Improving flow dynamics and storage longevity of a low-cost phosphorescent fingerprint powder.

An inexpensive, commercially available doped strontium aluminate phosphor with long-lived afterglow was prepared as a luminescent fingerprint dusting powder suited for challenging, highly patterned substrates; however, prolonged exposure to humidity was found to reduce that powder's affinity for fingermarks. Here, an enhanced preparation for synthesizing that fingerprint dusting powder is presented that prevents powder aggregation and loss of function upon exposure to humid environments. This was achieved by introducing a flow regulator during synthesis: hydrophobic silica SIPERNAT® D10 or SIPERNAT® D17. Increasing the hydrophobicity of the powder prevents aggregation by inhibiting the uptake of water, thereby improving the material's flow dynamics and transfer behavior from brush to fingermark. The angle of repose and flow characteristics made by the modified powders were quantified, with excellent affinity for fingermarks observed, even after being stored under 85% (±5%) humidity for 4 weeks. A preliminary comparison of the performance of the modified hydrophobic powders relative to the unmodified precursor revealed that more of the SIPERNAT® treated powder typically adhered to fingermarks while simultaneously imparting less background development. In addition, fewer clumps of particulate were observed in the developed fingermarks after addition of a hydrophobic flow regulator. This technical report outlines the updated method for synthesizing the fingerprint powder, with summarized flow performance results, and a demonstration of the modified powder's affinity for simulated fingermark evidence.

Showcasing water-based delivery of an amino acid targeting fingermark developer in a hydrogel.

Most recommended methods for visualising fingermarks on paper rely on chemical developers that target and react with amino acids. Traditionally, these developers are sprayed onto paper substrates in solutions of per- and polyfluoroalkyl substances (PFAS), but now those same PFAS chemicals are undergoing phaseout or phasedown, which threatens to undermine forensic capabilities. This situation provides an opportunity to pivot towards greener approaches to fingermark visualisation. The ideal methodology would be a water-based treatment, as these provide superior safety for practitioners, combined with environmental sustainability. A major hurdle to implementing a water-based fingermark developer targeting amino acids is that water, as a universal solvent, can dissolve the eccrine components in fingermarks, as well as any optical or luminescent dyes that are created, causing the ridge detail to run or dissolve. This work circumvents this problem by delivering the amino acid developer alloxan in a hydrogel, which enables sharp fingermark ridge details to be observed despite it being a water-based treatment. Alloxan dissolved in a viscous hydrogel is shown here to react with the amino acids in fingerprint residues to form the coloured dye murexide, supported by optimisation and characterisation studies.

Disposable gloves: An innate source of transferable chemical residues.

As workers in medicine, food science, and advanced manufacturing have learned, pristine disposable gloves are an innate source of chemical contamination from the moment they are first donned. Given the typically low extent of chemical contamination on the surface of gloves post-manufacture, many fields overlook, or simply discount, this source of transferable chemical evidence. However, forensic science should not adopt this approach. Instead, the trace chemical signatures left after handling objects while wearing different brands and types of disposable gloves could provide new avenues of forensic intelligence when assessing crime scenes. Similarly, an appreciation of the potential for disposable gloves to transfer innate chemical residues is an important consideration when surface analyses of evidence are envisioned. This review summarises past reports of chemical transference originating from pristine gloves drawn from the fields of medicine, food science, and material science, as well as the few examples highlighting the implications of such events for forensic investigations. Correlations between the chemical identities of the contaminants and the material of glove manufacture are provided here where known, with energy-intensive chemical extraction of glove material, and passive transference of chemical residues through simple contact, both explored. Finally, discussions pertaining to the implications of disposable glove residues, coupled with opportunities for future research, are outlined.

Solvent-free strategies for developing latent fingermarks on paper: a review.

With growing environmental concern and supply chain uncertainty, now is a fitting time to re-evaluate solvent-free methodologies in forensic chemistry processes. Here, this paper reviews solvent-free approaches for fingermark visualisation, including chemical fuming and vapour phase treatments, dry-transfer treatments, application of heat, and thermal paper specific treatments. After providing historical context, three objectives have been emphasised: identify feasible scenarios for implementing solvent-free methods; showcase the effectiveness of solvent-free methods relative to their nearest solution-based equivalent; and estimate the technological readiness level of each method discussed. Having reviewed the literature, dry-transfer methods of developing latent fingermarks on paper were found to be the most promising and feasible solvent-free approaches for near-term implementation. Such methods make use of standard materials and equipment commonly found in forensic laboratories, are effective at fingermark visualisation, and mitigate most of the pressing issues pertaining to environmental concern and solvent scarcity.

