. Upon the thermo-induced collapse, the adsorbed liposome satellite layer is squeezed until the initially spherical liposomes explode and release their payload (antitumor drug doxorubicin) into the surrounding. This burst release mechanism, taking place over a narrow temperature range, is newly reported and of possible biomedical importance.

Complexes were formed via the electrostatic interaction between 30-50 nm anionic liposomes and a star-shaped polyelectrolyte, poly{[2-(methacryloyloxy)ethyl]trimethyl ammonium iodide}, having cationic arms that radiate from a silicon-based central core. The complexation was investigated with attention given to assessing the capacity of the cationic stars for the anionic liposomes (both liquid and solid); the integrity of the complexed liposomes; and the stability of the resulting star/liposome complexes in aqueous salt solutions. We have found that by changing the content of anionic groups in the liposomal membrane as well as the phase-state of membrane, the stability of star/liposome complexes in aqueous salt media can be controlled. The liquid liposomes with 0.1 mol fraction of anionic palmitoy-loleoylphosphatidylserine (POPS1-), and solid liposomes with 0.1 mol fraction of POPS1-, retain their integrity when bound to the stars, with the resulting star/liposome complexes being stable in physiological solution, i.e. [NaCl] = 0.15 M. Multi-liposomal complexes containing up to 12 liposomes per star seem to hold promise as carriers for biologically active compounds. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract The motions of Newton’s cradle, consisting of several steel balls hanging side-by-side, have been analysed in terms of a sound pulse that travels via points of contact among the balls. This presupposes a focused energy beam. When the pulse reaches the fifth and final ball, the energy disperses and dislocates the ball with a trajectory equivalent to that of the first ball after it was released. The pulse passes unchanged through the internal balls without, therefore, causing movement of these balls. Lack of movement can be affirmed by immobilising one or more of the balls, thereby disproving both the gap and vibrating lattice models. This also contrasts with previous mechanisms that postulate complete energy dispersal within a ball prior to transferring the energy to another ball. Inserting an inelastic barrier between the second and third balls disrupts the pulse such that it spreads out to reach regions that are not in contact with another ball. As a result, the normally stationary third ball is forced into a forward motion, thereby pushing the fourth and fifth ball with it as a single unit. The model is valuable in explaining a fact that has puzzled physicists for generations: why is only one motional mode observed among a multitude of motions that maintain a constant momentum and kinetic energy as required by the laws of physics? The answer lies in the fact that all motions, except the one that is actually observed, require a rebound in one or more of the balls. Since the energy beam formed upon impact is unidirectional, reverse motions are not accommodated.

Small unilamellar liposomes, 40-60 nm in diameter, composed of anionic diphosphatidylglycerol (cardiolipin, CL(2-)) or phosphatidylcerine (PS(1-)) and zwitter-ionic egg yolk lecithin (EL) or dipalmitoylphosphatidylcholine (DPPC), electrostatically complex with polystyrene microspheres, ca. 100 nm in diameter, grafted by polycationic chains ("spherical polycationic brushes", SPBs). Polymer/liposome binding studies were carried out using electrophoretic mobility (EPM), dynamic light scattering (DLS), fluorescence, conductometry, differential scanning calorimetry (DSC), and cryogenic transmission electron microscopy (cryo-TEM) as the main analytical tools. By these means a remarkably detailed picture emerges of molecular events inside a membrane. The following are among the most important conclusions that arose from the experiments: (a) binding of liposomes to SPBs is accompanied by flip-flop of anionic lipids from the inner to the outer leaflet of the liposomal membrane along with lateral lipid segregation into "islands". (b) The SPB-induced structural reorganization of the liposomal membrane, together with the geometry of anionic lipid molecules, determines the maximum molar fraction of anionic lipid (a key parameter designated as ν) that ensures the structural integrity of liposomes upon complexation: ν=0.3 for liposomes with conically-shaped CL(2-) and ν=0.5 for liposomes with anionic cylindrically-shaped PS(1-). (c) The number of intact liposomes per SPB particle varies from 40 for (ν=0.1) to 13 (ν=0.5). (d) By using a mixture of liposomes with variety of encapsulated substances, multi-liposomal complexes can be prepared with a high loading capacity and a controlled ratio of the contents. (e) In order to make the mixed anionic liposomes pH-sensitive, they are additionally modified by 30 mol% of a morpholinocyclohexanol-based lipid that undergoes a conformational flip when changing pH. Being complexed with SPBs, such liposomes rapidly release their contents when the pH is reduced from 7.0 to 5.0. The results allow loaded liposomes to be concentrated within a rather small volume and, thereby, the preparation of multi-liposomal containers of promise in the drug delivery field.

