Crystal engineering: from molecule to crystal

How do molecules aggregate in solution, and how do these aggregates consolidate themselves in crystals? What is the relationship between the structure of a molecule and the structure of the crystal it forms? Why do some molecules adopt more than one crystal structure? Why do some crystal structures contain solvent? How does one design a crystal structure with a specified topology of molecules, or a specified coordination of molecules and/or ions, or with a specified property? What are the relationships between crystal structures and properties for molecular crystals? These are some of the questions that are being addressed today by the crystal engineering community, a group that draws from the larger communities of organic, inorganic, and physical chemists, crystallographers, and solid state scientists. This Perspective provides a brief historical introduction to crystal engineering itself and an assessment of the importance and utility of the supramolecular synthon, which is one of the most important concepts in the practical use and implementation of crystal design. It also provides a look to the future from the viewpoint of the author, and indicates some directions in which this field might be moving.

Photoluminescence decay rate engineering of CdSe quantum dots in ensemble arrays embedded with gold nano-antennae

We discuss experimental results on the ability to significantly tune the photoluminescence decay rates of CdSe quantum dots embedded in an ordered template, using lightly doped small gold nanoparticles (nano-antennae), of relatively low optical efficiency. We observe both enhancement and quenching of photoluminescence intensity of the quantum dots varying monotonically with increasing volume fraction of added gold nanoparticles, with respect to undoped quantum dot arrays. However, the corresponding variation in lifetime of photoluminescence spectra decay shows a hitherto unobserved, non-monotonic variation with gold nanoparticle doping. We also demonstrate that Purcell effect is quite effective for the larger (5 nm) gold nano-antenna leading to more than four times enhanced radiative rate at spectral resonance, for largest doping and about 1.75 times enhancement for off-resonance. Significantly for spectral off-resonance samples, we could simultaneously engineer reduction of non-radiative decay rate along with increase of radiative decay rate. Non-radiative decay dominates the system for the smaller (2 nm) gold nano-antenna setting the limit on how small these plasmonic nano-antennae could be to be effective in engineering significant enhancement in radiative decay rate and, hence, the overall quantum efficiency of quantum dot based hybrid photonic assemblies.

Engineering New Layered Solids from Exfoliated Inorganics: a Periodically Alternating Hydrotalcite - Montmorillonite Layered Hybrid

Two-dimensional (2D) nanosheets obtained by exfoliating inorganic layered crystals have emerged as a new class of materials with unique attributes. One of the critical challenges is to develop robust and versatile methods for creating new nanostructures from these 2D-nanosheets. Here we report the delamination of layered materials that belonging to two different classes - the cationic clay, montmorillonite, and the anionic clay, hydrotalcite - by intercalation of appropriate ionic surfactants followed by dispersion in a non-polar solvent. The solids are delaminated to single layers of atomic thickness with the ionic surfactants remaining tethered to the inorganic and consequently the nanosheets are electrically neutral. We then show that when dispersions of the two solids are mixed the exfoliated sheets self-assemble as a new layered solid with periodically alternating hydrotalcite and montmorillonite layers. The procedure outlined here is easily extended to other layered solids for creating new superstructures from 2D-nanosheets by self-assembly.

Model for triplet state engineering in organic light emitting diodes

Engineering the position of the lowest triplet state (T-1) relative to the first excited singlet state (S-1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. We have carried out model exact calculations of substituted polyene chains to understand the factors that affect the energy gap between S-1 and T-1. The factors studied are backbone dimerisation, different donor-acceptor substitutions, and twisted geometry. The largest system studied is an 18 carbon polyene which spans a Hilbert space of about 991 x 10(6). We show that for reverse intersystem crossing process, the best system involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. (C) 2014 AIP Publishing LLC.

Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different

CONSPECTUS: The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen center dot center dot center dot halogen interactions (X center dot center dot center dot X) and halogen center dot center dot center dot heteroatom interactions (X center dot center dot center dot B). Many X center dot center dot center dot X and almost all X center dot center dot center dot B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms halogen and hydrogen are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X center dot center dot center dot X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen center dot center dot center dot halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be used in the design of ternary cocrystals. Structural modularity in which an entire crystal structure is defined as a combination of modules is rationalized on the basis of the intermediate strength of a halogen bond. The specific directionality of the halogen bond makes it a good tool to achieve orthogonality in molecular crystals. Mechanical properties can be tuned systematically by varying these orthogonally oriented halogen center dot center dot center dot halogen interactions. In a further development, halogen bonds are shown to play a systematic role in organization of LSAMs (long range synthon aufbau module), which are bigger structural units containing multiple synthons. With a formal definition in place, this may be the right time to look at differences between halogen bonds and hydrogen bonds and exploit them in more subtle ways in crystal engineering.

Stress Engineering using Si3N4 for stiction free release of SOI beams

We report on the effect of thin silicon nitride (Si3N4) induced tensile stress on the structural release of 200nm thick SOI beam, in the surface micro-machining process. A thin (20nm / 100nm) LPCVD grown Si3N4 is shown to significantly enhance the yield of released beam in wet release technique. This is especially prominent with increase in beam length, where the beams have higher tendency for stiction. We attribute this yield enhancement to the nitride induced tensile stress, as verified by buckling tendency and resonance frequency data obtained from optical profilometry and laser doppler vibrometry.

Hydroxyapatite-titanium bulk composites for bone tissue engineering applications

The research work on bulk hydroxyapatite (HA)-based composites are driven by the need to develop biomaterials with better mechanical properties without compromising its bioactivity and biocompatibility properties. Despite several years of research, the mechanical properties of the HA-based composites still need to be enhanced to match the properties of natural cortical bone. In this regard, the scope of this review on the HA-based bulk biomaterials is limited to the processing and the mechanical as well as biocompatibility properties for bone tissue engineering applications of a model system that is hydroxyapatite-titanium (HA-Ti) bulk composites. It will be discussed in this review how HA-Ti based bulk composites can be processed to have better fracture toughness and strength without compromising biocompatibility. The advantages of the functionally gradient materials to integrate the mechanical and biocompatibility properties is a promising approach in hard tissue engineering and has been emphasized here in reference to the limited literature reports. On the biomaterials fabrication aspect, the recent results are discussed to demonstrate that advanced manufacturing techniques, like spark plasma sintering can be adopted as a processing route to restrict the sintering reactions, while enhancing the mechanical properties. Various toughening mechanisms related to careful tailoring of microstructure are discussed. The in vitro cytocompatibilty, cell fate processes as well as in vivo biocompatibility results are also reviewed and the use of flow cytometry to quantify in vitro cell fate processes is being emphasized. (C) 2014 Wiley Periodicals, Inc.

Effect of grain boundary engineering on the microstructure and mechanical properties of copper containing austenitic stainless steel

The present investigation deals with grain boundary engineering of a modified austenitic stainless steel to obtain a material with enhanced properties. Three types of processing that are generally in agreement with the principles of grain boundary engineering were carried out. The parameters for each of the processing routes were fine-tuned and optimized. The as-processed samples were characterized for microstructure and texture. The influence of processing on properties was estimated by evaluating the room temperature mechanical properties through micro-tensile tests. It was possible to obtain remarkably high fractions of CSL boundaries in certain samples. The results of the micro-tensile tests indicate that the grain boundary engineered samples exhibited higher ductility than the conventionally processed samples. The investigation provides a detailed account of the approach to be adopted for GBE processing of this grade of steel. (C) 2014 Elsevier B.V. All rights reserved.

Effect of solvent; enhancing the wettability and engineering the porous structure of a calcium phosphate/agarose composite for drug delivery