Preparation of a low-cost fingerprint powder that harnesses white light to emit long-lived phosphorescence.

An inexpensive, commercially available doped strontium aluminate phosphor with long-lived afterglow has been prepared and assessed in the role of a luminescent fingerprint dusting powder. Blue, green, and aqua phosphorescence persisting for ca. 30 s was obtainable from treated fingermarks after charging the powders with the white light (400-700 nm) setting of a forensic light source. Imaging the phosphorescent afterglow enabled the elimination of background emissions encountered during latent fingermark examination. This was demonstrated by visualising fingermarks on substrates that possess inbuilt fluorescent security features and highly patterned substrate backgrounds, without any need for bespoke scientific equipment.

Incorporating hydrogels into fingermark development: indicative viscosities for preserving ridge detail on paper surfaces.

Water-based fingermark development treatments for paper have long been held back by loss of ridge detail due to diffusion. Viscous hydrogels (≥2224 cP) show promise as a green method of delivering chemical developers that inhibits diffusion, thereby preserving fingermark ridge detail. This is demonstrated here with starch and xanthan gum hydrogels applied to iodine-fumed fingermarks.

Harnessing long-lived visible phosphorescence to eliminate background interference from fingermark images.

Minimising background fluorescence can enhance the visible details of treated fingerprints. Here, a 4-tpt fingerprint powder exhibiting long-lived phosphorescence is applied to this end. The powder was found to suppress background fluorescence, including on challenging surfaces, when using standard forensic equipment and eschewing specialized or bespoke imaging techniques.

Volatilised pyrene: A phase 1 study demonstrating a new method of visualising fingermarks with comparisons to iodine fuming.

Pyrene is a fluorescent polycyclic aromatic hydrocarbon that can be volatilised under mild conditions. When fumed, pyrene is rapidly absorbed into the sebaceous residues of fingermarks, enabling their fluorescent visualisation upon excitation with ultraviolet radiation. This new means of fluorescent fingermark detection is more sensitive than the non-fluorescent iodine fuming approach for nonporous surfaces. This is demonstrated here in a phase 1 study using split-print comparisons on metal and glass surfaces. Pyrene-treated fingermarks also retain the volatile fluorophore for comparably long time periods relative to iodine fuming (in the order of hours). The phase 1 study comprised four donors, and 80 natural fingermarks that were grouped into two time periods; aged 24h and 1 week. Iodine fuming was chosen as a reference to showcase the effectiveness of pyrene given it is the most closely-related chemical fuming method in routine use. This study demonstrates that pyrene fuming increases the quantity and quality of fingermark visualisations relative to iodine fuming, and is free of many of the latter method's drawbacks. Preliminary results shown here also show the effectiveness of pyrene fuming on highly patterned surfaces, and its compatibility with the use of gelatine lifters. Pyrene fuming is thus easy to effect, low-cost, and shows great promise as a new means of visualising fingermarks on non-porous surfaces.

Metastable 9-Fluorenone: Blueshifted Fluorescence, Single-Crystal-to-Single-Crystal Reactivity, and Evaluation as a Multimodal Fingermark Visualization Treatment.

A metastable form of 9-fluorenone (MS9F) has been characterized using Raman spectroscopy, fluorimetry, and X-ray diffraction techniques. MS9F emits blue fluorescence (λmax =495 nm) upon 365 nm irradiation and undergoes a single-crystal-to-single-crystal (SCSC) transformation to reach the ground state form (GS9F) over approximately 30 minutes, whereupon it emits the expected green fluorescence. A structure-property relationship for this fluorescent behavior has been posited. MS9F and GS9F were applied as a means of visualizing latent fingermarks on a nonporous surface. This approach identified three different modes of fluorescent fingermark visualization using 9-fluorenone.

Harnessing volatile luminescent lanthanide complexes to visualise latent fingermarks on nonporous surfaces.

Two commercially-available terbium and europium complexes, EuFOD and TbTMHD, provide luminescent visualisation of latent fingermarks placed on nonporous surfaces via sublimation. This is demonstrated using UV radiation from a forensic light source. The method was optimised on metal foil, with other archetypal nonporous surfaces (i.e. glass, ceramic) also suited to this method.