Spherical polycationic brushes (SPBs) were synthesized by grafting polycationic chains onto 100 nm polystyrene particles. These particles were exposed to unilamellar egg-lecithin (EL) liposomes with a mean diameter of 40 nm that had been rendered anionic via the presence of 10 molar% of phosphatidylserine (PS(1-)). The liposomes also contained 30 mole% of a morpholinocyclohexanol-based lipid (MOCH) that undergoes a conformational flip when the pH is decreased from 7.0 to 5.0. Mixtures of SPBs and liposomes at pH 7 gave an electrostatically-driven complex possessing, on average, about 40 liposomes for each SPB particle. It was found that the bound liposomes rapidly release much of their contents when the pH is reduced from 7.0 to 5.0 owing mostly to a MOCH conformational change that creates defects in the bilayer membrane. The drop in pH does not, however, induce a separation of the liposomes from the SPBs. Around 50-60% of the liposome contents escape before, it is reasoned, lateral and transmembrane motion of the membrane components heals the defects and prevents further release. Remarkably, the liposomes complexed with SPB release their cargo much faster than the identical but non-complexed liposomes.

Anionic liposomes are electrostatically complexed to a star-shaped cationic polyelectrolyte. Upon complexation, the liposomes retain their integrity and the resulting liposome-star complexes do not dissociate in a physiological solution with 0.15M NaCl. This provides a multi-liposomal container for possible use as a high-capacity carrier.

This paper has at its objective the assembling of liposomal assemblies onto nanoparticles. In this manner, one generates nanoparticles with a high loading capacity. Thus, spherical spherical polycationic "brushes" (SPBs) were synthesized by graft polymerizing a cationic monomer, (trimethylammonium)ethylmethacrylate chloride, onto the surface of monodisperse polystyrene particles, ca. 100 nm in diameter. These particles were complexed with small unilamellar anionic liposomes, 40-60 nm in diameter, composed of egg lecithin (EL) and anionic phosphatidylserine (PS(1-)) in PS(1-)/EL ratios from 0.10 to 0.54, a key parameter designated as ν. These complexes were then characterized according to electrophoretic mobility, dynamic light scattering, conductivity, fluorescence, and cryogenic transmission electron microscopy, with the following main conclusions: (a) All added liposomes are totally associated with SPBs up to a certain saturation concentration (specific for each ν value). (b) The number of liposomes per SPB particle varies from 40 (ν = 0.1) to 14 (ν = 0.5). (c) At sufficiently high liposome concentrations, the SPBs experience an overall change from positive to negative charge. (d) SPB complexes tend to aggregate when their initial positive charge has been precisely neutralized by the anionic liposomes. Aggregation is impeded by either positive charge at lower lipid concentrations, or negative charge at higher lipid concentrations. (e) The liposomes remain intact (i.e., do not leak) when associated with SPBs, at ν ≤ 0.5. (f) Complete SPB/liposome dissociation occurs at external [NaCl] = 0.3 M for ν = 0.1 and at 0.6 M for ν = 0.5. Liposomes with ν = 0.54 do not dissociate from the SPBs even in NaCl solutions up to 1.0 M. (g) Complexation of the PS(1-)/EL liposomes to the SPBs induces flip-flop of PS(1-) from the inner leaflet to the outer leaflet. (h) The differences in the ability of PS(1-) (a cylindrical lipid) and CL(2-) (a conical lipid) to create membranes defects are attributed to geometric factors.

