Double transfer printing of small volumes of liquids

We report here a technique to print small volumes of liquid on a hydrophobic substrate. This process is based on the control of the critical parameters that govern a quasi-equilibrium liquid transfer process from one surface to another. We present a qualitative model that describes the physics of a transfer printing process between hydrophobic surfaces, and we use the parameters outlined in this model to manipulate the amount of liquid transferred between surfaces. We demonstrate the printing of discrete, small volumes (approximately 70 fL) of different liquid inks on a polymer substrate starting with volumes that are 8 orders of magnitude larger (a droplet of approximately 10 microL) in a simple two-step procedure.     

The concept of protobranching and its many paradigm shifting implications for energy evaluations

Branched alkanes like isobutane and neopentane are more stable than their straight chain isomers, n-butane and n-pentane (by 2 and 5 kcal mol(-1), respectively). Electron correlation is largely responsible. Branched alkanes have a greater number of net attractive 1,3-alkyl-alkyl group interactions, there are three such stabilizing 1,3 "protobranching" dispositions in isobutane, but only two in n-butane. Neopentane has six protobranches but n-pentane only three. Propane has one protobranch and is stabilized appreciably, by 2.8 kcal mol(-1), relative to methane and ethane. This value per protobranch also applies to the n-alkanes and cyclohexane. Consequently, energy evaluations employing alkane reference standards, for example, of small ring strain and stabilizations due to conjugation, hyperconjugation, and aromaticity, should be corrected for protobranching, for example, by employing Pople's isodesmic bond separation reaction method. This reduces the ring strain of cyclopropane to 19.2 from the conventional 27.7 kcal mol(-1), while the stabilization energies of alkenes and alkynes due to hyperconjugation (5.5 and 7.7 kcal mol(-1) for propene and propyne) and conjugation (14.8 and 27.1 kcal mol(-1) for butadiene and butadiyne) are considerably larger than the traditional estimates. Widely diverging literature evaluations of benzene resonance energy all give approximately 65 kcal mol(-1) after adjusting for conjugation, hyperconjugation, and protobranching "contaminations." The BLW (block localized wavefunction) method, which localizes pi bonds and precludes their interactions, largely confirms these stabilization estimates for hyperconjugation, conjugation, and aromaticity. Protobranching is seriously underestimated by theoretical computations at the HF and most DFT levels, which do not account for electron correlation satisfactorily. Such levels give bond separation energies, which can differ greatly from experimental values.     

The existence of secondary orbital interactions

B3LYP/6-311+G** (and MP2/6-311+G**) computations, performed for a series of Diels-Alder (DA) reactions, confirm that the endo transition states (TS) and the related Cope-TSs are favored energetically over the respective exo-TSs. Likewise, the computed magnetic properties (nucleus-independent chemical shifts and magnetic susceptibililties) of the endo- (as well as the Cope) TS's reveal their greater electron delocalization and greater aromaticity than the exo-TS's. However, Woodward and Hoffmann's original example is an exception: their endo-TS model, involving the DA reaction of a syn- with an anti-butadiene (BD), actually is disfavored energetically over the corresponding exo-TS; magnetic criteria also do not indicate the existence of SOI delocalization in either case. Instead, a strong energetic preference for endo-TSs due to SOI is found when both BDs are in the syn conformations. This is in accord with Alder and Stein's rule of "maximum accumulation of double bonds:" both the dienophile and the diene should have syn conformations. Plots along the IRC's show that the magnetic properties typically are most strongly exalted close to the energetic TS. Because of SOI, all the points along the endo reaction coordinates are more diatropic than along the corresponding exo pathways. We find weak SOI effects to be operative in the endo-TSs involved in the cycloadditions of cyclic alkenes, cyclopropene, aziridine, cyclobutene, and cyclopentene, with cyclopentadiene. While the endo-TSs are only slightly lower in energy than the respective exo-TSs, the magnetic properties of the endo-TS's are significantly exalted over those for the exo-TS's and the Natural Bond Orbitals indicate small stabilizing interactions between the methylene cycloalkene hydrogen orbitals (and lone pairs in case of aziridine) with pi-character and the diene pi MOs.     

Yb‐fiber‐based,high‐average‐power,high‐repetition‐rate,picosecond source at 2.1 µm

We report a high‐repetition‐rate picosecond fiber‐based source at 2.1 µm offering exceptional performance capabilities over existing lasers near this wavelength, providing high average power and efficiency together with excellent spectral, power and beam pointing stability, in high spatial beam quality. This new source is based on a near‐degenerate MgO:PPLN optical parametric oscillator (OPO) pumped by an Yb‐fiber laser at 1064 nm, and incorporating a diffraction grating for spectral control. The device provides as much as 7.1 W of average power at 2.1 µm for a pump power of 18 W at an extraction efficiency of 39.4% in pulses of 20 ps at 79.3 MHz. The output exhibits passive power stability better than 1% rms over 15 hours, and a beam pointing stability ∼40 µrad over 1 hour, in high spatial quality with M² ∼ 3.5. The output beam is linearly polarized and the pulse train has an amplitude stability better than 3.4% rms over 2 µsec. Radio‐frequency measurements of the output pulse train also confirm high temporal stability and low timing jitter, indicating that the source is ideal for variety of applications including pumping long‐wavelength mid‐infrared OPOs. Photograph shows the temperature‐controlled, 50‐mm‐long MgO:PPLN crystal inside the cavity, used as nonlinear gain medium in the picosecond source operating at 2.1 µm. The visible light is the result of non‐phase‐matched second harmonic generation of the pump beam in the MgO:PPLN crystal.