Tissue engineering deals with the regeneration of tissues for bone repair, wound healing, drug delivery, etc., and a highly porous 3D artificial scaffold is required to accommodate the cells and direct their growth. We prepared 3D porous calcium phosphate ((hydroxyapatite/beta-tricalcium phosphate)/agarose, (HAp/beta-TCP)/agarose) composite scaffolds by sol-gel technique with water (WBS) and ethanol (EBS) as solvents. The crystalline phases of HAp and beta-TCP in the scaffolds were confirmed by X-ray diffraction (XRD) analysis. The EBS had reduced crystallinity and crystallite size compared to WBS. WBS and EBS revealed interconnected pores of 1 mu m and 100 nm, respectively. The swelling ratio was higher for EBS in water and phosphate buffered saline (PBS). An in vitro drug loading/release experiment was carried out on the scaffolds using gentamicin sulphate (GS) and amoxicillin (AMX). We observed initial burst release followed by sustained release from WBS and EBS. In addition, GS showed more extended release than AMX from both the scaffolds. GS and AMX loaded scaffolds showed greater efficacy against Pseudomonas than Bacillus species. WBS exhibited enhanced mechanical properties, wettability, drug loading and haemocompatibility compared to EBS. In vitro cell studies showed that over the scaffolds, MC3T3 cells attached and proliferated and there was a significant increase in live MC3T3 cells. Both scaffolds supported MC3T3 proliferation and mineralization in the absence of osteogenic differentiation supplements in media which proves the scaffolds are osteoconducive. Microporous scaffolds (WBS) could assist the bone in-growth, whereas the presence of nanopores (EBS) could enhance the degradation process. Hence, WBS and EBS could be used as scaffolds for tissue engineering and drug delivery. This is a cost effective technique to produce scaffolds of degradable 3D ceramic-polymer composites.

Engineering a Water-Dispersible, Conducting, Photoreduced Graphene Oxide

A critical limitation that has hampered widespread application of the electrically conducting reduced graphene oxide (r-GO) is its poor aqueous dispersibility. Here we outline a strategy to obtain water-dispersible conducting r-GO sheets, free of any stabilizing agents, by exploiting the fact that the kinetics of the photoreduction of the insulating GO is heterogeneous. We show that by controlling UV exposure times and pH, we can obtain r-GO sheets with the conducting sp(2)-graphitic domains restored but with the more acidic carboxylic groups, responsible for aqueous dispersibility, intact. The resultant photoreduced r-GO sheets are both conducting and water-dispersible.

Engineering a nanostructured ``super surface'' with superhydrophobic and superkilling properties

We present a nanostructured ``super surface'' fabricated using a simple recipe based on deep reactive ion etching of a silicon wafer. The topography of the surface is inspired by the surface topographical features of dragonfly wings. The super surface is comprised of nanopillars 4 mm in height and 220 nm in diameter with random inter-pillar spacing. The surface exhibited superhydrophobicity with a static water contact angle of 154.0 degrees and contact angle hysteresis of 8.3 degrees. Bacterial studies revealed the bactericidal property of the surface against both gram negative (Escherichia coli) and gram positive (Staphylococcus aureus) strains through mechanical rupture of the cells by the sharp nanopillars. The cell viability on these nanostructured surfaces was nearly six-fold lower than on the unmodified silicon wafer. The nanostructured surface also killed mammalian cells (mouse osteoblasts) through mechanical rupture of the cell membrane. Thus, such nanostructured super surfaces could find applications for designing selfcleaning and anti-bacterial surfaces in diverse applications such as microfluidics, surgical instruments, pipelines and food packaging.

Building upon Supramolecular Synthons: Some Aspects of Crystal Engineering

It has been 20 years since the concept of supramolecular synthon was introduced with the purpose of rational supramolecular synthesis. While this concept has been greatly successful in employing a retrosynthetic approach in crystal engineering, the past few years have seen a continuous evolution of supramolecular synthons from being a synthetic subunit to a basic unit for understanding the dynamics of crystallization. This review attempts to give a glimpse of such developments.

Novel Design of Honeycombs Using a Seamless Combination of Auxetic and Conventional Cores Toward Phononic Band Gap Engineering

A novel design for the geometric configuration of honeycombs using a seamless combination of auxetic and conventional cores- elements with negative and positive Possion ratios respectively, has been presented. The proposed design has been shown to generate a superior band gap property while retaining all major advantages of a purely conventional or purely auxetic honeycomb structure. Seamless combination ensures that joint cardinality is also retained. Several configurations involving different degree of auxeticity and different proportions auxetic and conventional elements have been analyzed. It has been shown that the preferred configurations open up wide and clean band gap at a significantly lower frequency ranges compared to their pure counterparts. In view of existence of band gaps being desired feature for the phononic applications, reported results might be appealing. Use of such design may enable superior vibration control as well. Proposed configurations can be made isovolumic and iso-weight giving designers a fairer ground of applying such configurations without significantly changing size and weight criteria.