Post-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution.

The Mannich reaction of the zirconium MOF [Zr6 O4 (OH)4 (bdc-NH2 )6 ] (UiO-66-NH2 , bdc-NH2 =2-amino-1,4-benzenedicarboxylate) with paraformaldehyde and pyrazole, imidazole or 2-mercaptoimidazole led to post-synthetic modification (PSM) through C-N bond formation. The reaction with imidazole (Him) goes to completion whereas those with pyrazole (Hpyz) and 2-mercaptoimidazole (HimSH) give up to 41 and 36 % conversion, respectively. The BET surface areas for the Mannich products are reduced from that of UiO-66-NH2 , but the compounds show enhanced selectivity for adsorption of CO2 over N2 at 273 K. The thiol-containing MOFs adsorb mercury(II) ions from aqueous solution, removing up to 99 %. The Mannich reaction with pyrazole succeeds on [Zn4 O(bdc-NH2 )3 ] (IRMOF-3), but a similar reaction on [Zn2 (bdc-NH2 )2 (dabco)] (dabco=1,4-diazabicyclo[2.2.2]octane) gave [Zn3 (bdc-NH2 )1.32 (bdc-NHCH2 pyz)1.68 (dabco)]⋅2 C7 H8 5, whereas the reaction with imidazole gave the expected PSM product. Compound 5 forms via a dissolution-recrystallisation process that is triggered by the "free" pyrazolate nitrogen atom competing with dabco for coordination to the zinc(II) centre. In contrast, the "free" nitrogen atom on the imidazolate is too far away to compete in this way. Mannich reactions on [In(OH)(bdc-NH2 )] (MIL-68(In)-NH2 ) stop after the first step, and the product was identified as [In(OH)(bdc-NH2 )0.41 (bdc-NHCH2 OCH3 )0.30 (bdc-N=CH2 )0.29 ], with addition of the heterocycle prevented by steric interactions.

Evaluating Iodine Uptake in a Crystalline Sponge Using Dynamic X-ray Crystallography.

The uptake of gaseous iodine into the crystalline sponge material [(ZnI2)3(tpt)2]·0.7triphenylene·0.3PhNO2·0.7C6H12 1 (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine) has been monitored by dynamic X-ray diffraction and thermogravimetric analysis. The X-ray analyses have enabled the location, quantity, uptake rate, and subsequent chemistry of the iodine upon inclusion into the pores to be determined. An uptake of 6.0 wt % (0.43 I2 per formula unit) was observed crystallographically over a period of 90 min before crystal degradation occurred. The included iodine molecules interact with the iodine atoms of the ZnI2 nodes at three different sites, forming coordinated I3- ions. The results contrast to recent observations on [(ZnI2)3(tpt)2] without the triphenylene guests which show the presence of I42- ions with low quantities of absorbed iodine.

The growing importance of crystalline molecular flasks and the crystalline sponge method.

This article showcases recent advancements made using crystalline molecular flasks and the widening list of prospective applications for the crystalline sponge method. This expansion has coincided with an increasing number of materials termed crystalline sponges, and a report of a predictive means of identifying candidates from crystallographic databases. The crystalline sponge method's primary application has been determination of absolute configuration, and this has evolved from the analysis of carefully chosen planar aromatic guests to more diverse identification of natural products, biological metabolites, and analysis of volatile chemical components. However with time-resolved X-ray crystallography providing arguably the most informative atomic scale insights of dynamic chemical processes, this application of the crystalline sponge method may soon eclipse structural determination in terms of importance.

Hard X-ray-Induced Valence Tautomeric Interconversion in Cobalt-o-Dioxolene Complexes.

Valence tautomeric interconversion (VTI) is a reversible process occurring in metal complexes in which an intramolecular metal-ligand electron transfer is accompanied by a change of metal ion spin state, creating two switchable electronic states (redox isomers). Herein, we describe the low-temperature, 30-100 K, single-crystal study of the [Co(diox)2(4-CN-py)2]·benzene complex (1) (diox = 3,5-di-t-butylsemiquinonate (SQ•-) and/or 3,5-di-t-butylcatecholate (Cat2-) radical; 4-CN-py = 4-cyano-pyridine) using hard synchrotron X-ray radiation with different intensities. We demonstrate for the first time that hard X-rays can induce VTI, and that the interconversion molar fraction is dependent on both intensity and exposure time. This in turn shows that X-rays, as a probe, might be altering the very nature of many structures under investigation at low temperatures, and consequently their properties. Our findings add new perspectives to VTI studies and might be of significant interest to the entire community investigating photoresponsive complexes.