     

A Catalyst‐free Green Protocol for the Synthesis of Pyranopyrazoles Using Room Temperature Ionic Liquid Choline Chloride‐urea

An efficient and rapid four component reaction of aldehydes, malanonitrile, β‐ketoesters and hydrazine hydrate (or phenyl hydrazine) in environmentally benign room temperature ionic liquid choline chloride‐urea has been developed for the synthesis of substituted 4H‐pyrano[2,3‐c]pyrazoles.     

Compact, 1.5 mJ, 450 MHz, CdSiP2 picosecond optical parametric oscillator near 6.3 μm

We report a compact, efficient, high-energy, and high-repetition-rate mid-IR picosecond optical parametric oscillator (OPO) based on the new nonlinear material CdSiP(2) (CSP). The OPO is synchronously pumped by a master oscillator power amplifier system at 1064.1 nm, providing 1 μs long macropulses constituting 8.6 ps micropulses at 450 MHz, and it can be tuned over 486 nm across 6091-6577 nm, covering the technologically important wavelength range for surgical applications. Using a compact (～30 cm) cavity and improved, high-quality nonlinear crystal, idler macropulse energy as high as 1.5 mJ has been obtained at 6275 nm at a photon conversion efficiency of 29.5%, with >1.2 mJ over more than 68% of the tuning range, for an input macropulse energy of 30 mJ. Both the signal and idler beams are recorded to have good beam quality with a Gaussian spatial profile, and the extracted signal pulses are measured to have durations of 10.6 ps. Further, from the experimentally measured transmission data at 1064 nm, we have estimated the two-photon absorption coefficient of CSP to be β=2.4 cm/GW, with a corresponding energy bandgap, E(g)=2.08 eV.     

Interferometric output coupling of ring optical oscillators

We demonstrate the successful deployment of an antiresonant ring (ARR) interferometer within a ring optical resonator and its use for absolute optimization of output power. The integration of the ARR interferometer in a folded arm of the ring oscillator provides continuously variable output coupling over broad spectral range and under any operating conditions. We demonstrate the technique using a picosecond optical parametric oscillator (OPO), where we show continuously adjustable output coupling and optimization of the output power for different pump power conditions, from 3.5 W to 13.5 W. By operating the OPO under an optimized output coupling at 14 W of pump power, we obtain >5 W of extracted signal power, more than 2.6 times that with a ~5% conventional output coupler. We also show that the inclusion of the ARR interferometer has no detrimental effect on the spatial, temporal, and spectral characteristics of OPO output.     

Theoretical insights into the mechanism of carbon monoxide (CO) release from CO-releasing molecules

We used density functional theory to investigate the capacity for carbon monoxide (CO) release of five newly synthesized manganese-containing CO-releasing molecules (CO-RMs), namely CORM-368 (1), CORM-401 (2), CORM-371 (3), CORM-409 (4), and CORM-313 (5). The results correctly discriminated good CO releasers (1 and 2) from a compound unable to release CO (5). The predicted Mn-CO bond dissociation energies were well correlated (R(2) ≈0.9) with myoglobin (Mb) assay experiments, which quantified the formation of MbCO, and thus the amount of CO released by the CO-RMs. The nature of the Mn-CO bond was characterized by natural bond orbital (NBO) analysis. This allowed us to identify the key donor-acceptor interactions in the CO-RMs, and to evaluate the Mn-CO bond stabilization energies. According to the NBO calculations, the charge transfer is the major source of Mn-CO bond stabilization for this series. On the basis of the nature of the experimental buffers, we then analyzed the nucleophilic attack of putative ligands (L' = HPO(4)(2-), H(2)PO(4)(-), H(2)O, and Cl(-)) at the metal vacant site through the ligand-exchange reaction energies. The analysis revealed that different L'-exchange reactions were spontaneous in all the CO-RMs. Finally, the calculated second dissociation energies could explain the stoichiometry obtained with the Mb assay experiments.     

Dynamics and mechanism of DNA repair in a biomimetic system: flavin-thymine dimer adduct

To mimic photolyase for efficient repair of UV-damaged DNA, numerous biomimetic systems have been synthesized, but all show low repair efficiency. The molecular mechanism of this low-efficiency process is still poorly understood. Here we report our direct mapping of the repair processes of a flavin-thymine dimer adduct with femtosecond resolution. We followed the entire dynamic evolution and observed direct electron transfer (ET) from the excited flavin to the thymine dimer in 79 ps. We further observed two competitive pathways, productive dimer ring splitting within 435 ps and futile back-ET in 95 ps. Our observations reveal that the underlying mechanism for the low repair quantum yield of flavin-thymine dimer adducts is the short-lived excited flavin moiety and the fast dynamics of futile back-ET without repair.