The essay deals with sentence structure, style, and logical flow when writing scientific text. Ten suggestions for optimizing sentences are presented followed by ten published examp les of stylistic variations. Although the emphasis is on chemistry, the reco mmendations are applicable to all areas of non-fiction writ ing.

Two-phased: Complexation of liposomes to spherical polycationic brushes induces lipid segregation in the liposomal membrane. The greater the initial anionic lipid content in the membrane, the more the electroneutral lipid dilutes the induced anionic clusters.

In this study the treatment efficiency of different ultraviolet (UV)-enhanced ozonation processes for degradation of two surfactants, sodium dodecylbenzene sulfonate [200 mg/L or 0.3 critical micelle concentration (CMC)] and a nonylphenol ethoxylate with 40 oxyethylene units (200 mg/L ~0.5 CMC), were investigated in laboratory-scale experiments at ambient temperature. The absorbance band of the aromatic ring of the surfactants was monitored during the oxidation process. The reduction in chemical oxygen demand (COD) and total organic carbon (TOC) of the surfactant solution was evaluated. The results showed that a combination of UV irradiation and ozonation was considerably more efficient than the individual processes (at least two times more efficient in terms of COD and TOC reductions). The synergistic effect of ozonation and UV irradiation was particularly pronounced when medium-pressure UV irradiation was used. By adding alkali to the solution, the efficiency of the UV-enhanced ozonation increased with respect to COD reduction but decreased with respect to TOC reduction. This indicates partial oxidation with lower degree of mineralization of the surfactants.

Enolization of acetaldehyde catalyzed by the combined action of a general base (ammonia) and a general acid (formic acid) was examined by density functional theory at the B3LYP/6‐311 + G(3df,2p) level while manipulating distance relationships among the reactants. Computations were carried out in the gas phase, in the presence of four water molecules, and with a dielectric constant of 78.4. Enolization involves an early transition state where general‐base catalysis is more developed than general‐acid catalysis. Although formic acid does not promote enolization by itself, it does facilitate α‐proton transfer from acetaldehyde to the general base by several orders of magnitude. Formic acid accomplishes this feat via a hydrogen bond at a van der Waals distance to the carbonyl oxygen as opposed to forming a low‐barrier hydrogen bond. A low‐barrier hydrogen bond would indeed be capable of accelerating the enolization were it not for the energy cost of generating it. Formic acid may also facilitate enolization by internal solvation of the ammonium ion that is partially formed in the transition state via carbon‐to‐nitrogen proton transfer. General‐base catalysis by trimethylamine, which is out of position to coordinate with the formic acid carboxyl, actually has lower activation energy than that of ammonia catalysis, possibly owing to basicity/shielding effects. Computations also demonstrate that the proton removed by the ammonia nitrogen remains on the nitrogen throughout rather than being transferred via low‐energy rotation processes and secondary proton transfers to an oxygen atom of formic acid or the enol itself. Finally, stepwise and concerted mechanisms for enolizations have been proposed in the literature, with experimental evidence being provided for both. The concerted/non‐concerted disagreement seems to stem from the continuum of organic mechanisms that Nature bestows onto organic chemistry. Thus, acid/base catalysis varies from stepwise at one extreme to synchronous at the other extreme with an infinite number of concerted mechanisms in between. Since the degree of concertedness undoubtedly depends upon the particular acid, base, substrate, and solvent, disparate enolization models are to be expected. Copyright © 2012 John Wiley & Sons, Ltd.

Coacervates are colloidal systems that are comprised of two immiscible aqueous layers, the colloid-rich layer, so-called coacervate, and the colloid-poor layer, so-called equilibrium liquid. Although immiscible, the two phases are both water-rich. Coacervates are important for prebiotic chemistry, but also have various practical applications, notably as transport vehicles of personal care products and pharmaceuticals. Our objectives are to explore the potential of coacervates as prebiotic chemical reactors. Since the reaction medium in coacervates is water, this creates a challenge, since most organic reactants are not water-soluble. To overcome this challenge we are utilizing recent Green Chemistry examples of the organic reactions in water, such as the Passerini reaction. We have investigated this reaction in two coacervate systems, and report here our preliminary results.