Magnetic coupling in a hybrid Mn(ii) acetylene dicarboxylate.

The design of ligands that mediate through-bond long range super-exchange in metal-organic hybrid materials would expand chemical space beyond the commonly observed short range, low temperature magnetic ordering. Here we examine acetylene dicarboxylate as a potential ligand that could install long range magnetic ordering due to its spatially continuous frontier orbitals. Using a known Mn(ii)-containing coordination polymer we compute and measure the electronic structure and magnetic ordering. In this case, the latter is weak owing to the sub-optimal ligand coordination geometry, with a critical temperature of 2.5 K.

Furnishing Amine-Functionalized Metal-Organic Frameworks with the ß-Amidoketone Group by Postsynthetic Modification.

Postsynthetic modification (PSM) of amino-functionalized metal-organic frameworks (MOFs) to those bearing pendant ß-amidoketone arms using diketene is herein reported. Three unique MOF families demonstrate the scope of this transformation, which both is atom-economical and yields high conversions. In each case, the crystallinity was retained, and instances of exceptional solid-state ordering were observed in the PSM products, which has allowed detailed crystallographic characterization in multiple instances.

An Iodine-Vapor-Induced Cyclization in a Crystalline Molecular Flask.

A vapor-induced cyclization has been observed in the host environment of a crystalline molecular flask (CMF), within which 1,8-bis(2-phenylethynyl)naphthalene (bpen), a diarenynyl system primed for cyclization, was exposed to iodine vapor to yield the corresponding indeno[2,1-α]phenalene species. The cyclization process, unique in its vapor-induced, solvent-free nature, was followed spectroscopically, and found to occur concurrently with the displacement of lattice solvent for molecular iodine in CMF⋅0.75 bpen⋅2.25 CHCl3 ⋅H2 O. The cyclization occurred under mild conditions and without the need to suspend the crystals in solvent. The ability of CMFs to host purely gas-induced reactions is further highlighted by the subsequent sequential oxidation reaction of cyclized 7-iodo-12-phenylindeno[2,1-α]phenalene (ipp) with molecular oxygen derived from air, yielding 12-hydroxy-7-iodo-2-phenylindeno[2,1-α]phenalen-1(12H)-one (hipp).

Ion flow in a zeolitic imidazolate framework results in ionic diode phenomena.

Ionic transport (for applications in nanofluidics or membranes) and "ionic diode" phenomena in a zeolitic imidazolate framework (ZIF-8) are investigated by directly growing the framework from aqueous Zn(2+) and 2-methylimidazole as an "asymmetric plug" into a 20 µm diameter pore in a ca. 6 µm thin poly-ethylene-terephthalate (PET) film.

A facile single crystal to single crystal transition with significant structural contraction on desolvation.

5-Ethynyl-1,3-benzenedicarboxylic acid (H2ebdc) reacted with lead(II) acetate trihydrate yields a 1D ladder network, [Pb(ebdc)(MeOH)]2·H2O (1). Removing crystals of 1 from the mother liquor results in a facile single crystal to single crystal transition, yielding 2D [Pb(ebdc)] net (2) with a change in space group from I2/a to P1̄.

Synthesis, characterisation and adsorption properties of a porous copper(II) 3D coordination polymer exhibiting strong binding enthalpy and adsorption capacity for carbon dioxide.

The synthesis and characterisation of microporous coordination polymers containing copper(II) or cobalt(II) and 2-(pyridin-4-yl)malonaldehyde (Hpma) is described and the gas adsorption properties evaluated. Single-crystal X-ray structure determinations identified the structures as [M(pma)(2)]·2X (M = Cu, 1; Co, 2; X = MeOH, MeCN), which contain 3D networks with rutile topology and continuous 1D rectangular channels with diameters ranging from 3 to 4 Å. The materials exhibit low BET surface areas of 143 m(2) g(-1), but possess large capacities for carbon dioxide capture of 14.1 wt%. The small pore channels are shown to account for this, delivering a particularly strong binding enthalpy to adsorbed CO(2) of 38 kJ mol(-1), and a very large adsorption capacity relative to the low surface area.